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By C. R. Claus, G. A. Standish

Since March. 1945, the Magnolia Petroleum CO. has drilled 39 wells in Southwest Coastal Louisiana. All wells were drilled within a comparatively small radius, but the area provides a large variety of problems. The deepest well drilled was 13,518 ft, and the total depth averaged 10,977 ft. Throughout this period drilling mud control and types of mud handled were: (I) phosphate, (2) red lime (late conversion), (3) red lime starch (early conversion), (4) red lime starch oil emulsion, (5) precision controlled low alkalinity-low lime content. and (6) gel muds for completion purposes. Improvement has been obtained in effecting some or all of the following: (I) more rapid penetration, (2) reduction in drilling hazards, (3) better evaluation of cores and logs, and (4) better completions. The geological sequence of zones penetrated range from recent sediments at the grass roots through the Frio section. Anticipation of high-pressure zones and incompetent formations entails precision control of drilling mud weights, and the unconsolidated nature of the various zones requires constant attention to the filtrate, viscosity, and gel strength values. In the Chalkley field, particularly, this combination of problems exists, where the formation pressures and overburden weight density values are in very close proximity. Design of casing and drilling mud programs must be modified to fit each well. INTRODUCTION Field and research work on drilling fluids has made constant progress, enabling operators to prospect progressively deeper horizons. Numerous papers have been written on the theoretical aspects of drilling fluid devel- opment, but in the field engineers have found it difficult to evaluate the role of specific mud constitutents when dealing in terms of thousand barrel mud systems. For that reason field data is somewhat lagging in technical report writing. However, applications of new techniques in the field have usually paralleled, and in numerous instances preceded, research work. The information obtained by Magnolia Petroleum Co. in the course of drilling 39 wells within a comparatively small area in Southwest Coastal Louisiana provides an excellent opportunity of reviewing a specific example of drilling mud evolution. A large variety of problems has been coped with, the most important result being that every well was successfully drilled to its projected total depth. The discussion begins with the advent of deep drilling in this area in March, 1945, and is concluded with a resume of recent drilling operations in the Chalkley field. The primary purpose of this paper is to describe the evolution in types of drilling fluids as it occurred and its application in the solution of various drilling problems. All of this information and experience resulted in the successful drilling of the three wells in the Chalkley field, where a combination of the most sound techniques was necessary in carrying drilling operations to the projected total depths. Other operators along with service company engineers have contributed considerably through the interchange of ideas and information to this paper, but the data and conclusions which are contained are based on first-hand observation of Magnolia Petroleum Company's drilling operations. The 39 wells drilled by Magnolia Petroleum Co. average in depth 10,977 ft per well, while the maximum depth penetrated was 13,518 ft. The cost of drilling fluids have varied from $8,700 to $165,000, with the over-all drilling costs ranging from $74,000 to $543,000 per well. This wide variance illustrates the unpredictable nature of each well and the effects on over-all cost when high density muds are required to control

