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By D. C. Hilty

C. E. SIMS*—This is a most interesting and important paper. It is important from two standpoints. First, it has as-spects of being highly accurate and therefore extremely useful to the operating man in showing how far he can go in oxidizing carbon from a steel bath while retaining chromium and the effect of temperature on this limit. Fig 5 is undoubtedly the highlight of the paper, and in checking it against available data, it seems capable of predicting actual results. The other important aspect is the apparently significant fact that reactions within a steel bath, such as between carbon and an oxide, are homogeneous reactions which do not require equilibrium with an external phase. In this case, it seems obvious that the reaction and the equilibrium established were between dissolved carbon (or carbide) and dissolved CrO. The classic reaction which requires equilibrium with solid Cr2O3, did not fit the data. It was recognition of this principle that made Fig 5 possible. G. R. FITTERER*—It might be in assuming the CrO is dissolved in the metal that you are actually approaching the correct factor for activity. If that is true and if the percentages that were used represent an equilibrium constant, this would mean, in effect, that the minimum temperature at which chromium would be reduced by an equivalent percentage of carbon would be about 2400°F from your equation. I believe that is in line with my experience particularly if you deal only with low percentages. J. CHIPMAN†—The author in discussing the equilibrium of the reaction offers two choices of explanation. One postulates an effect of chromium on the activity coefficient of carbon; it would require perhaps more data than are available to us at the present time to test this thoroughly. The other postulate which he offers is a reaction with CrO. This explanation is consistent with physical and chemical principles provided that a solid phase CrO is present, and that is essentially what he is postulating. If that oxide were present one would expect and, I think, almost require the kind of results that he obtained. The weakness of that postulate lies in the lack of confirmatory evidence regarding the presence of solid CrO as such. This should offer an interesting subject for further study. It seems a pity that the theoretical arguments revolving around CrO should have obscured for a moment the very real excellence of this paper. E. CARTER*—I think there is a problem that presents itself in practical application where the metal temperature is from 3200 to 3300 and the temperature desired in pouring is considerably less. B. M. LARSEN†—I get the impression from some of the work that was done earlier that there is probably a localized zone of high temperature at the slag metal interface which effects the removal of the carbon. Without that I wonder if the effect is possible to have a localized superheat and an equilibrium there favorable to low carbon content and

Jan 1, 1950

By R. S. Hoch, Roy A. Bobo

Maintenance of desirable plastic flow properties of weighted drilling muds may be greatly simplified by use of centrifugal classification to control the drilled solids content. The new application of a decanting type centrifuge to separate and reject the low density solids from the weighting material results in a drilling mud of greatly improved quality with lower values of yield and rigidity. Its practicality and economy has been proven in field operation. The degree of separation of light and heavy solids is not limited by the machine, but by the particle size distribution of the solids in the mud. Removal of the low density component of drilling mud that makes chemical treatment necessary permits a marked reduction in chemicals. The main uses of the centrifugal process are the treatment of muds while drilling, the reclaiming of discorded muds, cleaning up of workover muds, and the reduction in lime content of mud for completion. INTRODUCTION Drilling mud in any circulatory system is made viscous and difficult to pump by gradual accumulation of drilled solids which pass through the shale shaker and are continually reground. In a weighted mud containing a large proportion of barite by volume, the amount of drilled solids that may be tolerated is greatly reduced. Much effort has been expended to control by chemical treatment the effects of such solids. Though chemical treatment is quite effective, the time eventually comes at deeper depths after enough drilled solids have entered the system when a portion of the mud must be discarded and replaced with water and more weighting material. Once begun, this process is generally continued at frequent intervals with resultant high maintenance costs. At the termination of drilling, mud highly contaminated with light solids and spent chemicals is poorly suited for completion operations.' It is likewise limited in utility for other drilling operations. This investigation was conducted for the primary purpose of determining an acceptable mechanical means of removing the lightweight solids from weighted drilling muds in order to maintain viscosity at a minimum. A decanting type of centrifuge was selected from the various possible methods of mechanical separation. The centrifugal process has been employed in this country for this purpose in central mud reclamation systems in California in earlier years. It also was used for treatment of weighted muds on the Gulf Coast.' In more recent years only sporadic attempts have been made to employ it in the field on weighted muds. DISCUSSION OF PROCESS Selection of Apparatus Two factors favor mechanical procedure for the separation and removal of drilled solids or clays from the mud circulatory system. First, the greater specific gravity, 4.1 to 4.3, of the barite would promote more rapid settling than the clays whose specific gravity range is from 2.5 to 2.7. Second, the relative coarseness of the barite particles also facilitate faster settling of this phase. A decanting type of centrifuge was preferred for this process over other possible methods for these reasons: 1. Requires no costly additives or excess dilution. 2. Centrifugal force affords greatly accelerated separation as compared to gravity.

