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By A. J. Griest, P. D. Frost, H. A. Robinson

The flow characteristics and uniform elongation of alpha-beta titanium alloys in the solution-treated condition were shown to be markedly affected by the solution temperature. Two classes of alpha-beta alloys were distinguished, based on the effect of solution temperature on the uniform elongation. Martensitic alpha-beta alloys, which are relatively weakly beta-stabilized, showed decreasing values of uniform elongation as the solution temperature was initially increased. However, after solution-treatment at still higher temperatures in the alpha-beta field, the uniform elongation of these alloys was again high, and often attained its maximum value. Nonmartensitic alpha-beta alloys, which are more heavily beta-stabilized, showed a continuous decrease of uniform elongation with increasing solution temperature. The behavior was rationalized in terms of the alpha-beta ratio and the alloy content of the beta existing at the solution temperature. The data indicate that in commercial practice close temperature control may be required to get maximum uniform elongotion, and hence, maximum potential formability, in solution-treated sheet. Bend-test data also were obtained for the solution-treated conditions. A MOST important objective of current titanium research is the development of age-hardenable alloys with superior formability in the solution -treated condition. Alpha-beta titanium alloys have been shown to be amenable to high-strength aging treatments after solution-treatment in the alpha-beta field.' However, heat-treatment data on the properties of solution-treated sheet, such as uniform elongation, minimum bend radius, and flow properties, which have a bearing on the potential formability, have not been widely available. This paper presents only the most significant results of a research program conducted at Battelle for the Air Force in an effort to develop sheet alloys that can be formed readily as solution-treated and subsequently aged to very high strengths. Data for 10 compositions representative of the more than 25 alloys studied in this program are presented. A primary objective of the paper is to demonstrate the pronounced dependence of the flow characteristics and uniform elongation on solution-treatment temperature. This effect is believed to be vitally important in the commercial heat-treatment of age-hardenable titanium sheet alloys. Experimental Procedures Melting and Fabrication—The nominal and actual compositions, beta transi temperatures, and rolling temperatures of 10 of the 30 alloys studied are presented in Table I. Stock :€or two of the alloys, E (Ti- 8Mn) and J (Ti-6A1-4V) was obtained from commercial heats. The remaining heats, except D and I, were double melted as 10-lb heats in a consumable-electrode furnace. Melting stock was 120 Brine11 hardness sponge. The oxygen and hydrogen analyses spotted throughout the heats indicate the range of interstitial levels resulting from the melting practice used. Heats D and I were melted as 20-lb ingots with the same grade of sponge. These ingots were cut in half and one portion used in the present evaluation. The ingots, which were about 4 in. diam and 4 in. in height, were upset forged and drawn at 1750°F to sheet bar 5/8 in. thick by 2 1/2 in. wide in such a manner that the top of the ingot corresponded to the top of the sheet bar. Slabs of the sheet bar, 5 1/2 in. in length were scalped to 1/2 in. thickness and rolled at the temperatures indicated in Table I to approximately 0.055 in. sheet. Elongation during rolling took place at 90" to the original forged length. The fabrication procedure used is described in some detail since the experimental heats showed considerable directionality in mechanical properties. The rolling procedures for the commercial heats were unknown, but were such as to produce essentially isotropic properties. All heats, as rolled, showed microstructures typical of alpha-beta alloys worked in the alpha-beta field; that is, the structures consisted of equiaxed alpha particles in a beta matrix. Heat Treatment— The effects of solution and aging heat-treatments on the properties of the alloys were evaluated uSing longitudinal and transverse tensile and bend coupons sheared from the sheet. Two or three solution-treated conditions were evaluated for each alloy. In addition, the alloys were also tested after annealing at 1200°F for 4 hr and furnace cooling. The solution-treated and annealed conditions were those in which the alloys might be expected to