Jan 1, 1955

The authors of T.P. 4179 have conducted a large number of experimental water floods, and the data are reported in a very clear manner. These data show significant variations of residual oil saturation with changes in wettability, interfacial tension, flooding rate, and oil-water viscosity ratio. Furthermore, some of the data obtained cover a range of variables not previously reported in the literature. It is our opinion that at least some of the observed variation in oil recovery can be obtained only in floods made under conditions identical with those used by the authors. There are other systems which may be said to have the same wettability, but which exhibit an entirely different qualitative dependence of oil recovery on the experimental variables. In this regard, we would like to direct attention to several items which we feel are not given sufficient consideration in the paper. The first of these items has to do with wetting equilibrium. A survey of the current literature will reveal that little is known, and even less is understood, about wetting equilibrium. This is particularly true of the relation between contact angle measurements made under static conditions, and the wettability existing under the dynamic conditions of floods carried out at relatively high rates. We feel that this is a very important consideration, particularly in the floods the authors performed under what they consider to be "water-wet" conditions. It is our opinion that wetting equilibrium did not exist in these floods, except possibly at the very lowest rates. This opinion is in part based on some flooding tests we have made which are very similar to some of those described by the authors. These floods were made in unconsolidated cores, 6 in. long and 13/4 in. in diameter, made up of carefully graded glass spheres of the approximate size of the sand grains used in the subject paper. The cores were mounted vertically, and distilled water was used to displace a refined oil equivalent to the authors Soltrol C. The glass spheres had previously been carefully cleaned so that they were strongly wet by the water. The floods were made with and without an interstitial water saturation. When interstitial water was present, the solid surfaces were mostly covered with water prior to injecting the flooding phase. Consequently, a condition very near wetting equilibrium existed throughout the flood. The data in Fig. A show that under these eircumstances, rate had no influence on residual oil at flood-out, over the range of rates studied. On the other hand, in the absence of interstitial water, the surfaces are all covered with oil before the displacement. To achieve wetting equilibrium the injected water must displace the oil from the surfaces themselves. This is not a fast process. Therefore, the effective dynamic wetting condition in floods of this type must depend upon the flooding rate. When the flood rate is very low, compared to the rate at which wetting equilibrium is attained, the residual oil saturation at flood-out is essentially the same as the residual obtained when interstitial water is present. This is shown in Fig. A, and occurs because the dynamic wetting conditions are the same in both cases. However, at moderately high flooding rates, the rate has an important bearing on the amount of oil recovered because in this case the attainment of surface equilibrium is the slow step. We believe that, in the absence of an interstitial water saturation, oil recovery varies with rate because of the reasonably slow approach to wetting equilibrium which occurs during the displacement. In fact, as the rate is increased, the oil recovery performance indicates the core is becoming progressively less water-wet. At the highest rate there is even considerable simultaneous production of oil and water after breakthrough. This does not occur at the lower flooding rates, nor is there appreciable simultaneous oil and water produc-

Jan 1, 1957

By A. Stanley, J. C. Mead

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941,when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948. The magnetite concentrate produced in the milling operation was too fine (minus 20 mesh) to be used directly in iron blast furnace operation, and most of the magnetite had to be stockpiled in 1942 and 1943. In 1943, the Defense Plant Corp. built a Greenawalt sintering plant at Tahawus, N. Y., to put the magnetite concentrate in a more suitable form for use in the iron blast furnace. The Greenawalt sintering plant consists of three 10 by 25 ft sintering pans designed to produce 1800 gross tons of sinter per 24 hr. The vacuum to each pan is produced by two Greenawalt fans in series, pulling approximately 30,000 cu ft of air per minute at 50 in. water gauge vacuum. The plant started operation in August 1944. The present plant production averages 25 tons per operating pan hour (approximately 224 lb per operating hour per square foot of grate area) of plus 1 in. sinter. Raw feed to the plant consists of 61 pct magnetite, 4 pct anthracite coal culm, and 35 pct minus 1 in. return fines which are conveyed to a pug mill where the materials are mixed thoroughly and water added to give the mixture 5.5 to 6 pct moisture. The mixed prepared feed is conveyed to two 4 by 10 ft vibrating screens where the minus 1 in. plus 5/8 in. return fines are screened out and discharged into a surge bin for use as a hearth layer. The minus % in. prepared feed is discharged into another surge bin for use as prepared feed. A charge car, electrically operated, having a capacity of one charge of prepared feed and several charges of hearth layer, lays a thin layer of plus 5/8 in. return fines and 9 1/2 in. depth of prepared feed into the pans. A fluffing roll and a vibrator on the car fluffs and spreads the prepared feed into the pans. An ignition car, electrically operated, ignites the top of the bed with a 30 sec flash burn. The 9 1/2 in. bed sinters in approximately 13 min. Dumping the pan, and recharging and igniting the bed requires 2 min. To improve the quality of the ilmenite concentrate produced in the mill and to reduce the amount of titanium dioxide lost in the mill tailings and in the magnetite product, extensive research work and pilot plant operations have been done on grinding the crude ore to minus 65 mesh size (rather than to minus 20 mesh) and concentrating it by a combination of magnetic separation (for magnetite recovery) and flotation (for ilmenite recovery). These tests have proved successful in increasing ilmenite recovery and grade. With the development of the ilmenite flotation process to a stage where a full scale flotation plant was in the design stage, the problem arose of handling the 65 mesh magnetite concentrate that would be produced. In order to study and solve the problems of handling and sintering the 65 mesh magnetite in the sinter plant, a pilot sinter plant was plus from John E. Greenawalt. The effect of using 65 mesh magnetite in the sintering operations was then studied on the 2.4 sq ft test pan, operating under conditions as similar to the large plant as could be set up in the laboratory. A series of tests were run in the test pan on present sinter plant feed that had been mixed in the plant pug mill. An average production and an average quality of sinter produced in this series

