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By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3'4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By Wallace W. Wilson

The Cook Ranch Field produces from a very permeable lens of Cook Sand of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The field was discovered in 1926, and has been operated with low pressure gas injection since July, 1927, one of the first such projects in Texas. Cumulative recovery to Dec. 31. 1950, was 14,701,131 bbl of crude oil, an average of 1,013 bbl per acre-ft of oil rection. and 72.5 per cent of the oil originally in place. Analysis of the reservoir performance indicates that grav-ity drainage has been an important factor in the producing mechanism. The high permeability and uniformity of the reservoir were extremely Favorable tor this type of operation. INTRODUCTION The Cook Ranch Field is the largest of a number of relatively small, shallow producing areas near .Albany, in Shackelford County, Texas. This field is one of the first to be operated by gas injection in Texas, and probably is the most successful low pressure gas injection project ever attempted. The field is owned entirely by Koeser and Pendleton, Inc., and Continental Oil Co., and has been operated by Roeser and Pendleton, Inc., since it was discovered. This study has been made possible through the cooperation of Roeser and Pendleton, Inc.. in making availahle a remarkably complete set of records covering all phases of their operations. The purpose of this paper is to present a summary of the history of the operations through Dec. 31, 1950, and to analyze some of the factors which appear to be responsible for the success of the project. Information concerning the physical plant and the early gas injection history has been presented in an earlier paper.' RESERVOIR CHARACTERISTICS production in the Cook Ranch Field is from a large lens of Cook Sand. of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The average dip of the sand body, as shown in Fig. 1. is only about 50 ft per mile to the northwest. The reservoir has an area of 930 acres and contains 15,512 acre-ft of Sand, consisting of about 14.512 acre-ft of produc-tive oil zone. and an estimated 1.000 acre-ft of primary gas-cap. The iso-pachous map (Fig. 2) was prepared from drillers' logs. Recent coring in the field has proven these logs to be quite accurate. The productive limits of the field are defined by shale on all sides but the southwest where a small zone of edgewater was encountered. This water does not appear to have encroached into the reservoir, and water production has been small. A smaller producing area to the south of the Cook Ranch Field also produces from the Cook Sand. but is separated from the reservoir under consideration by a band of shale. The sand consists of well sorted, coarse grained. rounded and subangu-lar quartz fragments. very poorly cemented. The analysis of 46 chip-core samples from two recently completed test wells indicates a range of porosity values between 12.5 and 28.2 per cent. wit11 an arithmetic average of 24.0 per cent. Air permeability values range between 50 and 2,300 md, with an arithmetic average of 1.200 md. The reservoir where cored is a Solid sand body. with no discernible major shale breaks or impermeable streaks. Vertical permeability appears to be of the same magnitude as the horizontal permeability. A core of the Cook Sand was cut ill the smaller field to the south, using lubricating oil as drilling fluid. The connate water content of the sand in this core was found to average about ten per cent, and the porosity and permeability were comparable with the values reported above. No analysis was made of subsurface or recombined hydrocarbon samples,

Jan 1, 1952

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,' Mc Quillan,' Van Thyne et dl.,' and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger' discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95' *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By R. G. Grieves, G. Thodos