Jan 1, 1955

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By S. W. Churchill

A digital computer was used to obtain an exact numerical solution for the transient behavior of the insulation and earth adjacent to an isothermal, submerged flat surface for a single set of parametric values. Comparison of the computed results with analytical solutions for limiting conditions revealed that a complete and general solution for all parametric values could be constructed from these limiting solutions. Complete and general solutions for insulated spheres and cylinders can also be constructed from limiting solutions. The procedure is illustrated in part for an insulated spherical tank. The heat flow was found to fall rapidly to a pseudo-steady state; after some time, it then decreased slowly to zero for a flat plate and cylinder, and to a low steady-state rate for a sphere. The accumulative heat flow during the initial falling-rate period may be a significant fraction of the heat flow during the entire first year. INTRODUCTION Underground storage of liquefied natural gas and liquefied petroleum gas has received considerable recent attention. The rate of heat flow from the earth to the storage cavity and the resulting temperature field in the earth are important factors in the technical and economic evaluation of such storage facilities. The objective of this paper is to indicate how complete solutions can be developed for the transient flux and temperature field for various geometrical configurations. The representative properties and dimensions, and the resulting parameters utilized in the illustrative results, are indicated in Table 1. The results presented herein are for dry earth. The effect of the latent heat of solidification of water in the soiI will be described in a subsequent paper. The temperature field in the insulation and earth is determined by energy balances, boundary conditions and initial conditions. The physical problem can be described mathematically with virtually no idealizations insofar as physical properties are known. It appears possible to solve the equations by numerical integration on a high-speed digital computer for any geometrical configuration and conditions. For complex situations, however, the computations are expensive and the results are highly specific. Analytical solutions have been developed for a few simple but important geometrical configurations and conditions, including one-dimensional heat transfer from (or to) earth at an initially uniform temperature to (or from) flat plates, spheres and circular cylinders. The solution for an insulated flat plate has also been derived but is in the form of a slowly converging series involving taklated functions. It was planned to use a computing machine to evaluate this series for a number of representative conditions. However, upon examination of the results of preliminary computations it was discovered that a complete, general and accurate solution could be developed by interpolation between several much simpler solutions for limiting conditions. This technique then was used to develop a a complete solution for an insulated sphere. The equations presented herein are derived in Carslaw and Jaegerl and other books on applied mathematics, or they are simple extensions of these previous results. Hence, all derivations are omitted. Emphasis is instead placed on the results and their

THE discussion of this topic at the Open-hearth Conference at Detroit on Nov. 3, 1927, was opened by statements of the general principles involved, made by manufacturers of molds. Because of their general interest they are printed below. WILLIAM HAIL RAMAGE,* Hubbard, Ohio.-I did not come prepared to read a paper, thinking. the most I would be called upon to do would be to make a few, remarks by way of discussion. A number of our friends have pre-viously asked questions. similar to this which really does not permit a direct "yes" or "no" answer. If I may he pardoned for so doing, I believe it advisable to discuss rather what we consider the principal factors which in-fluence mold life. I think possibly a little undue weight has been given to the subject of the analysis of the metal. For the last eight years we have spent a lot of time, effort, and money investigating this very problem from a chemical, physical and microscopic standpoint. We have had the benefit of complete records and history of over 100,000 molds in service at a variety of plants and over long periods of time. Obviously, I cannot be so specific that I should divulge information that is really a trade secret. In our opinion the principal factors influencing mold life are: (1) design of the mold; (2) process of manu-facture, including workmanship; (3) care in the steel plant or what might be termed "the use or abuse" in the steel plant; (4) the analysis of the iron and the physical con-dition of it. Under normal conditions these factors are of importance in the order named, although in specific cases they might be rearranged in any order you choose. For instance, the best mold made can be destroyed in one or two pours by subjecting it to certain conditions which are occasion-ally met in steel plant practice. Obviously, in that case, nothing else matters but that one item. On the other hand, I have seen molds made of such a terrible design that it was a foregone conclusion it would have to be broken after the second pour of the ingot to get it out. In that case, nothing but design mattered. As to the effect of process of manufacture, let me cite a case. Some years ago there were two batches of molds sent to a certain company. They were the same sized molds, used under the same conditions and in the same kind of service. There were, 20 molds in each batch. The second batch sent gave ten times the life of the first batch. It is true that the design was changed a little, but not very much, and it was not. a bad mold to begin with. It is possible that the iron may have been better in the second consignment but not very much. In my opinion, it is con-servative to say that of the 900 per cent improvement in life, 5 per cent was probably due to better iron, 25 per cent to better design and the remaining 870 per cent to process of manufacture and workmanship.

