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By H. T. Clark

NO previous determinations of the deformation or recrystallization textures of titanium or of titanium-base alloys have been reported in the literature. The room-temperature structure of titanium is hexagonal close-packed with a c/a ratio less than 1.633. It would be expected, therefore, to have a rolling texture similar to that of other hexagonal close-packed metals, namely (0001) [1010]. Burgers and Jacobs1 have shown that zirconium, a metal isomorphous with titanium in its structure and similar in many of its properties, has such a texture with a scatter of the basal plane toward the transverse direction. This scatter is in the opposite direction from that found in magnesium by Bakarian2 but similar to that reported by Smigelskas and Barrett3 or beryllium. The rolling and annealing textures reported here for high-purity iodide titanium are significantly different from the . textures of any other hexagonal close-packed metal. All titanium used during this investigation was prepared by the iodode process." The annealed hardness of this material varied from 73 (material used for sample No. 2) to 97 Vickers hardness number. An estimate of the chemical composition of this grade of titanium has been reported by Finlay and Snyder.5 With one exception, shown in table I, the as-deposited titanium was cast into 10 to 20 g ingots in an electric arc furnace in purified argon before being rolled to sheet. The cast ingots were forged and ground until their cross-section was approximately rectangular, annealed 1 hr at 700°C in vacuum and cold rolled. Rolling was carried out in a two-high, 4 in. diam mill, using reductions no greater than 10 pct per pass. The direction of rolling was reversed after each pass, and, in order to avoid temperature effects, the sheet was allowed to cool after each pass. Unless the rolled sheet was sufficiently thin for X-ray penetration (about 0.004 in.), it was reduced to this thickness by pickling. Because of the possibility of introducing twinning or other deformation during grinding, no attempt was made to maintain uniform thickness of the sample during pickling by intermediate grinding or sanding operations. Those samples to be used for determining the annealed texture were recrystallized by vacuum annealing the cold-rolled sheet for 1 hr at 500°C. These thin samples were held between thick titanium sheets during annealing to prevent distortion. Table I outlines the rolling and annealing schedule of those samples for which photograms or texture patterns are shown. X-ray Techniques The usual techniques for determining textures were employed during this work. Molybdenum radiation was used for the transmission exposures and copper radiation for the glancing angle ones. Since titanium fluoresces under these conditions, it is necessary to employ a filter between the sample and the film. The Kß radiation filters are very satisfactory for this purpose. Sufficient grains having favorable orientation were present in both the cold-worked and in the cold-worked—500°C annealed samples to provide satisfactory patterns with the samples stationary. Because of the difficulties of comparing intensities of transmission photograms with those obtained

Jan 1, 1951

By AIME

In Emporia or Claremore, time was when a path was beaten to the door of the local sage. Nowadays, the beginnings of such a path are discernible in Tennessee, as folks of the metallurgical persuasion find it to their pleasure and profit to call upon the Sage of Copperhill. They come, more and more respectfully as the years go by, yet to ever fewer persons is he known as Mr. Myers, but to more, eloquently, as Jack. Find better ways to run your mill, find happier means of co-ordinating your humanities or serving your professional society, and it's just like the man said about the mousetrap. A druggist's son, born in Wisconsin, May 24, 1889, reared on the Bible in Ohio and Indiana, and completing his education in Colorado, this now indisputably 24-carat Tennesseean has had a checkered career. Going West as a laborer at the tail end of the 1907 panic, he did not make his fortune but he did gain an understanding of labor that in later years endeared him to his men. Graduating in 1913 from Colorado School of Mines with the degree of E. Met. and a string of football letters (also earned the hard way, at tackle) he went to work in Butte & Superior, just at the beginning of the Golden Age of flotation.

Jan 1, 1949

By Cresap P. Watson

ABOUT the time this magazine reaches its readers, Cresap P. Watson will celebrate his 53d birthday. If he spends that birthday at his West Los Angeles home, he won't be far, as distance is measured today, from Santa Barbara, where he was born on July 8, 1895. He is truly a member of a petroleum family; one brother, N. O. Watson, managed Royal Dutch Shell interests in Venezuela for years and is now general manager of the Caribbean Petroleum Co. at. Maracaibo; another brother, Rex, is vice-president of the Drilling and Exploration Co., while brother-in-law Ben Belt is an executive of Gulf Oil. His own life has centered in the petroleum industry since his first job in 1913 as camp cashier for a Mexican oil field at Tampico. Down on the isthmus of Tehuantepec he advanced to tool dresser and' production foreman for the company. The first World War interrupted his Mexican experience by transforming him into an artillery officer in France. Once the Army ceased to demand his services¬by then it was 1919-he returned to the task of furthering his professional career as agent for the Amerada Petroleum Corp. By 1927 he had reached the position in which he could be called an executive in the petroleum industry, having organized and become president of the Federal Royalties Co. His activities in local and national legislation affecting the petroleum industry increased as has his advocacy of the development of oil and gas fields under sound engineering and conservation principles through unitization or other co-operative forms of operation. Considerable amounts of his time go to the promotion of industry public relations.

