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By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By P. Breidt, E. S. Greiner

THIS note reports a determination of the melting point of germanium, and the liquidus of the Ge-Ga alloys; lattice constants of the a phase are given. The alloys were prepared by melting germanium (>20 ohm-cm resistivity) and gallium (99.6 pct) in evacuated silica tubes. The materials (50 to 70 g) were heated at 1000°C, held in the liquid state for about ¾ hr, and then cooled rapidly in the tubes. Points on the liquidus were obtained by thermal analysis which consisted of obtaining time-temperature data during heating and cooling the materials in high purity graphite crucibles and a helium at- mosphere. Temperatures were determined with a Pt—Pt-Rh thermocouple protected by a silica sheath. The couple was calibrated against a National Bureau of Standards calibrated couple and also against the freezing points of copper, silver, aluminum, and the 28.1 wt pct Cu, 71.9 wt pct Ag alloy eutectic. The samples for X-ray analysis were prepared by heating small pieces of the ingots in evacuated glass or quartz tubes at temperatures between 600" and 900°C for periods ranging from 2 hr to 22 days, periods deemed sufficient for equilibrium to be attained, followed by quenching in water. The heat-treated samples were ground to powder for X-ray analysis. The lattice constants of the germanium-rich phase (a) were determined with a baok-reflection focusing camera. The X-ray reflections (331 and 422 Cr Ka, 422 and 333 Cr KB) were corrected

Jan 1, 1956

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By B. F. Peters, J. Gordon Parr, E. R. Macgregor

A SERIES of seven hypoeutectoid alloys, up to 18.2 atomic pct Mn, was made by the levitation melting technique. The loss of weight on melting was considered to be entirely due to volatilization of manganese, and compositions were computed on this basis. Filed samples (—200 Tyler mesh) were helium quenched from 1000°C after soaking for 5 min by a technique already described.' Quenched Alloys -Assessments of the amounts of a phase produced and the hardness of the quenched alloys are summarized in Fig. 1. The experimental techniques and calculations involved have been described previously. The amount of a decreases as manganese content increases, until at 10.6 pct Mn only a trace of a' is observed. Previous

Jan 1, 1957

By Stephen Krickovic

AS it is commonly understood in the bituminous coal mining industry, pillaring means removal, as completely as is practical, of all pillars formed in the development of headings and rooms on first mining. The degree to which this can be accomplished, termed percent of recovery, is of course dependent generally upon the physical conditions of the bottom and the overburden, the system of min-

Jan 1, 1956

By F. D. Wright, H. D. Fara

The solution to the plastic and elastic stresses around a circular shaft in a hydrostatic stress field that has appeared in two editions of a widely used book on rock mechanics1 is in error. Although this is a relatively minor matter, the correct solution was not found by a literature survey, so it appears worthwhile to present it. For a homogeneous, isotropic, rigid plastic-elastic body in plane strain which obeys Tresca's yield criterion the following equations must be satisfied:'," In the plastic zone,

Jan 1, 1963

By L. J. Klinkenberg

It is pointed out that the current concept of pore size distribution is not unequivocally defined and that different methods aiming at a determination of such a distribution therefore do not lead to the same results. A pore size distribution should not be based on the idea that a core should, under all circumstances, behave as a bundle of straight non-interconnected capillaries of the same pore size distribution. This is illustrated by calculations and experiments on the displacement of miscible liquids. INTRODUCTION The introduction of the concept of pore size distribution has been an attempt to characterize the intricate geometry of the flow channels in porous media. As pores in a porous medium are interconnected it is impossible to describe exactly what is meant by a "pore" and, therefore, the term pore size distribution requires further amplification. In the visual method for the determination of pore size distribution "the pore" is considered to be the hole between the grains as observed on thin sections or on a polished surface of the rock under a microscope. In all other presently known methods,1,2 a displacement process is studied and it is ascertained what as- semblaae of straight cylindrical capillaries would show the same behavior. The distribution of the capillary diameters of this assemblage is said to represent the size distribution of the pores of the actual porous medium. From the foregoing it is already apparent that it is useless to try to decide which process or which method of investigation leads to a "correct" pore size distribution. To illustrate this further a displacement process in which a fluid is displaced by another miscible with it will be discussed and the results will be interpreted in terms of a pore size distribution. DISPLACEMENT EXPERIMENTS WITH MISCIBLE LIQUIDS OF NEARLY IDENTICAL VISCOSITY AND DENSITY Interpretation in the Form of a Pore Size Distribution If distilled water is displaced from a homogeneous unconsolidated sand pack by, for instance, a dilute solution of NaCI, the breakthrough recovery i.e., the amount of distilled water produced at the moment the first trace of NaCl can be detected in the effluent water, is between 95 and 100 per cent of the pore volume of the pack. This result can be understood by following in imagination the course of one particle of the liquid. Imagine a length, ?l, at the end of which a liquid particle has an independent chance of a renewed choice of pores of different diameters. In other words, the particle has a choice of traveling time, at, for any length ?l; instead