Jan 1, 1950

By Brian J. Gorval, Robert L. Kemeny

INTRODUCTION Financing, or providing adequate capital at low cost for developing and bringing a natural resource property into production, is a fundamental requirement for profitable operation. Under the present economic environment the cost of financing any project is gaining more importance than ever. The fundamental keys for success in mining are "the Four M's": Mineral, Market, Management and Money. In recent years, with capital and operating costs skyrocketing, increased emphasis on obtaining adequate and low cost capital funds for bringing in a prospect is essential. For a small mining company there are limited sources for raising funds. In most cases these companies have neither a substantial asset base, nor any cash flow, and they are deemed as risky investments. The issue of shares of capital stock of such a company is probably the most common method of raising funds via the public purse. Alternatively, debt could be used and a source of such capital might be private investors or financial institutions. The company which intends to raise funds from the investing public by way of the sale of equity, subsequently lists those shares for trading on a stock exchange. Going and staying public commits a company to a multitude of complex laws, rules and reporting requirements. The governing bodies are the watch dogs for the public. The largest of such an organization of this kind in the world is the Securities and Exchange Commission (SEC) in the United States. In Canada, the Securities Laws come from within provincial jurisdiction. Most provinces have their own Securities Act, and Securities Commission. It is the Commission which administers the Act, and hence controls the distribution and trading of securities within the province. Extra provincial registration is required for trading and distribution in more than one province. In British Columbia, prior to a public offering, the approval of the Superintendent of Brokers (SOB) and of the VSE must be obtained. THE VANCOUVER AND TORONTO STOCK EXCHANGES There are five stock exchanges in Canada which supply a trading forum in which mining companies may operate. The stock exchanges are located in Montreal, Toronto, Winnipeg, Calgary, and Vancouver. Of the five stock exchanges, the Vancouver Stock Exchange (VSE) and the Toronto Stock Exchange (TSE) are the most heavily used for resource-based issues and are the focus of this paper. The objective of this section is to provide a brief background on the VSE and TSE. The Vancouver Stock Exchange The VSE is Canada's predominant stock exchange for financing resource-based, junior issues. Since 1907, the VSE has acted as a source of funds for mining, exploration and energy companies throughout Canada and the world. Currently, there are over 1400 companies listed on the VSE. During 1983, over 3.1 billion shares traded at a value exceeding CDN$3.96 million. The VSE has developed a reputation as one of the few exchanges where a speculative resource venture may obtain a listing and subsequent financing in a relatively short time, generally five to ten months. The SOB, the Investment Dealer's Association of Canada (IDA), and the VSE all regulate trading at the Exchange. Any irregularities in a company's stock dealings are investigated and trading may be halted by the VSE until a satisfactory explanation has been received from the suspended company. Companies can be suspended from trading or delisted for various reasons. One reason is misrepresentation of facts in documentation submitted to the SOB, VSE, or to the public, through news releases.