Jan 2, 1928

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By John McGhee, Jack Newcombe, M. J. Rzasa

A series of water floods was made on laboratory prepared unconsoli-dated sand columns to study the effects on oil recovery of the solid-water-oil contact angle, the oil-water interfacial tension, flood rate, and oil viscosity. A procedure was developed for treating silica sand with silicone polymer to produce surfaces of varying degrees of wettability as evaluated by measuring the contact angle on a flat silica plate that had been simultaneously treated with the sand. Fluid interfacial tensions were changed by the use of surface active agents in the flood water. Water-wet, oil-wet, and intermediate wettability systems were studied at high and at low values of interfacial tension, at several flood rates, and with oils of different viscosities. For both oil-wet and water-wet systems and a low viscosity oil, recoveries were functions of the oil-water interfacial tension; also, increase in flood rate resulted in increased oil recoveries. High interfacial tension floods were more efi- cient than low interfacial tension floods on water-wet systems, while low interfacial tension floods were more eficient on oil-wet systems. Intermediate or neutral wettability systems were less sensitive to rate of flood advance and interfacial tension than either oil-wet or water-wet systems. The eflects of surface forces on oil recovery for high viscosity oils were not so well defined as for low viscosity oils. INTRODUCTION Reservoir rock surfaces vary in their wettability1, some being water-wet while others are apparently oil-wet. The factor of wettability enters into reservoir performance in both primary and secondary recovery, and into laboratory measurements of capillary pressure, connate water saturation, and relative permeabilities.' In theory, the degree of wettability is measured by the contact angle for the system solid-water-oil. A water-wet system is defined as one in which the advancing water contact angle is less than 90". An oil-wet system is one in which the advancing water contact angle is greater than 90°.3 The surface forces in a solid-water-oil system are related by the Young-Dupree equation as follows4: These surface forces are commonly expressed as the difference in adhesion tension, or the product of the water-oil interfacial tension and the contact angle. If the contact angle is less than 90°, the adhesion tension difference is positive and oil displacement by water from a solid surface will be spontaneous and favored by a high oil-water interfacial tension. If the angle is greater than 90" the displacement will not be spontaneous but will require less energy the lower the oil-water interfacial tension. The contact angle and interfacial tension also appear in the capillary pressure equation5: PC = 2ocosejr .... (2) The quantity cos was used by Rapoport and Leas6 s a factor in the generalized form of their "sealing coefficient." Warren and Cal-houn' presented the results of cos on oil recovery in oil-wet systems and correlated their data using a "scaling coefficient" suggested by Jones-Parra and Calhoun.8 The "sealing coefficients" were advanced to help correlate the effects of the variables influencing oil recovery by