Jan 1, 1958

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By L. S. Richardson, N. J. Grant

REACTIONS of oxygen and nitrogen at low pressures with titanium have recently been studied by a number of investigators.1-3 Gulbransen and Andrew' noted that the reaction with nitrogen followed the parabolic rate law whereas the reaction with oxygen deviated slightly from this law in the temperature range 300° to 800°C. In the work reported here, commercial titanium (75 A) was used as the test material. Cylinders 2.5 in. long and 0.25 in. in diameter were machined from heavier bar stock. The test pieces were given a metallographic finish, immersed for 30 min in cold concentrated HC1, washed in water, then acetone, and dried with lint-free cloth. Reaction rates were determined in a modified Sieverts type apparatus by measuring the decrease in gas pressure of the reacting gas contained in a constant volume. The amount of gas added could be measured in a calibrated gas burette to an accuracy of 0.01 mm. During the course of a run the temperature never varied by more than 10°C and then only for brief moments. After placing the specimen in the furnace, the system was first evacuated for 12 hr at room temperature, and then flushed with purified argon five times, adsorbed gases being discharged during this period from the glass system with a high frequency spark coil. The flushing and discharging were repeated at 400°C. This rather involved procedure was found necessary after a number of trial runs indicated extraneous effects traceable to the system. Reaction periods up to 2 hr were used, at initial gas pressures of 0.2 to 0.5 atm. Experimental Results Fig. 1 shows the decrease in oxygen pressure for tests at 0.5 atm at various temperatures as a function of the square root of the time. Deviations from linearity are minor and the parabolic rate law is obeyed. Fig. 2 shows the same plot for the nitrogen reaction. A definite deviation from linearity is noted; however, it is probable that the higher initial rates are caused by the presence of small amounts of oxygen contamination, the initial faster rate changing to the slower rate after about 5 to 10 min. Calculations of the rate constants were made on the basis of the latter portion of the curves. The parabolic rate law constants calculated from these curves are shown for oxygen and nitrogen in Fig. 3. In spite of some scatter the average curves are quite definite. Changes in gas pressure of the order of 20 pct did not result in a measurable change in the rate law constants. The activation energy for the oxygen reaction was calculated to be 47,400 cal per mol (above 700°C), which is not in agreement with the value quoted by Gulbransen and Andrew' for lower temperatures, their value being 26,000 cal below 600°C. The activation energy for the nitrogen reaction was calculated to be 45,400 cal per mol above about

