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By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By S. FROES ABRUE

No new oil fields were discovered in Brazil during 1945. Production for the year reached a total of 79.329 bbl., all coming from the four fields in the Baia basin; the Lobato-Joanes field produced 6728 bbl.; Aratu, 6717 bbl.; Candeias, 36,663 bbl. and Itaparica, 29,211 bbl. The total cumulative production from the Baia basin from 1939 to 1945 inclusive amounts to 210,000 bbl., all of which is utilized locally.

Jan 1, 1946

Edward Halse, Puerto Berrio, Colombia, S. A. (communication to the Secretary): I have read with much pleasure the interesting and valuable paper by Mr. Kunz, and hope that the following brief notes, gathered a few years ago, while a resident in Mexico City, may help to elucidate the subjcct: Turquoise.—This was known to the Aztecs as Xihuitl. Santiago Ramirez states that they found it in the Cerro Xicohtzonc, close to Atzcapatzalco, a suburb of the City of Mexico (compare page 59). Opal.—This was known to the ancient Mexicans, for they named it mezcuitlatt (compare page 63). Jade.—Under this was iucluded a third mineral, prehnite, not mentioned by Mr. Kunz. According to James D. Dana, part of the "jade " of China is prehnite; and Humboldt informs us, in his work on New Spain, that the same species of jade is known in some parts of Mexico as mahagua (majagua ?). The same writer says, in his Views of the Cordilleras, that the Aztec name Tecpatl included flint, hornstone, and green jade; and finally, in his Travels in South America," he discusses the nature of the ancient amazon-stones, and declares them to have been made out of a jade resembling " compact feldspar," one of the constituents of the gabbro verde di Corsica. IIence those stones were probably composed of nephrite. According to Humboldt, the form given to them most frequently is that of the Babylomian cylinder, longitudinally perforated, and loaded with inscriptions and figures. They were also cut by the natives into very thin plates, perforated at the center, suspended by a thread, and worn as amulets. According to the historian Clavijero, the specific name given by the Aztecs to the nephritic stone (jadeite) was Quitzalitztli,

Jan 1, 1902

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 Charles T. Holland

Miners have observed for many years that as pillars are removed in mining operations the pillar adjacent to those mined out frequently shows evidence of being compressed. Although this has been known for a long time, little or no information is available concerning how far from the mining area the pillars are affected in this manner, or how great is the magnitude of the compression, or concerning the manner or characteristic way in which the compression acts, as the mined-out area approaches the pillar under consideration. The writer made a study of pillar action in the Mona mine of the Arkwright Coal Co., partly to get some quantitative data on the deformation of coal-mine pillars. The study was not completed but it seems best to present the information that was obtained. Method of Measurement Fig. 1 shows the details of the apparatus used for measuring the deformation. This is permanently attached to the pillar. Fig. 2 shows the details of the gauge that records the deformation. This gauge is removable and was used to measure the deformation at all the stations. The recording dial is graduated in thousandths of an inch and records measurements up to one inch. Fig. 3 shows how the removable gauge is placed in the instrument. When installing the instrument in the side of the pillar, all loose coal near by was removed and a trench 4 to 6 in. deep, and approximately 1 ft. wide, was dug in the pillar. In this trench near the top and the floor, the holes holding the instrument were bored. These holes were then partly filled with thin cement and the rods were inserted. The remaining space in the holes was tamped full of cement. At this time, by carefully manipulating the permanent rods and clamps and adjustable pin, it was possible to adjust the instrument so that the removable gauge would stand true and measure any vertical deformation between the top and bottom rods. Fig. 4 is a photograph of one of the instruments installed, showing the removable gauge in place.