Jan 1, 1956

By Parke A. Dickey, Robert B. Bossler

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

By Richard F. Hinds, F. O. Reudelhuber

Application of the conventional depletion drive calculation methods to volatile oil reservoirs results in erroneous estimates of ultimate recovery. In view of the increasing number and importance of volatile oil reservoirs, a special technique has been developed which will result in more realistic predictions using laboratory data obtained from reservoir fluid studies of a specific type. The experimental data are designed to permit continuous material accounting and, therefrom, provide the hy-clrocarbon composition of both the flowing oil and gas phases. The resultant well-stream composition data are then used directly in surface recovery calculations utilizing equilibrium ratios. A step by step procedure, specifically designed for routine use by the practicing reservoir engineer, is presented in an appendix. An actual study performed on a deep Mid-Continent reservoir is used ay an il-lustrathe example. INTRODUCTION It has been a practice for many years to utilize the conventional ma- terial balance methods in conjunction with relative permeability concepts for the prediction of recovery from solution gas drive reservoirs.' Those who have performed such calculations recognize that compromises of several types are necessary in order to reduce the calculations to a reasonable degree of complexity. The most serious assumption involved results from the necessity of treating the produced oil and gas as separate fluids, independent of each other in their behavior. It is further assumed that the gas which is evolved in the reservoir as a result of pressure decline will not yield liquid upon the reduction of pressure and temperature resulting from production through surface equipment. Although these shortcomings have been recognized,' it has been difficult to attempt refinement of calculation procedures since the laboratory data available normally were not of the proper type or extent to permit such calculations. Three general procedures have been available for depletion drive calculations when laboratory fluid data are of the conventional type. Differential Procedure The most simple, and most widely used, method requires use of the formation volume factor and gas sol- ubility data obtained from a differential liberation performed at reservoir temperature. This procedure ignores the differences existing between the fluid behavior in the reservoir and its behavior as it is produced through surface separation equipment. The errors introduced are not serious when dealing with very low volatility fluids and this method may be utilized if the laboratory data indicate only slight differences between the differential data and the flash data obtained from separator tests. Modified Differential Procedure This method was developed when it became apparent that medium volatility fluids evidenced a wide difference between the flash and differential data. The differential data are adjusted by changing from a residual oil basis to a stock tank oil basis. All that is required is multiplication of the differential data by the ratio of residual oil to stock tank oil relative volumes existing for the original reservoir fluid at the determined saturation pressure. This procedure generally results in increased calculated ul-timate recovery; however, such results should be viewed critically. Upon examination it may become apparent that the results are influenced by errors in reservoir liquid

Jan 1, 1958

By W. A. Backofen, G. Mayer

Single crystals of iron, copper, and a Cu-7 wt pct A1 alloy were pulled through conical dies to simulate the constraint in a polycrystalline aggregate undergoing axisymmetric reduction. With Taylor-type hardening, dependence of the drawing stress, od, on the Taylor orientation factor, M, is predictable from the polycrystal stress-strain curve; in particular, for a power-law relationship, it should follow that d log od/d log M = (1 + n). A first-order agreement with analysis was found in the data from iron. For copper, the implied n from the observed d log od/d l°g M was -0, while for Cu-7Al it was negative. The trend was in the direction of random polycrystal behavior. Thus the idea of hardening only in response to the amount of prior slip loses validity as stacking fault energy (SFE) is lowered. Two possible explanations have been suggested: as stacking fault ribbons are widened, barriers from dislocation reactions become increasingly effective in dispersing slip and reducing the orientation dependence of the total glide strain dm that appears in alternatively, or conjointly, the polyslip shear stress, 7, acquires an orientation dependence of a kind which has the same leveling effect on M. The problem of relating the strain hardening of polycrystalline material to that of an isolated single crystal is still largely unsolved. In a new experimental approach from recent work, single crystals of different orientations have been deformed under the constraints found in an aggregate while measuring their deformation resistance. Procedures have involved drawing cylindrical crystals through conical dies1 and compressing slab-shaped crystals in plane strain.2'3 Predictions for the outcome of such experiments were made first by Taylor~ and later, in more general form, by Bishop and Hill.5'6 Taylor's example was the axisymmetric extension of an fcc crystal slipping on the usual {111}(110) systems or, equivalently, a bcc crystal undergoing 'kestricted" slip on {110}(111). In his solution, the deformation work supplied was equated to that dissipated internally in slip on all active systems. With o the single applied tensile stress, dc the resulting axial strain, and dyT the total glide strain on systems operating at resolved shear stress, 7: The orientation dependence of M was found by minimizing dyT for each orientation while activating five independent systems, Fig. l(a).? The Bishop and Hill analysis, based on a principle of maximum work, leads to essentially the same conclusion; the need for at least five active systems is recognized in the finding that either six or eight are actually brought into operation. The mean value from the entire stereo-graphic triangle in either case is M - 3.06. More recently, Hutchinson8 made a Taylor-type analysis for pencil glide in a bcc structure, from which piehlerg prepared Fig. l(b) as the counterpart in Fig. l(a); here M = 2.75. The obvious weakness in such analyses is the indifference to slip-system interactions. A condition of what might be termed "independent"