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

Jan 1, 1965

By M. R. Tek, R. L. Nielsen

The scaling laws as formulated by Rapoport relate dynamically similar flow systems in porous media each involving two immiscible, incompressible fluids. A two-dimensional numerical technique for solving the differential equations describing systems of this type has been employed to assess the practical value of the scaling laws in light of the virtually unscalable nature of relative permeability and capillary pressure curves and boundary conditions. Two hypothetical systems — a gas reservoir subject to water drive and the laboratory scaled model of that reservoir — were investigated with emphasis placed on water coning near a production well. Comparison of the computed behavior of these par ticular systems shows that water coning in the reservoir would be more severe than one would expect from an experimental study of a laboratory model scaled within practical limits to the reservoir system. This paper also presents modifications of the scaling laws which are available for systems that can be described adequately in two-dimensional Cartesian coordinates. INTRODUCTION Present day digital computing equipment and methods of numerical analysis allow realistic and quantitative studies to be carried out for many two-phase flow systems in porous media. Before these tools became available the anticipated behavior of systems of this type could be inferred only from analytical solutions of simplified mathematical models or from experimental studies performed on laboratory models. To reproduce the behavior of a reservoir system on the laboratory scale, certain relationships must be satisfied between physical and geometric properties of the reservoir and laboratory systems. Where the reservoir fluids may be considered as two immiscible and incompressible phases, the necessary relationships have been formulated by Rapoportl and others.2-5 Rapoport's scaling laws follow from inspectional analysis of the differential equation describing phase saturation distribution in such systems. It will be recalled that these scaling laws presuppose three conditions: (1) the relative permeability curves must be identical for the model and prototype; (2) the capillary pressure curve (function of phase saturation) for the model must be linearly related to that of the prototype; and (3) boundary conditions imposed on the model must duplicate those existing at the boundaries of the prototype. These three requirements seldom if ever can be satisfied in scaling an actual reservoir to the laboratory system because: (1) The laboratory medium normally will be unconsolidated (glass beads or sand) while the reservoir usually is consolidated. Relative permeability and capillary pressure curves are usually quite different for consolidated and unconsolidated porous media. (2) The reservoir usually will be surrounded by a large aquifer which could be simulated in the laboratory only to a limited extent. (3) Wells present in the reservoir would scale to microscopic dimensions in the laboratory if geometric similarity is to be maintained. In view of these considerations, rigorous scaling of even a totally defined reservoir probably would never be possible. The purpose of this paper is to assess the practical value of the scaling laws in the light of the unscalable variables. This has been done by carrying out numerical solutions in two dimensions to the differential equations describing the flow of two immiscible, incompressible fluids in porous media for a field scale reservoir and a laboratory model of that reservoir. While both the reservoir and the laboratory model were purely fictional, each has been made as realistic and representative as possible. The field problem selected as the basis for the investigation was an inhomogeneous, layered gas reservoir initially at capillary gravitational equilibrium and subsequently produced in the presence of water drive. The laboratory model of this reservoir was designed to utilize oil and water in a glass bead pack. The numerical treatment employed was similar to that of Douglas, Peaceman and Rachford6 and it included both capillary and gravitational forces as

By G. T. Smith, R. C. Moyer

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood

Jan 1, 1950

By F. G. Tahmoush, N. J. Grant, E. P. Abrahamson

The effect of grain size on the brittle -ductile transition temperature of pure iron and three dilute Fe-W alloys has been investigated by slow bend tests. The brittle-ductile transition temperature for pure iron increased with increasing grain sizes from 8000 to 500 grains per sq mm where the transition temperature then decreased with further increase in grain size. The dilute additions of tungsten lowered the transition temperature for fine grain sizes, suppressed a reversal of the curve in the coarse grained portion, and raised the transition temperature for this region. The frequency of twin occurrence increased with increasing grain size and decreasing temperature. The object of the present investigation was to re-examine the effect of grain size on the brittle -ductile transition of pure iron and several dilute Fe-W alloys. Current literature normally presents a simple relationship between grain size and the brittle-ductile transition temperature, namely, that the transition temperature increases with increasing grain size. Heslop and etch' have studied the transition temperature of mild steel by V-notch Charpy impact tests for the grain size range between 200 and 6000 grains per sq mm. The result was a linear plot of In 1-1/2 vs brittle-ductile transition temperature, where 1 is the grain diameter. Recent experiments by sipos2 revealed the possibility of a reversal in the slope of the grain size vs transition temperature plot for pure iron; however, his investigation was limited in scope, and the data obtained were insufficient to permit a definitive curve. The present investigation was undertaken in an effort to confirm or extend the grain size effect observed in iron by Sipos. PROCEDURE All alloys were vacuum induction melted, using 99.95 pct Fe containing 0.03 pct 0 and 0.004 pct C. Four ingots were made, ranging from pure iron to iron with 0.035 pct W. The chemical composition of each alloy, after processing, is given in Table I. The four alloys were prepared as 45 lb heats and cast into 4 in. diam by 16 in. molds. They were then extruded into 3/4 in. rods at 1800oF. Specimens for chemical analysis, taken from various positions along the rods, revealed no variation in tungsten content along the length. The extruded rods were reduced to 0.156 in. diam stock by a series of cold swaging operations involving intermediate vacuum annealing treatments. This procedure yielded a final cold reduction in area ranging from 10 to 90 pct. The swaged rods were chemically cleaned, cold pressed to a cross section of 0.10 by 0.18 by 1.0 in. long (2.54 by 4.73 by 25 mm). The specimens were wrapped in iron foil and vacuum sealed (10-4 mm Hg) in quartz. Various heat treatments at temperatures from 700" to 1300oC were utilized to produce grain sizes from 8000 to 1 grain per sq mm. Grain sizes were determined by measuring the average area of grains in a polished section. In specimens with grain size greater than 20 grains per sq mm, the total number of grains in the cross section was counted and then divided by the area to yield grains per sq mm. Grain size was measured both for longitudinal and transverse cross sections. The average of the two measurements was plotted vs transition temperature. An Instron Table Model testing machine was used to determine the transition temperature of specimens tested in three point horizontal bending. The specimen was supported by two 1/4 in. dowels one in. apart. Bending was accomplished with a push rod, the end of which had an 1/8 in. radius. The head speed was 50 in. per min. Temperatures were established through the use