Jan 1, 1948

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By C. E. Birchenall, C L. McCabe

IN attempting to extend vapor pressure measurements of the type previously reported by Schadel and Birchenall1 for silver and by Schadel, Derge, and Birchenall' for silver-silicon to other systems, it was observed that the materials melted at indicated temperatures 10" to 15" below their accepted melting points. Further investigation revealed that the thermocouple readings were in error due to appreciable conduction losses along the reference thermocouple wires. If the wire diameter of the reference couple inserted into the Knudsen cell was reduced, the correction for the indicating couple changed in a manner tending to explain the melting behavior. When extrapolated to zero wire diameter from measurements with several reference thermocouples of different wire thickness, the melting point of silver then agreed with the indicated temperature at which silver chips were observed to coalesce into a sphere. Approximately the same calibration was given by observing the melting of small wires of silver or gold in the Knudsen cell connected in series with an ammeter, where the leads into the cell were very fine in order to minimize heat conduction. Unfortunately neither of these methods seemed to yield a sufficiently precise temperature calibration to match the apparent precision of the other aspects of the vapor pressure measurement. It was decided. therefore, to redetermine the vapor pressure of silver in another setup under conditions permitting precise temperature measurement. The vapor pressure of pure silver could then be used as an internal calibration of temperature in the older unit in making runs on alloys. This has been done; the present report is a correction to ref. 1. Experimental Procedure The apparatus, shown in Fig. 1, was very similar to that employed by Harteck,3 except that the orifice sizes were smaller and the residual pressure in the vacuum system was probably much lower. A small, sharp-edged hole, nearly circular in shape, was ground into the rounded end of a quartz tube. The orifice area was then measured by tracing the image at known magnification on graph paper and counting the squares enclosed. The silver specimen was sealed into the tube to make a Knudsen cell. A tantalum jacket surrounding the cell served to increase the uniformity of temperature. This assembly was placed in the bottom of a long quartz tube with an inside diameter of about 1 in., which was connected to the vacuum system through a ground joint sealed with picein wax well removed from the furnace. A thermocouple tube inserted through the top of the vacuum line reached into the tantalum jacket so that the thermocouple junction was immediately adjacent to the Knudsen cell except for the protection tube wall. A resistance furnace could be raised to cover the end of the quartz tube containing the cell in such a way that the cell was in the uniform temperature zone 13 in. from the end of the furnace. An ionization gage was included in the vacuum system in the cold lines of wide diameter, immediately beyond the ground joint. The vacuum system consisted of a mercury one-stage diffusion pump, backed by a Welch duo-seal mechanical pump. The pumps were separated from the reactor chamber by a dry ice trap. The ionization gage always read less than 10-5 mm Hg after initial outgassing and before each run was started. Each newly filled Knudsen cell was evacuated at high temperature overnight before the first weighing was made. The cell was returned to the system, heated for a measured time at constant temperature, cooled, and reweighed. The heating and cooling times were quite short since the hot furnace was raised to receive the reactor at the beginning of the run and removed again at the end. The tube heated or cooled quickly. The total mass loss was attributed entirely to effusion of silver vapor from the quartz cell, since empty quartz cells maintained constant mass through similar heating cycles. The vaporized silver condensed on the cold walls of the quartz tube extending above the furnace. Earlier studies in the induction heated unit had shown that the same vapor pressure was found for silver, whether the silver was in contact with the tantalum metal cell or with porcelain or quartz liners. The Pt-Pt-10 pct Rh thermocouple was calibrated against a secondary standard of the same material and found to agree with the published tables. Always operating in air at temperatures below 100O°C,

Jan 1, 1954

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By A. Styka, G. Fischer, S. Tour