Jan 1, 1969

By Douglas A. Karvonen

INTRODUCTION Although the economy in the Province of Saskatchewan has historically been agriculturally oriented, a major source of wealth has been realized through natural resources such as petroleum and natural gas, coal and uranium and since the 1960's - potash. Potash or potassium chloride, in the form in which it is presently produced in Saskatchewan, is used primarily as fertilizer, a source of potassium, one of three essential elements required for healthy plant growth, with about 5% of production sold to the chemical industry for use in such products as soap and liquid detergent, glass and ceramics, textiles and some pharmaceuticals. Saskatchewan is estimated to have approximately 40% of known world potash reserves and its ten active mines account for some 25% of annual world production. POTASH CORPORATION OF SASKATCHEWAN In an effort to guarantee a fair and lasting economic benefit to the Province of Saskatchewan, the Potash Corporation of Saskatchewan (PCS) was created on February 4, 1975 through an Order-in-Council under the Crown Corporation's Act and later on April 1, 1976, the Potash Corporation Act provided for its continuation. PCS was given the mandate to acquire ownership of a significant portion of the potash mining capacity in Saskatchewan and to establish an organization capable of operating the facilities, marketing the product, and conducting all of the other activities necessary for a successful corporation competing in the world potash industry. The corporation is the largest potash producing and selling organization in the Western World - or third largest in the world. (See also Figure 1). PCS through its wholly-owned subsidiary, PCS Mining, has acquired a whole or partial interest in five geographically distinct producing properties or divisions, representing today more than 40% of Saskatchewan's potash producing capacity. The acquisition of each division was followed by a program designed to exploit and maximize the particular opportunities at each minesite for increased production. To that end, PCS Mining has taken an active lead in expanding to meet future demand and has implemented expansion programs at all properties except for its Esterhazy Division where it has a long-term processing agreement with International Minerals & Chemical Corporation (Canada) Limited. Through its wholly-owned subsidiaries, PCS Mining, PCS Sales and PCS Transport, this provincial crown corporation has the ability to operate as a producer and marketer of Saskatchewan's potash. In certain instances PCS, the parent company, assists in the financing of various projects undertaken by the subsidiaries and in other cases the subsidiary involved arranges its own financing. POTASH RESERVES As a background to the specific issue of financing, it is helpful to describe briefly the nature of the deposit which supports the industry - our collateral, if you like. The potash beds underlying Saskatchewan are sedimentary rock deposits formed by the gradual evaporation of an inland sea during the Middle Devonian period roughly 400 million years ago. Now known as the Prairie Evaporite, this formation stretches from North Dakota and Northeast Montana through Southern Saskatchewan into North-Central Alberta. These beds lie at mining depths ranging from 950 - 1000m (3,000 ft) below the surface, where conventional mining methods can be used, and to 1,650m (5,000 ft), where solution mining must be

Jan 1, 1985

By P. F. Gnirk, J. B. Cheatham

An experimental investigation has been made to study the effects of tooth angle and confining pressure on the force required for indentation of dry rock samples under confining pressure. In these experiments static single-tooth indentations were made on two standstones, a limestone, a schist and a slate under confining pressures of 5,000 to 15,000 psi. Sharp wedge-shaped teeth with included angles ranging from 30°to 105°were used. In all cases the force-displarenzent curves are approxinlately linear for rocks tested under confining pressure, as contrmted with the discontinuous curves obtained for silnilar rocks at atmospheric conditions. Photonzicrographs of thin sections through the craters indicate very little evidence of chip formation during indentation. In general the experimental data lie between calculated values for perfectly rough and perfectly smooth tooth-rock interfaces. INTRODUCTION The variables associated with ctrilling at depth are numerous and, in many instances, are not easity isolated and controlled. Also, many of these variables are interdependent; however, if the variables which are sufficiently independent of each other are held constant and are appropriately introduced, the dependent variables can be more easily studied and evaluated. It is the purpose of the present investigation to study experimentally the simplest case of bit tooth-rock interaction. In essence, the experiments have involved the static loading of sharp wedge-shaped tools on the surfaces of effectively semi-infinite dry rock samples subjected to confining pressures. During this investigation the following quantities have been maintained constant: 1. Pore pressure: atmospheric (i.e., the rock is dry). 2. permeability: although the rocks may be permeable, they are "jacketed" in such a manner that the fluid is not permitted to flow through them. 3. Temperature: 75F. 4. Rate of loading: essentially static (approximately 0.002 in./second). 5. Bit tooth: a sharp wedge-shaped tooth loaded normal to the rock surface. 6. Rock surface: smooth and flat. 7. Drilling fluid: hydraulic oil. In addition to the above conditions, the rock surface was free of a layer of cuttings. There was no indexing to previously indented surfaces, and the influence of corners of the borehole was neglected because the rock samples were effectively semi-infinite. The following quantities have been varied, and the resulting effects have been studied: 1. Rock a) Type (e.g., limestone, sandstone, etc.). b) Mechanical properties ) Necessarily dependent c) Porosity on type of rock. 2. Bit tooth (included angle of wedge-shaped tooth). 3. Depth of penetration. 4. cobfining pressure. On the basis of laboratory experiments which have shown that many rocks exhibit ductile behavior at confining pressures corresponding to depths usually reached during drilling,'.' a theory has previously been advanced which predicts the force required for penetration by a single sharp wedge tooth into a ductile* material.' The material is assumed to be isotropic, homogeneous and rigidly plastic (no elastic deformation) and to obey the Coubomb yield criterion (Figs. 1 and 2). Equations governing the force required for penelration are given for two extreme cases:** 1. A smooth, perfectly lubricated tooth-rock interface (fridionless boundary), in which the solution gives a minimum value for the penetrating force: in which F = force of the tooth, b = length of tooth edge,