Jan 1, 1963

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By David E. Nicholas

INTRODUCTION In this paper, a numerical process for selecting a mining method, with the emphasis on underground mass mining techniques, such as caving, induced caving, and stoping, is proposed. In the past, selection of a mining method for a new property was based primarily on operating experience at similar type deposits and on methods already in use in the district of the deposit. Then, the chosen method was modified during the early years of mining as ground conditions and ore character were bet- ter understood. Today, however, the large capital investment required to open a new mine or change an existing mining system make it imperative that the mining methods examined during the feasibility studies and the method actually selected have a high probability of attaining the projected production rates. Although experience and engineering judgment still provide major input into the selection of a mining method, subtle differences in the characteristics of each deposit, which may affect the method chosen or the mine design, can usually be perceived only through analysis of measured characteristics. The parameters that must be examined when choosing a mining method include: 1) geometry and grade distribution of the deposit; 2) rock mass strength for the ore zone, the hanging wall, and the footwall; 3) mining costs and capitalization requirements; 4) mining rate; 5) type and availability of labor; 6) environmental concerns; and 7) other site-specific considerations. This paper encompasses a detailed look at the first two parameters since they, plus mining costs, have the greatest impact on the selection of a mining method. The proposed method selection process is for a project where drilling has defined sufficient geologic reserves, but little or no underground development has been done. Since each deposit has its own characteristic geanetry/grade distribution, and rock mechanics properties, mining method selection should be at least a two-stage process. In Stage 1, the deposit is described in terms of geometry, grade distribution, and rock mechanics properties. Using these parameters, the mining methods can be ranked to determine which are most applicable; they can then be considered in general terms of mining and capitalization cost, mining rate, type and availability of personnel, environmental concerns, and other site-specific considerations. In Stage 2, the most likely mining methods are costed out, based on a general mine plan. Mining and capitalization costs are used to determine a cut-off grade fran which a minable reserve can be calculated; economic comparisons can then be made to determine the optimum mining method and economic feasibility. During the mine planning phase of Stage 2, rock mechanics information would be used to provide realistic estimates of underground opening size, amount of support, orientation of openings, and caving characteristics, and open pit slope angles. If ground control or operational problems should be encountered with the methods being considered, modifications could be made. Although planning on paper extends start-up time, it is cheaper to err on paper than to find the error after mining has begun. METHOD SELECTION - STAGE 1 The main purpose of Stage 1 is to select those mining methods which should be considered in greater detail. The simplest way to do this is by defining those characteristics required for each mining method and then determining whether the characteristics of the deposit are suitable. However, no one mining method is so restrictive that it can be used for only one set of characteristics, as indicated by the classification system proposed by Boshkov and Wright (1973). In the mining method selection proposed, geometry, grade distribution, and rock mechanics characteristics are ranked according to their acceptability for ten general mining methods.