Described herein are the results obtained during research work involving coating titanium alloys with molybdenum by vapor-deposition methods. Results show that the method can be used successfully to deposit hard adherent wear-resistant coating of methodmetallic molybdenum on titanium or titanium alloys without changing the microstructure of the titanium base. PRODUCTION and use of titanium and its alloys have increased tremendously in the past few years. The physical, mechanical, and chemical properties of this engineering metal have caused considerable enthusiasm among metallurgists and engineers. However, as with all materials, there are some drawbacks. For example, titanium is susceptible to seizing and galling on wearing surfaces. In order to produce a good wear-resistant surface, many investigations have been conducted evaluating oxidizing, carburizing, nitriding, carbonitriding, sili-conizing, and chromizing of titanium. All of these processes require high temperatures for rather extensive periods of time. It has been possible to produce hard surfaces on titanium and its alloys by a number of these processes at the expense of a deterioration of the physical properties of the base material. A practical solution to the problem of providing titanium and titanium alloy parts with a satisfactory wear-resistant nongalling surface must be one that does not involve excessive temperatures for long periods of time. Sam Tour & Co. Inc. has completed a research and development contract for the United States Army Ordnance Corps on vapor deposition of molybdenum on titanium and titanium alloys. On the basis of results obtained from the research program, titanium alloys can be coated successfully with molybdenum to provide a hard wear-resistant surface without harm to their base mechanical properties. The remainder of this article is a description of the techniques used to apply the coating and the results obtained from wear tests on molybdenum-coated titanium. Theory Basically, the technique used was the application of molybdenum by a vapor-deposition method, thermal decomposition of molybdenum hexacarbonyl [Mo(CO)] with hydrogen as the carrier gas. The selection of this method was based chiefly on the following considerations: 1—low plating temperature which would minimize excessive grain growth, 2— low decomposition temperature of the carbonyl, 3— possibilities of controlling the hardness of the plate by adjusting the carbon content using the plating temperature and pressure as the primary variables, 4—use of high vacuum, thereby avoiding unnecessary oxidation and other complex reactions with the atmosphere. Free energy data1 show the strong tendency for titanium to combine with O2 N2 or carbon from normal temperatures to temperatures above its melting point. To maintain the titanium in a film free condition, the use of as high a vacuum as possible is indicated. The literature' indicates that the reaction product of hydrogen with titanium is unstable in vacuum at around 400°C. 5—Although it is indicated from the thermodynamic standpoint that there is little possibility of removing carbon from either titanium or molybdenum, the work of Lander and Germer -ndicates that the use of a suitable H,/CO ratio is somewhat effective in minimizing carbon deposition. 6—Availability of molybdenum carbonyl. In the simplest form, the conditions of equilibrium3 in chemical reactions involving decomposition of carbonyl are as follows: Mo (CO) ? Mo + 6CO 2CO * C + CO,. The plating rate is proportional to the rate of evolution of CO from the decomposed carbonyl, i.e., it is proportional to the pressure of the gaseous decomposition products. Carbon released from CO gas is the significant constituent for the variability of the physical properties of the product. High carbon deposition is favored by increasing pressure. Limitations are imposed in the selection of plating temperature and pressure. Excessive temperature re-

Jan 1, 1956

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

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

The slip and twinning planes have been determined in deformed crystalsof titanium by an X-ray method of analysis. The slip planes are of the type {1010} and {1011}, while the twinning planes are of the type {1072}, {1121}, and (1122). In the case of the predominant (1010) slip, a type I digonal axis of indices <1120> was the effective slip direction. Microscopic observations on the appearance of the three twin types disclosed a distinct difference in their shapes, and an attempt was made to correlate this difference with the amount of twinning shear. The slip mechanism was discussed on the basis of the difference in c/a ratios for the common hexagonal close-packed metals. IT is a general rule that slip in metals occurs most easily on the planes of greatest atomic density and of the largest interplanar spacing, and that the direction of slip is a close-packed direction. Thus, of the hexagonal close-packed metals which have been investigated by the German school in the decade 1925 to 1935 (cadmium, zinc, and magnesium), it has been found that slip occurs on the basal plane (0001) and in a <1120> direction.&apos; In the case of magnesium above 225oC, slip occurs on a first-order pyramidal plane (1011) as well as on the basal plane.&apos; The hexagonal metals, moreover, deform in part by twinning, and, again with the exception of magnesium at elevated temperatures, the twinning plane has always been reported to be a second-order pyramidal plane {1012).&apos; In view of this consistency in the plastic behavior of these metals, it has been supposed that the same slip and twinning elements would be operative in the other important hexagonal close-packed metals (titanium, zirconium, and beryllium), although there are some reasons why this may not be so. Referring to the tabulation in Table I of the axial ratios of the important metals in this structural class, it may be seen that they can be categorized into three distinct groups depending on the value of their c/a ratios. In the first group are cadmium and zinc with large positive deviations from the ideal ratio for closest packing. This expansion in the direction of the c-axis would be such as to accentuate the basal plane as the slip plane, because it increases the interplanar spacing. The second group includes cobalt and magnesium, which closely approximate the ideal ratio. In the third group are zirconium, titanium, and beryllium whose axial ratios are decidedly less than the ideal. The lattice of the elements in this group is compressed along the c-axis which, in effect, tends to make the basal plane less favorable for slip inasmuch as it reduces the interplanar spacing and the atomic density of this plane. Thus, for metals in the third group, it may be said that there is a certain indefiniteness about the glide plane, in that planes other than the basal plane may be expected to operate. The fact that magnesium begins to exhibit planes other than the normal slip and twinning planes at elevated temperatures may indicate that this behavior will become more pronounced in metals of lower axial ratios. For this reason it might be expected that the slip and twinning behavior of zirconium, titanium, and beryllium would be different from that found in cadmium and zinc. One indication that there is a difference is reflected in the recent work which has been done on the deformation textures of these metals."&apos; As will be shown later, there is a significant difference between the rolling textures of cadmium, zinc, and magnesium on the one hand, and zirconium, titanium, and beryllium on the other, and this difference suggests that the mechanism of plastic flow is not the same in these two groups of metals. From these considerations, therefore, it may be seen that there are good reasons why it cannot be concluded that titanium will have the same crystal-lographic elements of slip and twinning as those exhibited by zinc and cadmium. For the complete determination of these elements it would be most advantageous to have single crystals. However, much valuable information can be obtained by using coarse grained polycrystalline specimens, provided the grains are sufficiently large to permit X-ray