Jan 1, 1938

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By Charles T. Holland

Miners have observed for many years that as pillars are removed in mining operations the pillar adjacent to those mined out frequently shows evidence of being compressed. Although this has been known for a long time, little or no information is available concerning how far from the mining area the pillars are affected in this manner, or how great is the magnitude of the compression, or concerning the manner or characteristic way in which the compression acts, as the mined-out area approaches the pillar under consideration. The writer made a study of pillar action in the Mona mine of the Arkwright Coal Co., partly to get some quantitative data on the deformation of coal-mine pillars. The study was not completed but it seems best to present the information that was obtained. Method of Measurement Fig. 1 shows the details of the apparatus used for measuring the deformation. This is permanently attached to the pillar. Fig. 2 shows the details of the gauge that records the deformation. This gauge is removable and was used to measure the deformation at all the stations. The recording dial is graduated in thousandths of an inch and records measurements up to one inch. Fig. 3 shows how the removable gauge is placed in the instrument. When installing the instrument in the side of the pillar, all loose coal near by was removed and a trench 4 to 6 in. deep, and approximately 1 ft. wide, was dug in the pillar. In this trench near the top and the floor, the holes holding the instrument were bored. These holes were then partly filled with thin cement and the rods were inserted. The remaining space in the holes was tamped full of cement. At this time, by carefully manipulating the permanent rods and clamps and adjustable pin, it was possible to adjust the instrument so that the removable gauge would stand true and measure any vertical deformation between the top and bottom rods. Fig. 4 is a photograph of one of the instruments installed, showing the removable gauge in place.

Jan 1, 1938

By Lewis Reeve

As. part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.1 Later a number of changes were introduced which resulted in. more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equip-ment was tied up, preventing its use for the analysis of further steel sam-ples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collect-ing the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative determination.

Jan 1, 1933

By E. M. Wise

THE practice of adding moderate quantities of nickel to a variety of bronzes has been employed by foundrymen for many years with several objects in view. In some instances it was desired- to harden the alloy; in others it was to increase the fluidity or to improve the solidity of the castings, or to refine their grain. These important matters have been considered in detail by Pilling and Kihlgren1 and by numerous other workers cited by them, and with the exception of the first will not be considered in the present communication. The possibility of reducing the cost of bronze by replacing a portion of the tin with nickel received attention some years ago by Burgess and Woodward,2 and, as will be shown later, offers attractive savings in cost under present conditions. The age-hardening characteristics of the nickel bronzes of appropriate compositions have been known for some time and were mentioned by Price, Grant and Phillips3 and discussed by Wise4 in connection with their paper. These matters are further considered in recent patents,5 and are becoming of commercial importance in the production of high-strength castings.

Jan 1, 1934

By W. H. Schacht

In the Lake Superior District, the air indoors must be heated continuously during eight months of the year and occasionally during the remaining months. Incident with mining in this district, therefor?, there is need for heating many of the buildings connected with these operations. In addition to the mine buildings, that is, shops, engine houses, offices, change houses, etc., such public buildings as schools, library, and theater, when close to the mines, are often supplied from the mine heating mains. At the Copper Range Company's mines, Champion, Trimountain and Baltic, the heating surface thus supplied from the mine mains is over 50,000 sq. ft. (4645 sq. m.) which requires a steam consumption, at times, of 18,000 Ib. (8165 kg.) per hour, or the equivalent of a rate of ovcr 50 tons of coal per day (were live steam used). This figure is based on a consumption of 1/3 Ib. per sq. ft. of heating surface during the coldest weather, and provided the system is not wasting steam by blowing it to the atmosphere or into the return line on account of leaky traps, which so often is the case. Under the latter conditions, steam consumptions of three to four times the above rate are not uncommon. This shows that the cost of heating is of enough importance to he given serious consideration, especially at this time of rising prices of fuel. The power and heating value of exhaust steam arc appreciated by most engineers, and its application for such purposes is general. At our stamp mills, the exhaust from the stamps is used to operate low-pressure turbines, thus reducing the former water rate per horsepower developed by more than 50 per cent. At the above-mentioned mines, electric motors have replaced the many small steam engines, so that this supply of exhaust steam has been practically eliminated. The larger engines are compound, triple, or quadruple condensing. The hoists, however, in all cases are simple and non-condensing and of two sizes, namely, 24 by 60 in. and 32 by 72 in. (61 by 152 cm. and 81 by 183 cm.). These hoists now offer the only available supply of exhaust steam; but as this flow is intermittent and varies from extreme violence to zero, the steam so discharged cannot be