Jan 1, 1985

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.' The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.' Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By J. S. Crump, C. R. Hocott, A. E. Hoffman

Planning of the efficient operation of a gas-condensate reservoir requires a knowledge not only of the gross phase behavior of the system but also of the equilibrium distribution of the various components between the gas and condensate phases. This equilibrium distribution can be calculated with appropriate equilibrium constants. In this paper are presented equilibrium constants determined experimentally for the oil and gas phases initially present in the same reservoir and for the gas and condensate phases of the gas cap material at a series of pressures below the original reservoir pressure. Also presented is a method for the correlation of the experimentally determined equilibrium constants. The utility of the correlation is demonstrated further by an example of its use in adjusting the equilibrium data to permit their application to another gas-condensate system of similar composition. INTRODUCTION Planning of the efficient operation of a gas-condensate reservoir requires a thorouugh knowledge not only of the gross phase behavior of the particular hydrocarbon system but also of the equilibrium distribution of the various components between the gas and condensate phases. At the initial conditions of reservoir temperature and pressure, the original hydrocarbon materials in a gas-condensate reservoir or in the gas-cap of an associated reservoir exist in a single, homogeneous vapor phase. However, some condensation of hydrocarbons to a liquid phase usually occurs in the reservoir as pressure declines incident to production. Because of this condensation. the produced gas changes composition continuously. The composition of the produced gas, as well as that of the condensed liquid, can be calculated from the composition of the original reservoir material through the application of appropriate equilibrium constants or "K"-values provided these values are known. Equilibrium constants have been used for many years in problems of surface separation of gas and oil and natural gasoline recovery. However, no satisfactory equilibrium data at reservoir conditions have been available for the higher boiling hydrocarbons which acquire abnormal volatility at high pressure and are therefore present in the gas phase in condensate reservoirs. Early work in this field indicated that the behavior of the higher boiling hydrocarbons largely determines the behavior of gas-condensate systems at high pressure.' Consequently, a portable test unit was designed to permit determination of the distribution of the heavier hydrocarbons between the gas and liquid phases of a gas-condensate system. This paper describes the test equipment and presents the results of an investigation of the reservoir fluids from an associated oil and gas reservoir in the Frio formation in Southwest Texas. Also presented is a method for correlation of the experimentally determined equilibrium constants, together with an example of the use of the method in adjusting these data for application to another gas-condensate system of similar composition. FIELD TESTING AND SAMPLING In order to determine the compositions of the reservoir fluids, field samples were secured from two different wells, one completed in the oil zone, and one completed in the gas cap. The oil well was completed through perforations in 51/2-in. casing at a depth of 6,822-6,828 ft subsea. Pressure and temperature traverses made in the well indicated the pressure and temperature to be 3,831 psig and 201 °F, respectively, at a depth of 6.828 ft subsea. Subsurface samples were taken from this well after a four-hour shut-in period.

Jan 1, 1953

By P. T. Bail, J. E. Bobek

In reservoirs containing soft shales interbedded with oil-producing sands, it is possible to have water movement from the shales into the sands during reservoir depletion. This paper presents the results of scaled flow-model tests performed to investigate the efficiency of oil displacement by this vertical influx of water into oil-producing sands. In these model tests, the effects of rate of influx and rock wettability were considered. Oil recoveries by shale-wafer influx and by water flooding were cornpared after 0.4 hydrocarbon volume of water entered the producing sand. This comparison was made for water-wet and oil-wet systems. In water-wet sand, shale-water influx produces slightly less oil than conventional water flooding; in oil-wet sand, shale-water influx produces about one-half as much oil as conventional water flooding. In another type of comparison, it was found that shale-water influx followed by water flooding recovers less oil than water flooding alone. This is true for both water-wet and oil-wet sands. A comparison of tests run at different rates of shale-water influx shows that oil recovery is insensitive to rate in water-wet sand; in oil-wet sand, oil recovery decreases with decreasing rate of influx. INTRODUCTION Localized subsidence of the earth's surface has accompanied the depletion of some oil reservoirs, particularly in California,1, 2 along the Texas Gulf Coast,3 4 and in the Bolivar Coastal fields of Venezuela. Subsidence occurs when fluid withdrawals reduce the pressure in the reservoir. The reasons for subsidence accompanying a reduction in reservoir pressure are not known with certainty.10° However, there is considerable evidence that compaction of soft shale beds adjacent to producing oil sands can be a major cause of this subsi-dence.3, 6, 10-12 When the shales compact, a limited amount of water moves from the shales into the producing sands. A schematic illustration of this oil-producing mechanism is shown in Fig. 1. As the pressure in the sand declines due to oil production, a predominantly vertical pressure gradient develops at the sand-shale boundary. This causes water to move from the shale into the sand as indicated by the solid arrows. This paper reports the results of scaled flow-model tests to investigate the efficiency of oil displacement by the vertical influx of shale water into producing sands. The model tests were not performed with the aim of duplicating the recovery behavior of any specific reservoir. The primary purpose of the tests was to obtain a better understanding of oil displacement by shale-water influx. A knowledge of the oil- and water-production characteristics of even a simplified reservoir system should be of value to engineers estimating the performance of reservoirs where shale-water influx is occurring in conjunction with other production mechanisms. The following limitations and assumptions apply to the model work. 1. The sand of the prototype reservoir is homogeneous and horizontal. 2. The shale-water influx is uniformly distributed along the top and bottom of the sand member being studied. 3. No effects of edge-water drive or dissolved-gas drive that might accompany shale-water influx are considered. PROTOTYPE RESERVOIRS Scaled-model tests were performed to study oil displacement from three prototype reservoir sections. The reservoir sections modeled consist of single sand layers out of a sequence of -sand and -shale layers, as illustrated in Fig. 1. Each prototype represents a homogeneous, high-permeability, unconsolidated sand layer. In the field, the prototype is oriented in such a manner that one end is at the radius of drainage of a producing well and the other end is pointed toward the producing well (Fig. 2). The sand and fluid properties and the dimensions of the three prototypes are given in Table 1. The capillary pressure relationships for the three prototypes are presented in Figs. 3, 4 and 5. The oil-water per-