Jan 1, 1954

By C. W. Thompson

Paul D. Suloff (Goodyear Tire and Rubber Co., Inc., Akron, Ohio)—I would like first to comment on problems of the conveyor belt discussed in Mr. Thompson&apos;s excellent paper, since that is what we hope we know most about. Twists in relatively wide conveyor belt unavoidably produce a lateral maldistribution of tension, raising tension at belt edges and reducing it at the center. They also produce a lateral collapsing force on the belt at the center of the twist owing to the inherent tendency of all the longitudinal elements of the belt to try to pass through a point at the twist center. Calculation of the twist geometry by the methods shown in Mr. Thompson&apos;s paper keeps these extraordinary forces within limits which the belt designer can tolerate. No reduction in belt life due to twisting need be contemplated when this geometry is maintained. There is a minor exception that belts of extreme lateral flexibility will tend to curl laterally at the center of the twist. However, any ordinary fabric construction will perform satisfactorily in this respect. These twists are always made in regions of low tension in the conveyor so that even in the edges of the twist, belt tension does not exceed the average tension found in highly stressed regions of the conveyor. Offsetting these out-of-ordinary belt stresses is the advantage that Mr. Thompson has brought out of getting the return run up out of the dirt where it can be seen. This not only makes it easier to train, but also, in the event that it is not properly trained, frees it of the normal return run edge wear hazard. It is well known that return run edge wear is a prominent cause of belt mortality underground. An interesting aspect of this two-way conveyor is that the belt may be made what is known as a Mobius Strip. A Mobius Strip is obtained by splicing a belt after turning one end of it 180" about its longitudinal axis. In other words, one end is turned upside down before splicing. A belt spliced in this fashion turns itself upside down every time it comes around, but the twist which has been put in the splicing, of course, stays at one location on the conveyor, in this case one of the twist sections at the end. Turning the belt over every revolution might have advantages in some cases. Belts could be made with equal covers and the two sides worn equally and simultaneously. In this case there would be no problem of getting belts on upside down by mistake. However, the two-way conveyor does not have to be a Mobius Strip. It can be twisted in such fashion that the same side is up on both runs. It is simply a question of which way the final 90" twist is made before joining the ends. Another interesting aspect of the two-way conveyor is the problem of operating two-way conveyors in series. Here the sequencing of starting brings up some new problems. It will be recognized, although not always at first glance, that if the starting sequence is planned for one run of the conveyor the reverse will result on the other run. With the two runs carrying bulk material in both directions a reverse sequence on one run would be intolerable. In this situation the only solution appears to be a simultaneous starting of all conveyors in the series. However, with the coal in one direction and intermittent supplies in the other it would be entirely practical to sequence the conveyors for the coal run and accept a reverse sequence on the supply run. The two-way conveyor also lends itself to new driving possibilities. First, it is quite possible to drive at the head end of each run, which of course, means a drive at each end of the two-way conveyor. Driving in this way a given belt can be extended to substantially greater lengths than a conventional conveyor with drive at one end only. In addition to this, under certain conditions the conveyor can be extended to extreme length by driving at one end and at some intermediate point on the most heavily loaded run. As a particular case, a belt carrying coal downgrade and supplies back upgrade could be extended to extreme lengths by driving at the head of the coal run and at an intermediate point of the supply run. Mr. Thompson has been a pioneer in belt conveyor transportation underground and his accomplishment here with the first two-way conveyor of any consequence is another notable addition to the art.