Jan 1, 1959

By E. T. Hayes, A. H. Roberson, M. H. Davies

R. F. Dornagala and D. J. McPherson (Armour Research Foundation, Chicago)—I should like to compliment the authors for a workmanlike job in determining the partial phase diagram of a system comprised of two rnetals which are certainly not easy to work with. We are completing work at Armour Research Foundation on an Atomic Energy Commission-sponsored project for the determination of eight zirconium binary diagrams. Work on the Zr-Cr system has been completed and should be published within the next year. For our work, Westinghouse Grade 3 iodide crystal bar served as the zirconium melting stock. Johnson-Matthey, electrolytic chromium, specially treated for oxygen removal, was employed. The overall constitution of the system determined at Armour Research Foundation is in very good agreement with the present work. We found a eutectic at 18 pct Cr and 1280 °C, somewhat lower than the value reported. This temperature was confirmed by thermal analysis, incipient melting studies, and regular isothermal anneals. The eutectoid was located close to 1 pct Cr and 835°C by metallographic analysis of annealed specimens. Maximum solubility of chromium in /S zirconium was 4.5 pct at the eutectic temperature. Chromium solubility in a zirconium was less than 0.28 pct at all temperatures. We found the compound at 53 pct to melt around 1700°C, with an open maximum, but determined its crystal structure to be hexagonal close-packed (MgZn, type). The lattice parameters were in excellent agreement with those determined by Wallbaum in 1942. The diagrams are in substantial agreement, and .part of the differences are undoubtedly due to the use of different zirconium melting stock. M. K. McQuillan (Birmingham, England)—I read this paper with a great deal of interest, as it covered the same field as some work of my own.' There are a number of points in the present paper on which I would like to comment. First, I should say that I, too, used zirconium prepared by magnesium reduction of the tetrachloride and electrolytically prepared chromium, and melted the alloys in a Kroll-type arc furnace. The purity of my alloys should, therefore, be comparable with the purity of those of the present authors, and any differences in our observations would not be expected to be attributable to this cause. The differences between my observations and theirs concern the presence of the eutectic, the temperature of the eutectoid, and the melting point of the compound. I would be very much interested in any further evidence the authors may have for the occurrence of the eutectic at 1380°C. During the course of my work I noted that a number of my alloys containing 60 to 90 pct Zr melted at about 1400 °C, and for a time assumed that a eutectic occurred at this temperature as described in the paper. On further investigation, however, I found that the structures of the as-melted alloys could not be made to fit in with this interpretation of the system. If a eutectic exists in this region of the system it would be expected that the as-melted alloys would show the usual type of cast structure, i.e., dendrites of the compound plus eutectic. This, however, does not occur, as may be seen from Fig. 9. The compound seen there is not dendritic in form, and the remaining material is by no means certainly eutectic. It may be argued that a compound such as ZrCrl would not form dendrites but would tend to crystallize in geometric shapes. In this case, however, I have evidence to the contrary, as on the chromium side of the compound, where a eutectic occurs at about 1545"C, the compound formed from the liquid takes on a conventional dendritic form, and the eutectic is observed in the interdendritic spaces in the usual way. There is no reason to suppose that the compound would behave differently in an alloy lying on the zirconium side of the compound composition if a eutectic existed there too.

Jan 1, 1953

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard's law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever's4 work on iron. Barnett's7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By J. B. Evans

Maintaining overall optimum profitability at a mine site necessitates constant reassessment of operating strategies. In essence, each strategy is a particular combination of envisaged capital expenditure, income flow and elapsed time. Selecting a strategy, based on profita¬bility potential requires each contemplated strategy being subjected to discounted cash flow analysis; even with a computer such analysis can be cumbersome. The chapter discusses a 'shortcut' technique which assigns profitability rankings to alternate strategies and iden¬tifies those aspects of a. strategy which impact heavily on profitabil¬ity. This technique can yield quick assessments of sufficient accuracy for many operating strategy decisions. taken on site at on-going mines.