Jan 1, 1922

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By David W. Mitchell

WHILE pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superheating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is miscible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetallic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck' states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones6 who studied the physical properties of low iron magnesium alloys observed a

Jan 1, 1948

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947

By W. F. Netzeband

Jan 1, 1927

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By R. A. Greenkorn

This project originated in a practical problem—we needed five tracers that could be used together to locate flow paths in a pilot flood. While tracers for subsurface liquids have been used since the turn of the century,1-15 none of those reported in the literature appeared to be either consistent or quantitative enough for our purposes. Most were used in field systems without controlled experiments to determine the accuracy and precision of analysis, and many were tracers that could not be used collectively. The ideal tracer, of course, would follow the fiuid of interest exactly, traveling at the same velocity as the fluid front. But the ideal is impractical to attain because adsorption-desorption effects cause the tracer to lag behind the front; these effects, plus diffusion-dispersion effects, cause the tracer front to spread more than the fluid front. Thus, our objective was not to locate a tracer that would be ideal for all circumstances but rather, to find one that would approximately follow the fluid, or one that under controlled conditions could be corrected to calculate the movement of the fluid front. We considered tracers satisfactory—(1) if they were easy to analyze; (2) if their breakthrough-elution curves were not too different from those for the chloride ion, a tracer believed to follow the fluid front closely; and (3) if we could calculate from the curves a material balance, at 1.25-PV (pore volume) injected, within 5 per cent of that calculated from chloride curves. Of a possible 35 materials, we selected 13 tracers that could be quickly and easily identified and whose analysis was claimed to be accurate within 5 per cent. Only one of these, tritiated water, was a radioactive tracer. Radioactive tracers are easy to detect even in small quantities, but they require special handling and special equipment. Also, those that can be used together are limited because special equipment is required to separate emissions from the various tracers. Two of the original 13 tracers were eliminated in static tests to determine how accurately and precisely they could be analyzed, and to check on gross adsorption. The remaining 11 were flowed through a 9-ft linear sandstone model, and breakthrough-elution curves were obtained. Finally, three tracers were field-tested as breakthrough tracers. These tests are described in the following sections. The 13 tracers considered in these experiments were EDTA (ethylene diamine tetra acetic acid), fluo-rescein, picric acid, salicylic acid and ammonium, boron (as borate), bromide, dichromate, iodide, nitrate and thiocyanate ions, plus chloride ion and tritiated water. All but the chloride ion and tritiated water were subjected to static sand tests to eliminate the tracers that could not be analyzed quickly and accurately and to eliminate those that showed excessive adsorption. All but two of the tracers, EDTA and salicylic acid, qualified for flow tests on this basis. The procedures used in the static tests (see Appendix A for analytical details) were as follows. Each tracer (in the amount shown in Table 1) was dissolved in 1,000 ml of water. Then, 800 ml of this solution was added to 500 gm of sand, and the remaining 200 ml was reserved as a control standard. The sand-tracer mixture was agitated once a day over a 10-week period, and during this period we analyzed five duplicate samples from this mixture, along with five duplicate samples from the control solution. From the control-sample analyses, we constructed a control chart on which the sand-tracer analysis results were plotted. The control chart, and its use to determine accuracy and precision of analytical results, as well as the amount of adsorption, is described in Appendix B. The results of the static tests are summarized in Table 1, which lists the concentration c (concentration at time t) divided by c, (initial concentration). If there was no adsorption, c/c, = 1. The acceptable deviation from this value varied from tracer to tracer, depending upon the limits of analytical precision established for the different tracers. The best results were obtained with boron, bromide and dichromate, with all values falling within limits of accuracy and precision. Ammonium, iodide, nitrate and picric acid also were satisfactory, although the ammonium results were erratic. Flourescein and thiocyanate were unsatisfactory ini-