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By Leo F. Reinartz

Part III of a four-part series on the history of steelmaking in the US, describes furnace developments, improvements during the last few decades, and the contribution of the AIME. THE invention of the dolomite machine was a great boon to the open-hearth furnaceman. By speeding up bottom making, it helped to increase tons per hour and decrease cost. The first homemade unit was built and operated before 1925 at the South Side works of Jones & Laughlin Steel Corp., Pittsburgh The first commercial machine, similar to those known today, was built for the Donner Steel Co., Buffalo, N. Y., in 1925. Heavy slab buckstays, 6 in. by 15 in., supplanted lighter I-beam buckstays as furnace framework in the middle 1920's. They greatly improved the rigidity of the furnace binding. Although the first sloping back wall had been in- stalled prior to 1920 on a small basic open-hearth foundry furnace at Columbus, Ohio, the impetus to install such back walls universally in ingots shops came after S. Naismith installed the first one on an open-hearth furnace at Illinois Steel Company's South works in June 1924. Before that event, back- wall life had already been improved somewhat by the use of chrome rock or metal-encased basic brick. Here again, these changes heralded major for- ward steps in furnace design, decreased costs, in- creased production, and improved safety and working conditions on the back standing of the furnace. Fuels Up to 1930, a number of different kinds of fuel were used to melt and refine steel in American open hearth furnaces. During World War I, powdered coal was used in a few plants as an open-hearth fuel, but because of the high sulfur and ash content in the coals, many operational difficulties arose. There were also dust, explosion, and accident hazards, so that after the War its use was discontinued. In some steel-manufacturing centers, natural gas was available as a fuel and gave good performance. In most steel-manufacturing centers, operators had to rely on producer gas made from bituminous coals in producer gas houses. Low-sulfur low-ash, high-fusion coals required for the manufacture of such gas were not readily available. The quality of producer gas was uncertain. The gas had to be pre-heated. Maintenance problems connected with the use of this fuel were serious. Tons per hour per month was unsatisfactory. Although petroleum had been first discovered by Edwin L. Drake at Titusville, Pa., in 1859, it was not until the early 1930's that heavy fuel oil residues for open-hearth use began to appear on the market. They were cheap; the calorific value was high, and it was not necessary to pass this fuel through the checkers to preheat it. Various plants began to use such oil as an open-hearth fuel. Others used it in combinations with tar, coke-oven, and/or blast-furnace gases. Because of its low calorific value, blast-furnace gas had to be preheated in the checkers. These fuels were cleaner and more dependable than producer gas. The dirty gas house adjacent to the open-hearth shop was no longer needed, and

Jan 1, 1961

By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.' The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By D. W. Fuerstenau, D. A. Sullevan