Jan 1, 1978

POSITIONS VACANT (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons.) Two metallurgical chemists for permanent positions in Siberia; one man to have charge of laboratory dealing with the products of a mill working silver-lead-zinc ores, the other to have charge of laboratory in connection with smelting these products. Established camp; living conditions and climate good. Married men preferred. No. 57. An electro-metallurgist for small zinc plant now under construction. Moderate salary to start but likelihood of substantial increase if plant proves successful. No. 58. Assistant engineer in office of consulting engineer for large mining and smelting company. Man desired with technical education and broad experience in mechanical line in connection with mining and smelting operations, capable of taking charge of office and drafting room. No. 59.

Jan 1, 1916

By W. L. Falke, A. A. Cochran

Vast deposits of low-grade manganese ore exist in the United States, yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.1 A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the U.S. Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.2 Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4

Jan 3, 1967

By Charles H. Hopkins, J. M. Lohr

A commercial development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common types of glass under consideration varies from 2.7 to 10.4 X 10-6 per degree Centigrade, over the range 20" to 400' C. For reference, the t,hermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1939

By Charles H. Hopkins, J. M. Lohr

A commercial development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common types of glass under consideration varies from 2.7 to 10.4 X 10-6 per degree Centigrade, over the range 20" to 400' C. For reference, the t,hermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1939

By Macelwane

WHAT characterizes a geophysical engineer and sets him apart from all other engineers? This is a question that is important not only for accrediting purposes but is assuming increasing importance in the licensing of professional geophysical engineers by state boards. What is the basis of distinction of one type of professional engineer from another type is answered in part by the need which brought each type into being precisely because that need could not be satisfied by pre-existing types and which nevertheless demanded the special outlook, training, and abilities of an engineer. The need which called for the civil engineer was the adaptation to the tasks of civilian life of the capabilities developed by the military engineer for the design and construction of roads, bridges, dams, earthworks, military buildings, and other structures and of mechanisms required by military operations.

Jan 4, 1954

By Charles H. Hopkins, J. M. Lohr

A COMMERCIAL development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge' of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common [ ] types of glass under consideration varies from 2.7 to 10.4 X 10-s per degree Centigrade, over the range 20° to 400° C. For reference, the thermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1938

By D. A. Dukelow

By using the U. S. Steel oxygen sensor to measure the oxygen content of the steel, deoxidation practices have been developed for silicon-killed fine-grain steel produced by the basic oxygen process. Measurements of oxygen content taken at final turndown are related to the amount of the aluminum addition to the ladle necessary to obtain the desired aluminum analysis for proper grain refinement. In comparison with heats deoxidized by the standard approach, which is based on carbon content, the heats deoxidized according to the oxygen-sensor-based schedule showed a 25 percent decrease in variability from the desired aluminum content. As more heats of a particular grade are made, it is expected that improved quality will result in decreased rejections and better analysis control. Sensor-based deoxidation schedules are also being developed for semikilled, rimmed, and capped steels.

Jan 1, 1972

For some years MINING ENGINEERING has published abstracts of the articles appearing in each issue and also of the Transactions papers published in the Quarterly. Beginning this month, a list of key words is being given with each abstract as an aid to indexing the articles for ease in retrieving them when they are needed. The value of a home or office system of indexing and retrieving technical articles is hard to over-estimate. How often is it that a technical problem comes up and someone says: "Oh yes, I've read something about that." Many hours can be expended tracing down that nebulous source. A modest indexing and retrieval system will save those tedious hours, and the person who is able to produce technical documents when they are needed will achieve an enviable status for being on the ball.

Jan 1, 1964

By D. J. Crouse, W. D. Arnold

The potential behavior of radionuclides released in an underground nuclear detonation to fracture copper ore for subsequent in-situ leaching and copper recovery was studied with regard to contamination of the copper product and hazards to operating personnel. The laboratory test results indicate that only small fractions of the radioactive fission products would be dissolved on leaching the ore. Tritium (as tritiated water) would be the dominant radionuclide in the circulating leach liquor, assuming use of a fusion explosive. The test results showed solvent extraction to have important advantages over cementation for recovering copper from the leach liquors. While the radioactivity of the copper metal product produced by either method should be extremely low, the solvent extraction process provides a more effective separation of copper from the radioactive contaminants and entails fewer radiation protection problems. For these reasons it is the preferred process.

Jan 1, 1976