Jan 1, 1981

By H. Kenworthy, R. B. Fisher, R. G. Knicherbocker, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2, with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite-type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore. History The occurrence of titanium minerals in the Magnet Cove area of Arkansas was recognized as early as 1890, but it was not until about 1912 that any appreciable prospecting for the minerals was undertaken. At that time drilling was begun, a shaft was sunk, and several drifts were driven, but beneficiation to recover the titanium minerals was not attempted. The only successful mining and milling operation of the Magnet Cove rutile deposit was begun in 1932 by the Titanium Corp. of America and continued until 1942. The ore was washed by means of a rotary scrubber and then deslimed in a drag classifier. The discharge was ground in a rod mill, classified, and tabled to recover a rougher rutile concentrate, which was screen-sized and retabled on cleaner tables. The cleaner concentrates were given a reducing roast, screen-sized, and magnetically separated to produce a finished rutile concentrate. Most of the rutile produced during this period was sold abroad. In 1942, the Titanium Alloy Corp. of Arkansas (a subsidiary of the Titanium Alloy Manufacturing Co. of New York) purchased the property and rebuilt the mill. Subsequently, the plant and property were acquired by the Magnet Cove Rutile Co., Inc., of Little Rock, Ark., the present owners. Very little titanium has been produced since 1942. Although the Titanium Corp. activities yielded enough returns to allow continued operation for approximately 10 years, certain factors must be recognized. These are: (1) production of rutile in that period was during a low in the economic cycle which permitted low-cost operation on a small scale, and (2) a considerable portion of the production was above the water level and no drainage problems existed. Prior to this paper there has been no published report of any mineral-dressing investigation of the lower levels of the ore body. Reference is made in another paper1 to an earlier investigation of Magnet Cove rutile by the Rolla laboratory, in which it is stated that recoveries of 12 to 17 pct of the rutile were obtained. The present investigation was undertaken to improve the known milling processes and to provide adequate metallurgical information about the ore treatment. Titanium Technology The titanium mineral of primary interest in the present investigation was the titanium dioxide, rutile. Rutile is one of the industrial minerals whose annual consumption is relatively small but strategically important. The domestic production of rutile was 7100 tons in 1948. The imports of rutile in the same year were approximately 8000 tons.2 A major use of rutile is in the production of welding-rod coatings, for which a product containing a minimum of 92 pct titanic oxide is desired. Other constituents, such as lime, silica, and sulphur, must be held to a minimum, but hard-and-fast specifications for these elements cannot be drawn. It is necessary to incorporate the rutile in a welding-rod coating, make a sufficient number of test welds, and then determine the tensile strength of the weld metal in the as-welded and stress-relieved conditions. Such a test gives

Jan 1, 1950

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By M. Prats

The effect of a sand-filled vertical fracture of limited radial extent and finite capacity (fracture capacity is the product of the permeability and width of the fracture) on the flow behavior of a cylindrical reservoir producing an incompressible fluid through a centrally located well has been investigated mathematically. The shape of the lines of equal pressure near the fracture is essentially independent of the size of the reservoir, provided that the field radius is of the order of the fracture length or larger. For reasonable values of production rates and of fluid, reservoir and fracture properties, the total pressure drop between the end of the fracture and the well is gelrerally negligible compared with the pressure drop in the reservoir. With regard to production response, the effect of vertical fractures can be represented by the production response of an equivalent or effective well radius. For a high-capacity fracture, the effective well radius is a quarter of the total fracture length, decreasing with the fracture capacity. When invasion effects are simulated by decreasing the width of the damaged zone with distance from the well, the effect of formation damage around a fracture on the production response is not so seriolls as indicated by the literature. This suggests that frac fluids with a conventional filter-loss response are better than high-spurt-loss frac fluids, provided the effective permeability of the damaged zone is the same. INTRODUCTION This paper considers the effect of the fracture capacity, as well as the formation damage which can result from fracture treatments, on the productive capacity of vertically fractured wells. Other publications, notably those of van Poollen,l,2 consider these same effects. In addition to providing more general results for vertical fractures than are available from the liter- ature, the present paper gives the equivalent well radius of fractures having different lengths and capacities and, also, includes pressure distributions in and around the fractures. The effect of a damaged zone around a fracture on the production response was not found to be so great as that reported by van Poollen. 2 This difference probably stems from the fact that we consider a damaged zone which is widest (but is still small) near the well and thins out toward the extremities of the fracture, whereas van Poollen considers a damaged zone having a uniform width for the entire fracture length. Simple, but adequate, equations which describe the effect of these variables on production response are presented (in Appendixes A and B). Thus, results can easily be extended to values of the variables not specifically considered here. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The liquid is incompressible. It is assumed that, after the well is fractured, the cylindrical outer "boundary" is at a uniform potential, provided that it is not too near the fracture. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir).3 Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir described above. If gravity effects are neglected, the flaw behavior in the reservoir will be independent of the vertical position ill the oil sand. This means that the flow behavior in the fractured reservoir can be described by the two-dimensional flow behavior shown in the horizontal cross section of the reservoir, Fig. 2. PARAMETERS The effect of a fracture on the pressure distribution in the fracture itself and in an otherwise undamaged (no skin) reservoir indicates that the pressure distribution is a function of three parameters.