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By H. Kurushima, S. Tsunoda

An investigation of the hydrometallurgy of Cu-Zn concentrates by The Dowa Mining Co. of Japan is described and a detailed flowsheet of the Kosaka hydro-metallurgical plant is given. Sufficient operating experience has shown that the Dorrco FluoSolids system has proven successful for recovery of both zinc and copper by roasting in a fluidized bed. At present, 2400 metric tons of concentrates per month are being treated and recoveries of 93 pct Cu and 65 pct Zn are being effected. A SURVEY of the Japanese chemical industry in 1949 revealed, among other things, that sulphur-bearing blast furnace gas from the Kosaka smelter of The Dowa Mining Co. Ltd., Kosaka, Japan, was being exhausted to the atmosphere as waste. In addition, it was costing that company an average of ten million yen ($28,000) annually for damages to the surrounding property caused by the sulphur dioxide in the gas. It was recommended by this survey that the gas be utilized for the production of sulphuric acid by the contact process. Mr. Kurushima visited the United States in May 1950 to investigate the engineering, construction, and operation of a contact acid plant. Any acid produced at Kosaka would necessarily have to be 98 pct H,SO, to prevent corrosion in railroad tank cars transporting it to the point of use. However, the production of 98 pct acid requires constant volume and SO, content of the gas. As the converter gas at Kosaka fluctuates in both volume and quality, it was decided to evaluate the smelting process with relation to other methods of recovery. This evaluation revealed a relatively new type of roaster, the Dorrco FluoSolids reactor, which was reported to be capable of roasting the copper sulphide concentrate in an excess of air with the production of an SO1 gas strong enough for acid production and a water-soluble copper sulphate calcine. The copper sulphate then could be leached from the roasted ore and electrolytic copper recovered from the leach solution in much the same manner as practiced by the Chile Exploration CO. for treating naturally occuring copper sulphate ores. Use of a reactor of this type would eliminate the need for a blast furnace and converter and, in addition, would effect savings in labor and fuel. The Kosaka ore is a microscopically fine mixture of copper, zinc, and lead sulphides. The lead and a small amount of the barite present can be separated by flotation, but any separation of copper and zinc proved extremely difficult. In blast furnace operation at Kosaka, zinc had been slagged off until a stockpile of about 12,000,000 tons containing 5 pct Zn had been accumulated. Mr. Kurushima felt that if any of the zinc in the concentrate was sulphat-ized and leached with the copper, it also could be recovered electrolytically. The Dorr Co., sponsors of fluidization technique in the metallurgical field, suggested that sulphate roasting be tested out on a laboratory scale and that, if successful, a commercial Dorrco FluoSolids system be constructed. They indicated that the results from such laboratory tests could be transposed to a commercial scale without pilot planting the roasting operation. It was therefore decided to send samples of flotation concentrate to the West-port Mill, laboratories of The Dorr Co., for testing. The objective of Mr. Kurushima's visit to the United States thus had changed from investigation of sulphuric acid plants to a fundamental examination of the hydrometallurgy of copper and zinc. Testing Program In February 1951, Mr. Tsunoda went to the United States to witness the application of the FluoSolids system to sulphate roasting at The Dorr