Jan 1, 1954

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3&apos;, as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

T.B.King (Depaytment of Metallurgy, Massachusetts Institute of Technology)— A valuable contribution of the authors is in the factual information which they have been able to gather; this type of information is quite difficult to obtain. In many respects, however, it would have been better if they had not subsequently embarked on a discussion of the chemistry of the converter process. It seems inconceivable that the authors do not refer to the papers of Schuhmann and his associates14 which have set the thermodynamic foundation for the whole copper smelting operation. In addition, a very useful review on the physical chemistry of copper smelting by Ruddle 5 appeared as long ago as 1953. An examination of this literature would have convinced the authors that there is no cause to be surprised at a correlation between the magnetic content and the silica content of converter slags, though they rightly point out that one should distinguish between the total magnetite content of the slag and the amount of magnetite which may be considered to be in solution. It is not true that the lowest melting converter slag is that corresponding to the eutectic between ferrous oxide and silica. The simplest slag system which can be considered is a three-component system, since both ferric and ferrous iron are present. As Schuhmann, Powell, and Michal have shown, there are lower melting compositions than this eutectic in the ternary system. The most unfortunate impression given by this paper is that the driving force for chemical reaction is determined by the heat of reaction: of course the entropy change must be taken into account. It would have been more correct to list, in Table VI, values for free energies of formation. Nor can it be said that the data in Table VI represent the "best available data." They do not corregtond with any of the recent, acknowledged sources. F. E. Lathe and L. Hodnett(author&apos;s reply)— We are pleased that Dr. King finds the factual information in our uawer of some interest. Dr. King suggests that it would have been better if our analysis and discussion of the data had been omitted, largely because our list of references is so. incomplete. If he will carefully read our introduction, he will see that the questionnaire was sent out in the hope of obtaining data which would throw light on certain questions relating to the use of converter refractories. We did not attempt (nor would the AIME have published!) a complete review of the literature on copper converting, as Dr. King has apparently assumed, nor indeed a complete analysis of the data submitted, but tried only to find a sound basis for the choice of refractories, taking into consideration common variations in converter practice. We hope our paper indicates that, by raising the silica content of the converter slag and operating at a higher temperature, the normal circulating load of magnetite can be greatly reduced, and the whole reverberatory-converter operation improved to a major degree, with resultant important savings. Under such operating conditions, chrome-magnesite brick may be expected to stand up better than those of straight magnesite. Regardless of the choice as between these brick types, however, we find the cost of converter refractories to be so low in comparison with other converter costs as to justify operation under the more severe conditions suggested. Valuable as are the papers by Schuhmann and associates and the book by Ruddle, we make no apology for omitting reference to them, nor for using heats of reaction without mention of entropy changes or free energies of formation. Our primary object was to interest the practicing copper metallurgist, with whose language we may claim to be fairly familiar; we think it would have been unwise to include the highly theoretical phases of the subject which Dr. King suggests. The interest shown in our preliminary paper presented at the New York meeting in 1956, and the trends in practice whtat we have observed since that time, suggest that we did not wholly miss the target. In conclusion, we sincerely hope that Professors King and Schuhmann will independently review the data obtained in our questionnaire and submit a paper giving their own recommendations as to the choice of refractories and the particular converter operating conditions which will result in the lowest overall cost of copper smelting and converting.

Jan 1, 1960

By Clyde Evarts Weed

SOME one once affirmed his great belief in luck, adding that he had found that the harder he worked the more luck he had. Clyde Weed is a firm believer in this method of courting the fugitive lady. He is at work early and late, often leaving his staff at Anaconda&apos;s offices at 25 Broadway breathless trying to keep up with the ideas teeming from a fertile brain and the actions those ideas entail. Miles ahead of his assistants much of the time, he still manages to be an agreeable fellow to work with, no small accomplishment as many can testify. Mr. Weed arrived in the world at Moorestown, Mich., on Aug. 8, 1890. Sixteen years later he entered Michigan Agricultural College, a lowly freshman. The following year, with the experience and wisdom expected of a sophomore, he transferred his studies from the reaping of a harvest on the surface of the earth to delving into the deeper, unpredictable bowels of the earth, his studies now shifted to the Michigan College of Mines. Last June his alma mater conferred upon him the degree of Doctor of Engineering.