In the experimental work for this comparison of wet and dry grinding, it was found that the size distributions for wet grinding operations are characterized by a constant value of the distribution modulus, (a; whereas, for dry grinding the distribution modulus decreases slightly with increased size reduction. Wet grindability seems independent of the weight of material in the mill while dry grindability depends on weight. Experimental data and eqmtions for each process are presented for noncleavable isotropic material, for cleavable or material in which there is some form of internal stress, and for energy consumption. The equation ED/EW=BK-? (where ED and Ew are, respectively, energy for wet and dry grinding, k is the size modulus, and B and ? are constants) was found to give the ratio of energy. Dry grinding is generally considered to require more energy than wet grinding. Taggart' states that power consumption in wet grinding ranges from 60 to 90 pct of that required for dry grinding. Bond' states that dry grinding requires one third more power than wet grinding. It is interesting that Rose and Sullivan' note this same difference in power required for wet and dry grinding, but they state that on purely mechanical grounds it is difficult to see any great difference in fundamental principles between wet and dry milling, since dry milling may be regarded as wet milling with a fluid of low viscosity (i.e., air vs water). Yet it must be the viscosity of the fluid that is responsible for the differences between wet and dry grinding. Probably the most comprehensive investigation comparing wet and dry grinding has been that made by Coghill and Devaney. They compared the grind-ability of both chert and dolomite in a 19x36-in. batch ball mill under both wet and dry conditions. In these tests the weight of ore in the mill was varied from 35 to 200 lb and each grinding test was carried out for such period of time that the amount of -200-mesh material in the product was essentially the same for each test with a given material. Cog-hill and DeVaney's data for the grindability of dolomite, which are reproduced in Fig. 1, show that a comparison between wet and dry grinding is com- plex. The comminution of a material by a wet grinding method is characterized by a constant grindability over a wide range of mill loadings. Since grindability is the weight of material comminuted per unit of energy expended, it is equivalent to (w)/ (p)(t), where W is the weight of material being ground, P is the power, and t is the grinding time. In the case of wet grinding, the grindability of dolomite in the Coghill and DeVaney experiments was 0.546 * 0.009 ton per hp-hr when the load of dolomite in the mill ranged from 50 to 200 lb. On the other hand, for dry grinding no such simple relationship was found to exist between power, time, and weight of material in the mill. Dry grinding efficiency appears to depend greatly upon the amount of material within the mill. When the mill contained

Jan 1, 1961

By J. E. Pavlick, A. G. Guy

The total creep of tin alloys containing antimony in solid solution was observed to decrease with increase in antimony content. However, near the solubility limit an anomalous maximum in deformation was. found, in agreement with similiar observations by Bochvar. IT has long been recognized that alloys may deform more rapidly under stress if there is a tendency for a phase change or other structural change to occur simultaneously. However, the phenomena involved are complex and in some instances the opposite effect, strengthening, may result.' This area of research has not attracted much interest in the western world, and although Russian investigators have studied it for the past 15 years their work has not received due attention here. Recently diametrically opposing views on one aspect of this problem have been espoused by two Russian investigators, Kornilov and Bochvar. The question is this: in certain binary alloys tested in creep at the temperature where the solute is at the limit of solid solubility, does the incipient formation of the second phase strengthen or weaken the alloy? Korni-lov's arguments in favor of strengthening were presented at the 1954 Symposium at the National Physical Laboratory, =Creep and Fracture of Metals at High Temperatures.The most recent statement of Boch-var's theory of weakening is in Oding's new book on creep and rupture.3 Although Bochvar agrees that strengthening occurs in some alloy systems, he argues that in certain alloys an anomalous weakening is observed. However, the extensive work of Korni-lov's group on creep properties of alloy systems has not revealed any anomaly of this type, but instead has tended to refute Bochvar's theory. This clear-cut controversy offered a good opportunity for a simple experiment to resolve the problem. The experiment and its results supporting Bochvar are the subject of this paper. However, it will be helpful first to sketch the present status of the larger question of the effect of a phase change or other structural change on plastic deformation. PREVIOUS WORK One of the first researches in this area was by Pfei1,37 who investigated the creep resistance of an 80 Ni-20 Cr alloy containing varying amounts of titanium. He found that the resistance to creep increased rapidly as the solid solubility limit in the alloy at 775'c was approached and slightly exceeded. With further addition of titanium the creep resistance decreased, presumably because of precipitation effects. Bochvar's first work in this field was a study in 1945 of "superplasticity" in zinc alloys containing 15 to 25 pct Al.4 He found that alloys quenched from about 400 had anomalously low hardness when tested below this temperature. The following year, in a paper on the dependence of mechanical properties on the composition and structure of alloys,5 he extended some observations of Kurnakov to predict that at high temperatures of testing the hardness values for solid-solution alloys might be lower than those for the component metals. He also pointed out the influence of changes in solidus temperature in affecting curves of hardness vs composition, and he

Jan 1, 1962

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964