Jan 1, 1956

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By R. E. Smallman, I. Milne

The deformation behavior of single crystals of Nb-Mo alloys has been investigated with particular reference to the influence of composition, orientation, and temperature. Strong solid-solution hardening was observed reaching a maximum at the equiatomic cotrlposition and can be attributed to the difference in atomic size between niobium and molybdenutrz. Changes in the form of stress-strain curve, as shown by a high work-hardening rate and restricted elongation to fracture, were observed at a composition of Nb-85 pct Mo and are attributed to the presence of MozC DreciDitate. Conjugate slip was only extensive in dilute alloy samples; at the 50/50 composition deformation rnainly occurred by primary slip, and the onset of conjugate slip gave rise to failure by cleavage on (100). The variation of yield stress of Nb-50 pet Mo with orientation was consistent with slip on (011)(111) slip systems. The temperature deperndence of the yield stress between -196" and 250°C was similar to that of pure bcc metals, but at a much higher stress level; no evidence for twinning %as found. IN recent years the deformation behavior of various pure metals in groups VA and VIA has received considerable attention, but surprisingly little work has been carried out on binary alloys made by mixing metals from the two groups. Such an investigation would be of interest since single crystals of metals of group VA have been shown to deform characteristically with a multistage deformation curve1"3 while a parabolic type of deformation curve has been reported for most of the group VIA metals.4'5 It has been suggested by Law ley and Gaigher~ that the difficulty encountered in obtaining multistage deformation curves for molybdenum in group VIA was possibly because of the presence of a microprecipitate of MozC which they observed even at carbon contents as low as 11 ppm. Recently a multistage deformation curve has been reported for molybdenum ," although the stages are not so definitive as those for group VA metals. The binary alloys of the particular refractory metals which have been investigated in single-crystal form include Ta-w,' Ta- Mo,' and Nb- Na." While a large amount of hardening was observed for alloys of the Ta-W and Ta-Mo systems, associated with room-temperature brittleness for alloys approaching the equiatomic composition, Ta-Nb remained ductile over the complete composition range with little or no solution hardening. Other systems have been investigated by hardness measurements on polycrystalline material and a discussion of the hardening of these alloys has been presented by ~udman." The purpose of the present investigation was to examine the deformation behavior of Nb-Mo alloys in detail, with particular reference to alloy composition and single-crystal orientation. In this way it was hoped to shed some light upon the restricted ductility of these alloy specimens. 1) EXPERIMENTAL PROCEDURE The starting materials were obtained in the form of beam-melted niobium rod and sintered molybdenum rod of suitable dimensions. Since niobium and molybdenum form a complete solid-solution series at all temperatures, alloy single crystals were produced by melting the two constituents together in an electron bombardment furnace (EBM). To produce specimens free from segregation a molten zone was passed over the length of each rod six times in alternate directions at a speed of 10 in. per hr. Typical specimens were analyzed for interstitial impurities by gas analysis and for metallic impurities by spectrographic analysis. The results of this analysis are shown in Table I. Many of the tensile specimens were also analyzed (after testing) by scanning the gage length in an electron beam microanalyzer, from which it was found possible to predict the approximate composition of a specimen from the original proportions of each element in the EBM. The tensile specimens were made with a gage length of 0.5 in. and diameter of 0.075 in., using a Servomet Spark machine. By careful machining on the finest range for the final i hr of this technique, surface cracks could be reduced to the level where they were easily removed by electropolishing in a solution of nitric and hydrofluoric acids. The specimens were strained at a rate of 10 4 sec-' using friction grips designed to prevent accidental straining and maintain a good alignment before straining. The orientations of the individual specimens tested are shown in Fig. 1 and the corresponding compositions listed in Table I1 together with collated experimental data. 2)RESULTS a) General Deformation Behavior. The effect of composition on the room-temperature deformation curves of similarly oriented specimens is shown in Fig. 2. The yield stresses of the pure constituents, while not the lowest reported to date, were at least comparable with existing data. Although the solution hardening was large for alloys at either end of the phase diagram, and comparable with the Ta-W solution-hardening data of Ferris et a1.,8 the low work-hardening rate characteristic of niobium was sustained until a composition of Nb-85 pct MO had been reached. Associated with the peak yield stress ob-