Jan 1, 1947

By D. C. Hilty

It has long been known that in melting high-chromium steels, some of the carbon might be oxidized out of the melt without excessive simultaneous oxidation of chromium, and that higher temperatures favor retention of chromium. The advent of oxygen injection as a tool for rapid decarburization of a steel bath permits significantly higher bath temperatures, and it was quickly recognized that the use of oxygen injection facilitated the oxidation of carbon to low levels in the presence of relatively high residual chromium contents. Up to the present time, however, specific data pertaining to the chro-mium-carbon-temperature relations in chromium steel refining have not been available. Individual steelmakers have evolved practices more or less empirically, but there has been very little real basis for predicting how effective any given practice can be in permitting maximum oxidation of carbon with minimum loss of chromium. The current investigation, therefore, was undertaken in an effort to establish the fundamental carbon-chromium relationship in molten iron under oxidizing conditions. As reported below, the equilibrium constant and the influence of temperature on that constant have been derived for the iron-chromium-carbon-oxygen reaction in the range of chromium steel compositions with what appears to be a fair degree of precision. The practical application of the result will be obvious. Experimental Procedure The laboratory investigation was carried out on chromium steel heats melted in a magnesia crucible in a 100-lb capacity induction furnace at the Union Carbide and Carbon Re- search Laboratories. The charges for the heats consisted of Armco iron, low-carbon chromium metal, and high-carbon chromium metal, the relative proportions of which were calculated so that the various heats would contain from approximately 0.06 pct carbon and 8 pct chromium to 0.40 pct carbon and 30 pct chromium at melt-down. When the charges were melted, the bath temperatures were raised to the desired level, and the heats were then decarburized by successive injections of oxygen at the slag-metal interface through a ½-in. diam silica tube at a pressure of 30 psi. The duration of the oxygen injections was from 30 sec to 2 min. at intervals of approximately 5 to 30 min. It did not appear that length or frequency of the injection periods had any significant effect on the results; cansequently, no effort was made to hold them constant and they were controlled only as was expedient to the general working of the heats. Between successive injections, the heats were sampled by means of a copper suction-tube sampler that yields a sound, rapidly-solidified sample representative of the composition of the molten metal at the temperature of sampling. This sampling device is a modification of the one described by Taylor and Chipman.1 An attempt was made to vary bath temperatures between samples, but it quickly became evident that, unless the variations were small or unless the new temperature was maintained for a minimum of 15 min. during which an injection of oxygen was made in order to accelerate the reactions, a very wide departure from equilibrium resulted. For most of the runs, therefore, temperature was maintained relatively constant at approximately 1750 or 1820°C. A few reliable observations at other temperatures, however, were obtained. Temperature Measurement The high temperatures involved in this investigation were measured by the radiation method, utilizing a Ray-O-Tube focused on the closed end of a refractory tube immersed in the metal bath. The immersion tubes employed were high-purity alumina tubes specially prepared by the Tona-wanda Laboratory of The Linde Air Products Co. These tubes were quite sturdy under reasonable mechanical stress at high temperature. They were unusually resistant to thermal shock, and chemical attack on them by the melts was slow. With care, it was found possible to keep these tubes continuously immersed in a heat for as long as 5 hr at temperatures up to 1850°C, before failure by fluxing occurred. The Ray-O-Tube—alumina tube assemblage was similar to those supplied commercially for lower temperature applications. In operation, the alumina tube was slowly immersed in the molten metal to a depth of approximately 5 in., and the device was then clamped solidly to a supporting jig where it remained for the duration of the run. A photograph of the equipment, in operation with Ray-O-Tube in place and oxygen injection in progress, is shown in Fig 1. When in position in a heat, the instrument was calibrated by means of an immersion thermocouple and an optical pyrometer. For calibration through the range of temperatures from 1500 to 1650°C, a platinum -platinum + 10 pct rhodium thermocouple in a silica tube was immersed alongside the alumina tube. Output of the Ray-O-Tube in millivolts and the

Jan 1, 1950

By D. A. Augenstein, L. V. Amundson

Operators of coal preparation plants use equipment such as large-capacity dump trucks and bulldozers to haul, spread, and compact refuse material to conform to federal and state regulations governing the disposal of solid waste. For example, federal regulations require that refuse be spread and compacted in layers not more than 0.6 m (2 ft) thick. If the refuse layers or piles have poor load-bearing characteristics, movement of equipment over them becomes extremely difficult. The increasing cost and limited space for the construction of settling ponds extensively used for fine refuse disposal are leading to the growing practice of dewatering the fine refuse by means of vacuum disk filters and combining the resulting filter cake with coarse refuse for waste bank disposal. However, this filter cake usually contains more than 25% moisture. Therefore, when it is combined with coarse refuse, the moisture level of the total refuse may become high enough to impair the load-bearing strength of the refuse. Precisely this problem and the attendant difficulties of moving heavy equipment arose when vacuum disk filters were installed at a preparation plant in West Virginia. Combining the moist filter cake with the coarse refuse generally results in a 12% moisture level for the total refuse at this plant. At this moisture level, the refuse can still be handled with some dif¬ficulty by the equipment. However, the problem has frequently been compounded after rains. The experimental program described in this paper tested the following methods of improving the load-bearing properties of coal refuse: moisture reduction, addition of crushed coarse refuse, addition of fly ash, addition of lime, and addition of a mixture of lime and fly ash. In terms of a balance between economic and technical considerations, the most effective method was demonstrated by laboratory and plant tests to be a 2% to 5% addition of lime. Test Program During formulation of a test program aimed at improving coal refuse stability, a number of treatment techniques were selected for evaluation of their effect on refuse load-bearing characteristics. The reduction of refuse moisture was the first technique considered, since moisture content plays a key role in the bearing strength of a bulk solid. The reasoning was that a very small reduction in refuse moisture, provided it could be accomplished with minimal effort and cost, would be sufficient for eliminating refuse disposal problems most of the time. At the same time, it was recognized that periods of rainy weather would offset moisture-reduction measures. Other techniques selected for evaluation because of their potential for improving refuse-bearing strength at reasonable cost were: addition of crushed coarse refuse, the addition of fly ash, and the addition of lime. A simple one-dimensional laboratory compaction test was designed for evaluating the effect of each of these techniques on refuse-bearing strength. Those techniques that gave best results in the laboratory would then be tested in the preparation plant in West Virginia. Laboratory Tests The laboratory test for evaluating each of the techniques involved the application of weight to a load module placed on a refuse sample in a container. The distance the load module sank with an increasing amount of applied weight was measured, and the relationship between module displacement and loading was obtained. The refuse container was large enough to minimize the influence of wall effects, and to decrease the effect of the container bottom, a test was terminated when the load module sank to about three fourths the depth of the container. Initially, an attempt was made to conduct compaction experiments with samples of total plant refuse. However, the presence of + 0.13 m (+ 5 in.) material in the refuse interfered with the mechanics of the test, and the large amount of material required for a representative sample made testing extremely tedious and time-consuming. To avoid this problem and because it was believed that only the fine components of the refuse were the major cause of the stability problem, tests were conducted with 13 mm X 0 (1/2 in. X 0) material from the total plant refuse. The equipment consisted of a 0.46 m (18 in.) cubic container, a loading module with 62 cm2 loading area, weights totaling 450 kg, and a portable concrete mixer for combining water and additives with the refuse. Refuse samples of about 110 kg dry weight were used for each test. Experimental compaction test data were evaluated by plotting the linear displacement of the load module vs. loading. During compaction tests, the vertical displacement of the load module was measured at each loading value. The plot of