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By G. W. Neighbor, M. S. Abrahams

The actice slip plane in InSb is found to be of the {111} type by using the method of two-tmce anulysis. Measurements of the rotation of the tensile axis with increasing plastic shear strain indicate that the tnacroscopic slip direction is a <110>. Recrystal-lization is first observed at a sheav strain of about 70 pct for a crystal deformed at a temperatzcre of 473° C and at a shear strain rate of 2.90 times 10- %ecc-I; the dislocation density corresponding to this value of the strain is 1 x 108 em-&apos;. At a shear strain of about 170 pct, the recrystallization process is complete. This appears to be the fimt time re-crystallization has heen observed in a semiconductor. V HE operation of the {Hi} glide plane in Ge was first noted by Gallagher.&apos; This finding was confirmed by Treuting who also extended the result to Si. Using X-ray techniques, Treuting3 demonstrated that the macroscopic slip direction in Ge was of the <110> type. The choice of the (111) <110> slip system in Ge is exected since in the diamond-type structure the {Ill7 plane is the plane of highest density and the <110> direction is the direction of closest packing.4 There is little reason to expect that the glide elements of InSb are different from those of Ge, since the zinc-blende structure characteristic of InSb is quite similar to the structure of Ge. With regard to InSb, Allen5 has indicated that the glide plane is the {111} type. There appears to be no quantitative determination of the glide direction, however. The present work was undertaken to establish both the glide plane and glide direction in InSb and also to see if recrystallization occurs at large shear strains. EXPERIMENTAL PROCEDURE Mechanical Deformation. The single crystals of InSb used in this investigation were deformed in uni-axial tension. The tensile axis of the specimens was [145] and the periphery was bounded by (111) and (321) planes as shown in Fig. 1. The metallographi-cally polished specimens were deformed in a dynamic atmosphere of He, using an Instron machine. The tensile tests were performed at temperatures in the range of 300°C to the melting point (525OC) and at shear strain-rates varying between 1.94 X 104 sec-&apos; to 1.94 x 103 sec-&apos;. Additional details concerning the preparation and deformation of the specimens have been presented previously.&apos; Analysis of the Glide Elements. The traces of the active slip plane in both (111) and (321) planes were analyzed according to the usual method of two-trace analysis." The macroscopic slip direction was determined by measuring the rotation of the tensile axis as a function of plastic strain,8 These measurements were made from Laue back-reflection X-ray photographs. The X-ray beam was perpendicular to the (111) plane. A given crystal was used for only one measurement of the rotation of the tensile axis after it had been strained to a predetermined value. Therefore, care was taken at all times to insure that the X-ray beam was parallel to the [Ill ] direction of all the samples. RESULTS AND DISCUSSION Glide Plane. After 3.4 pct plastic shear-strain, at a temperature of 369°C and a shear strain-rate of 1.94 x 104 sec-&apos;, the slip traces on the (111) and (3.21) planes appear as in Figs. 2(a) and 2(b), respectively. The results of an analysis of these glide markings demonstrate that the slip plane is (111). The operation of this plane is expected on the basis of the orientation of the specimen, since glide on this plane and in the [I011 direction will result in

Jan 1, 1962