Jan 1, 1969

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation'-' despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By H. R. Cooper, T. S. Mika

T. S. Mika (Department of Mineral Technology, University of California, Berkeley, Calif.) - Dr. Cooper's attempt to establish a correlation between process behavior and operational variables on the basis of a statistical analysis after imposing a reasonable process model is a very commendable improvement on the use of standard regression techniques. However, it must be recognized that the imposition of a model has the potential of yielding a poorer representation if its basic assumptions or mathematical formulation are invalid. It appears that at least two aspects of his treatment require some comment. First, the limitations on the kinetic law where xta represents a hypothetical terminal floatable solids concentration (cf. Bushell1), should be mentioned. Most current investigations2-9 appear to utilize the concept of a distribution of rate constants rather than a single unique value, k, to describe flotation kinetics. A distributed rate constant is certainly a more physically meaningful concept than that of a terminal concentration. The study of Jowett and safvi10 strongly indicates that xta is merely an empirical parameter, whose actual behavior does not correspond to that expected from a true terminal concentration. Rather than being a strictly mineralogical variable, as Dr. Cooper's treatment implies, it apparently represents the hydromechanical nature of the test cell as well as the flotation chemistry. The extension of batch cell kinetic results to full-scale continuous cell operation is a suspect procedure if the effect of such nonmineralogical influences on x,, remain unevaluated. There is evidence that introduction of a terminal concentration is necessitated by the inherent errors which arise in batch testing and are eliminated by continuous testing methods.' Possible lack of validity of the author's use of Eq. 1 is indicated by two unexpected results of the statistical analysis of his batch data. The first is the apparent corroboration of the assumption that the rate constant, k, is independent of particle size, i.e., of changes in the size distribution of floatable material. This assumption directly contradicts numerous results 2,4,11-l8 for cases where first order kinetics prevailed and ignores the phenomenological basis for the analysis of flotation in terms of a distribution of k's. It must be recognized that, if the rate constant is size dependent, the lumped over-all k would be time dependent; Eq. 1 would then no longer be valid. Cooper's x,, is determined by batch flotation of a distribution of sizes for an arbitrary period of time. If the size dependence of k is artificially suppressed, x,, will become a function of the experimental flotation time used in its determination. Upon reviewing the rather extensive literature concerning batch flotation kinetics, there appear to be few instances where constant k and x,, adequately adsorb variations in floatability due to particle size. The second surprising result is the low values of the distribution modulus, n, determined. Contrary to Cooper's assertion, most batch grinding (ball or rod mill) products yield values of n > 0.6, which increase as the material becomes harder.'' It is likely that the values of n = 0.25 and n = 0.42 for Trials 1 and 2, respectively, are completely unreasonable, and even the value n = 0.54 obtained for Trial 3 is unexpectedly low. Possibly, this indicates inherent flaws in the three trial models considered, in particular the assumed particle size independence of the rate constant, k. The above does not necessitate that Eq. 1 (and the terminal concentration concept) is invalid; it could constitute a good first approximation. However, the qualitative arguments used by Dr. Cooper in its justification are somewhat frail and require verification, particularly since much of the flotation kinetics literature is in opposition. Apparently, no effort was made to test these hypotheses on the actual data; in fact, since they pertain to a single batch test time, his data cannot be utilized to evaluate the kinetics of flotation. To evolve a control algorithm on the basis of this infirm foundation seems a questionable procedure. Another difficulty in his analysis arises in consideration of the froth concentrating process. As Bushel1 ' notes, for Eq. 1 to be valid it is necessary that the rate of recycle from the froth be directly proportional (independent of particle size) to the rate of flotation transport from the pulp to the froth, a restrictive condition." Harris suggests that it is more realistic to assume that depletion occurs in proportion to the amount of floatable material in the pertinent froth phase volume (treating that volume as perfectly mixed).12,21,22 The physical implications of