Jan 1, 1980

By B. G. Matson, M. A. Whitfield, G. R. Dysart

This paper describes the development of u computer program to calculate changes that occur in the length of tubular goods due to temperature and pressure changes during stimulation operations. Due to the numerous variables involved and the uncertainty of all static and dynamic conditions that could exist, it becomes a staggering task for individuals charged with completions to perform the necessary mathematical calculations. The computer program permits advance calculations for several sets of conditions. INTRODUCTION In the Delaware basin of West Texas alone, 50 wells were contracted or drilled to 15,000 ft or deeper in 1965. Deep well activity is continuing in this and other areas on an expanding scale. Many of these deep wells require extensive stimulation for successful commercial production, and during these operations, pressures and temperatures are encountered that have a pronounced effect on the length of tubular goods. This length change during a large-volume, high-pressure stimulation treatment utilizing fluids considerably cooler than bottom-hole temperature can be of such a magnitude that permanent damage to casing and tubing will result unless mechanical design, pressures and fluid temperatures are evaluated and controlled. These pressure and temperature effects can be calculated. However, the process lends itself well to computer solutions because of the mathematical nature of the problem and the calculating hours involved in arriving at an answer. The engineering-hour demand becomes more severe as tapered strings are involved. On initial treatments on a given well, surface pressure and injection rate conditions are unknown, and offset well conditions have not proven to be a reliable method for making predictions. For these reasons, it has become rather standard procedure for operators to compensate for these uncertainties by placing unnecessary pressure and fluid temperature restrictions on stimulation design. On a number of occasions treating fluids have been preheated to as much as 160F as a means of compensating for thermal contmction resulting from pumping cool fluids. The maintenance of packer seals has been treated by Lubinski, Althouse and Logan&apos;,&apos; and the problem of therma1 effects on pipe has been explored by Ramey." These works were expanded and the results made applicable to everyday oilfield terminology before submitting them to computer programming. The pressure and temperature effects on tubing movement previously mentioned occur simultaneously as fluid moves through the pipe. The pressure changes, for purposes of explanation, are categorized here as to the various effects these pressures have on a tubing string. These divisions are (1) the piston-like results of forces acting on horizontal surfaces exposed to pressure, (2) swelling or ballooning of the tubing along its entire length due to the forces of pressure acting against the tubing walls, (3) the elongation of tubing due to frictional drag and (4) corkscrewing of the pipe due to internal pressure. Thermal changes are also of great importance, as their results may be more significant than any of the pressure effects. Steel is an excellent conductor of heat and the earth is a relatively poor conductor. It has been calculated that pipe temperatures at depths of more than 20,000 ft approach within as little as 25" the temperfature of the surface fluid after pumping for 2 hours, or a drop in temperature in some treatments of more than 220F. The equations presented in this paper were developed for computer programming and simplicity of input information; therefore, numerical constants such as Young&apos;s modulus for steel (28 X 10\ si), the coefficient of thermal expansion of steel (6.9 X 10."IF) and Poisson&apos;s ratio for steel (0.3) are included with unit conversion factors. The moment of inertia of tubing cross-sectional area with respect to its diameter was changed to a constant times (D&apos; — d&apos;) where D is outer diameter and d is inner diameter. Units in the equations are length in feet, diameter in inches, density in pounds per gallon, pressure in psi, rate in barrels per minute and time in hours. PISTON-LIKE REACTIONS A change in tubing internal dimensions and the exposure of other horizontal surfaces to different pressures on the inside and outside of the tubing result in a reaction much like a piston under pressure. Such is the case when the internal diameter changes in a combination string of pipe, when seals of a slick joint assembly are subject to pressure and in the end effects of a tubing string. The change in tubing length due to the piston effects of a slick joint packer is affected by the various diameters involved, the tubing pressure Ap,, the casing pressure ,Ap,, length of pipe L, densities of fluid in the tubing before and during pump-