Jan 1, 1955

By D. H. Davis, I. Fatt

Oil bearing rocks, usually found at depths of 2,000 to 10,000 it, are elastically deformed by overburden pressure. Although the change in porosity with pressure in a number of example rock.: has been shown to be small, it was thought that overburden pressure might have a significant effect on permeability. This note presents results of an investigation to determine the magnitude of the change in permeabilty with pressure. In routine core analysis permeabilities are measured on rock samples which are not under overburden pressure. If permeablity measured in this way differs from permeabilities measured under overburden pressure, a systematic error is introduced into well productivity calculations. The experiments described in this report were made to determine the magnitude of the change and thus to give an estimate of the error introduced into the calculations. The error introduced by the neglect of the change in permeability when overburden pressure is removed may account for part of the difference between well productivity calculated from core analysis and the actual well productivity. The results obtained in this investigation have only quali-tative significance because of the difficulty in reproducing in the laboratory the stress conditions on the rock buried in the earth. The assumption which is usually made is that the rocks in the earth are under a uniform pressure equal to the weight per unit area of the vertical overburden column from the rock in question to the surface of the earth less the pressure of the liquid in the pores of the rock. For an overburden consisting of sandstones and shales (of assumed average specific gravity of 2.3) and for a liquid pressure equal to the pressure in a salt water column (of specific gravity 1.0) reaching from the rock to the surface, the resulting net pressure on the rock is approximately 0.56 psi per ft of depth. EXPERIMENTAL METHOD Clean, dry sandstone core plugs one in. in diameter and about three in. long were mounted in a copper foil jacket as shown in Fig. 3 or molded in a Lucite jacket as shown in Fig. 4. All cores except those labeled "2" in Fig. 1 and "8" in Fig. 2 were measured in the copper foil jacket. Cores "2" and "8" were measured in the Lucite jacket. The jacketed core was placed in a high pressure hydraulic bomb in which the liquid pressure outside the jacket could be raised to 15,000 psi. Flow lines from the core were brought out of the bomb through special fittings in the bomh head and connected to a laboratory type gas permeameter. Measurements were made with nitrogen gas; the maximum mean gas pressure in the core was 16.1 psia. RESULTS The specific permeability of sandstone decreases with in. crease in overburden pressure. Most of the decrease takes place over the range of zero to 3,000 psi overburden pressure. If the net pressure on the rock is assumed to be 0.56 psi per ft of depth as discussed above, 3,000 psi of overburden pressure is equivalent to about 5,000 ft of overburden. At 3,000 psi overburden pressure, the permeability of the eight sandstone core samples tested ranged from 59 to 89 per cent of the permeability without overburden pressure. Figs. 1 and 2 show the permeability reduction as a function of overburden pressure. The permeability of the eight cores without overburden pressure ranged from 4.35 md to 632 md; these permeabilities are listed in Figs. 1 and 2. REFERENCES 1. Carpenter and Spencer: "Measurements of Compressibility of Consolidated Oil Bearing Sands," U. S. Bureau of Mines, R.I. 3450, (1940). * * *

Jan 1, 1952

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By H. W. Paxton, C. C. Busby

IT has been shown previously' that strain aging can markedly improve the tensile properties of low carbon martensites, especially the yield-tensile ratio, without seriously affecting the ductility. In view of interest in high strength steels, an investigation has been made of the effect of strain aging following tension or rolling on the tensile properties of A1S1 4340 in an attempt to obtain a tensile

Jan 1, 1957

By W. Rostoker, R. P. Elliott

TWO intermediate phases enter into equilibrium with the primary solid solutions of titanium.' The TiMn2 phase was identified by Wallbaum2 as of the C14 type isomorphous with MgZn2. Contrary to Maykuth, et al.,¹ the phase occuring at about the 50-50 atomic proportion has been shown to derive from a peritectoid reaction.:' A 30 day anneal at 900°C of an alloy containing 52 wt pct Mn developed sufficient of the new phase to give a clear and predominant diffraction pattern. The powder pattern was taken in a 14 cm diameter powder camera using filtered Cu Ka radiation. In all, 75 lines were recognized and measured. Interplanar spacing and observed intensities for the first 26 of these are given in Table I.

Jan 1, 1954

By K. A. Natarajan, M. K. Yelloji Rao

Significance of grinding media wear and its effect on chalcopyrite flotation are discussed. Laboratory marked ball wear tests were conducted grinding chalcopyrite ore and quartzite dry, wet, and with collector added during grinding. The effects of oxygen and nitrogen on ball wear were evaluated by the addition of chalcopyrite mineral while grinding quartzite. The effect of dry and wet grinding on chalcopyrite flotation was also studied. Results show abrasive wear is greater in quartzite grinding than in grinding chalcopyrite. Oxygen increases the corrosive wear of high carbon low alloy steel balls in the presence of chalcopyrite ore. Chalcopyrite flotation was retarded due to wet grinding in the presence of oxygen. Though collector reagent increased the media wear, it improved the flotation of chalcopyrite. Probable electrochemical reactions encountered in a grinding mill are outlined.

Jan 1, 1991