Jan 1, 1968

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By R. V. McAfee

The fundamentals of vertical-lift performance are examined with the aid of computer-calculated flowing gradient charts. Flowing and gas-lift well performance characteristics are determined from available well test data. The effect of tubing size, gas-liquid ratio and wellhead pressure is discussed for both flowing and gas-lift wells. The effect of gas-injection pressure, formation gas, bottom-hole pressure and valve spacing is also discussed for gas lift wells. From these studies conclusions may be reached for improving or prolonging natural flow, obtaining optimum lift efficiency when natural flow ceases and improving existing gas-lift systems. The techniques perfected satisfy the requirement that the time involved to conduct an evaluation be practical for operating personnel. INTRODUCTION Flowing pressure gradients furnish the key to successful evaluation of vertical-lift performance in producing wells. Command of multiphase flow gradients in some readily usable form is a necessity before operating personnel can competently include vertical-lift performance evaluation of both flowing and artificial-lift wells in their over-all consideration of production efficiency. A readily usable form cannot be overemphasized since most of the decisions which confront the production engineer with a problem well must be made quickly. In moving a barrel of oil from the reservoir to the stock tank, the major portion of energy generally is expended in the vertical-lift phase. This may or may not be of concern during the flowing life of a well, depending upon the production requirements. It becomes of some concern when the flow performance of the well becomes erratic, and a conscious effort must be made to maintain natural flow. It is at this time that the first steps may be taken to modify existing conditions to relieve unnecessary limitations to proper flow. When natural flow ceases and some form of artificial lift must be installed, the amount of energy expended in lifting liquids becomes quite obvious. It is at this time, if no other, that lifting efficiency becomes important because that part which must be supplied from an outside source is now related directly as a cost per barrel of oil produced. Ten years ago, the majority of gas-lift wells were produced with gas-well gas. Today, the majority are produced by closed rotative gas-lift systems. This permits a direct evaluation of well performance in terms of horsepower requirements and has resulted in mixed conclusions as to the success of gas lift based upon the relative efficiency of a particular system. An increased awareness of the need to resolve vertical-lift performance on a readily usable, scientific basis was inevitable. An indication of the need for better applied science in this field is the often-asked question of whether or not gas-lift can efficiently deplete a given well or reservoir. This question cannot possibly be answered without first evaluating reservoir, surface and vertical-lift performance both as encountered today and as anticipated throughout the life of the well or wells. The technique presented in this paper was originally developed to upgrade gas-lift installation design from an applied art to an applied science. It has since been successfully used not only for this purpose, but also for the whole field of vertical-lift performance in its broadest sense. Lift efficiency should be considered important while the well is still flowing, as well as after natural flow ceases. Correct interpretation and proper modification of the vertical-lift performance of a producing well can provide dramatic improvement in production performance and/or efficiency. STATEMENT OF THEORY AND DEFINITIONS Fig. 1 illustrates the three divisions of production which will be used in this paper. The terms are a modified version of those presented in the very fine paper by Gilbert.' The fields of reservoir and surface performance both have been greatly improved over the years. A study of those writings which may be found indicates that the field of vertical-lift performance has not progressed as well. There are two possible reasons for this lack of progress. 1. It has not been recognized as a scientific field in itself by the oil companies, as has reservoir engineering. 2. The equipment companies have confined their efforts to mechanical design research rather than the more basic study of vertical-lift performance of producing wells. Both organizations must have an economic stimulus for doing research in this field, and most of the results obtained in past work has been so erratic as to arouse little enthusiasm. The basic purpose of interpreting vertical-lift performance is to predict operating conditions below the surface of the ground from available data. The success of the interpretation depends upon the accuracy with