By K. E. Barrett

Exxon owns a uranium mill and holds two mining leases in Live Oak County, Texas, about halfway between San Antonio and Corpus Christi. The properties make up the Felder Uranium Operations which was reopened earlier this year. Exxon held an oil, gas, and other minerals lease on the J. C. Felder tract, which was adjacent to a relatively shallow uranium discovery by Susquehanna-Western, Inc. on the Marrs-McLean lease immediately south of the Felder property. Drilling in 1967 and 1968 confirmed the presence of reduced uranium mineralization in the basal sand unit of the Oakville formation on the Felder tract, which formed the major part of the roll-front deposit. In 1969 Exxon and Susquehanna-Western, Inc. entered into a sale and purchase agreement which provided for Susquehanna to mine and process Felder ore and purchase recovered uranium. Susquehanna moved an alkaline-leach mill from Wyoming, erected it on the Ray Point property, and placed it into operation late in 1970. Susquehanna mined and processed ore from the Felder and McLean properties through March 1973. Susquehanna ceased operations in March 1973. Exxon then acquired the mill and mill property. Exxon also purchased the mineral rights to the McLean lease, re-negotiated a mining lease for that property, and carried out shut-down programs for the mining and mill areas in the fall of 1973. The project was put on a standby basis until late 1973, when Exxon initiated mine feasibility studies for the project. MINE PLANNING EVALUATION The feasibility study for reopening the Felder Project began in late 1975 and was not completed until late 1976. I will discuss several areas of the feasibility study that required additional work prior to making the decision to renew operations. Ore Reserves Preparations for estimating the ore reserves began with the re-evaluation of more than 1500 natural radioactivity logs from exploration and pre-development drilling that had been completed on the property. These gamma ray logs of non-core rotary drill holes were the principal source of data used in making the estimate. Chemical assays of cores from the deposit were also used in the reserve determination. Electric resistivity and self-potential logs were made along with the gamma ray log. In December 1975 an additional core drilling project was undertaken to confirm the in-place density and radiometric equilibrium characteristics of the ore deposits. Comparison of chemical assays of cores with the U308 values calculated from the logs showed that the unoxidized ores were in radiometric equilibrium. In contrast, cores from anomalies occurring in near surface, weathered, and oxidized zones were in radiometric disequilibrium. Several important decisions were made in developing a mine plan or schedule of production from the Felder and McLean ore bodies. Disposal of Produced Mine Water: The ore bodies of the Felder Uranium Project occur at a point below the ground water table. The ore zones to be mined must first be dewatered to allow removal of mineralized material. In the open pit operations, this is accomplished by maintaining a perimeter ditch around the periphery of the open pit, allowing the interior of the pit to drain and collect into a sump and be pumped from the mine. In addition to anticipated water production from future mining operations, approximately 200M gallons of water was contained in three open pits left from prior mining operations. In two of these existing pits, the water was to be removed and disposed to allow for planned backfilling of waste material into these pits. The third pit would also have to be drained to allow continued mining of an area left from the prior operations. Essentially no ground water information was available for this area. The only data available was water production history from Susquehanna&apos;s mining operation. Two water wells were drilled early in 1976 on the Felder lease for use in obtaining hydrological data. A long term draw-down test was performed by pumping one water well and measuring water level drawdown in both the pumped well and the observation well. From these data, values for permeability and storage coefficient were calculated. These data were then used in modeling the aquifer to allow calculation of water influx into the mining area versus time. Once a schedule of water production, including the stored volume in the existing pits was calculated, alternate solutions for disposal were evaluated. The first system evaluated was a series of deep injection wells. The wells were designed to inject at a depth of approximately 3500 feet. Again very little information concerning reservoir characteristics of the receiving sand units was known. Using assumed values for reservoir permeability and storage coefficients, an injection well system was designed to allow for disposal of produced mine water. The biggest

Jan 1, 1979

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775&apos; and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,&apos; and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts&apos; gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts&apos; apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,&apos; oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955