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By O. L. Culberson, J. J. McKetta

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By J. J. McKetta, O. L. Culberson

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

By E. V. Foran

Among the many newer disclosures that have accompanied the petroleum industry's progressively deeper exploratory drilling is the increased frequency with which the operators are encountering reservoirs of which the products at the time of discovery exist wholly or predominantly in the gas phase. The popular term "distillate pool" is most often used within the industry when referring to this type of reservoir, and in this paper the term is used in that sense. These pools have been observed in many different surroundings. In some places the entire reservoir is filled with the wet gas containing its water-white condensible products in the gas phase but apparently with no dark oil or other hydrocarbon liquids in the reservoir. The 8200-ft. horizon in the Big Lake field in West Texas is a good example of this type. At other places the wet, or distillate-bearing, gas may form a large gas cap directly overlying and in contact with an extensive reserve of dark oil. Oklahoma City, Kettleman Hills, the 8500-ft. horizon in the Big Lake field, and many others are examples of this type. There are also many places in which the wet distillate-bearing gas fills nearly the entire reservoir space, while the dark oil occupies only a narrow, bandlike zone, which marks the boundary of the reservoir along its lowest productive contour. The heavier components of these deep pool gases are generally water white in color, a large portion of which are condensible in a conventional oil and gas separator, when operated under pressures of the order of 400 to 800 Ib. per sq. in. Although the water-white products recovered in the separator sometimes have end points of 650" F. and higher on standard Engler distillation, they occur only in the gas phase in the reservoir. It is entirely possible that even some small amounts of dark colored reservoir components may occur in the gas phase when the temperature is 300" F. and pressures exceed 6000 Ib. per sq. in. Close approaches to these conditions have been encountered in the deepest producing wells. The condensible content of the deep reservoir gases of the many pools that have been tested or produced to date shows a wide variation in both condensible content, per 1000 cu. ft. of gas, and physical character.

Jan 1, 1939

By E. V. Foran

Among the many newer disclosures that have accompanied the petroleum industry's progressively deeper exploratory drilling is the increased frequency with which the operators are encountering reservoirs of which the products at the time of discovery exist wholly or predominantly in the gas phase. The popular term "distillate pool" is most often used within the industry when referring to this type of reservoir, and in this paper the term is used in that sense. These pools have been observed in many different surroundings. In some places the entire reservoir is filled with the wet gas containing its water-white condensible products in the gas phase but apparently with no dark oil or other hydrocarbon liquids in the reservoir. The 8200-ft. horizon in the Big Lake field in West Texas is a good example of this type. At other places the wet, or distillate-bearing, gas may form a large gas cap directly overlying and in contact with an extensive reserve of dark oil. Oklahoma City, Kettleman Hills, the 8500-ft. horizon in the Big Lake field, and many others are examples of this type. There are also many places in which the wet distillate-bearing gas fills nearly the entire reservoir space, while the dark oil occupies only a narrow, bandlike zone, which marks the boundary of the reservoir along its lowest productive contour. The heavier components of these deep pool gases are generally water white in color, a large portion of which are condensible in a conventional oil and gas separator, when operated under pressures of the order of 400 to 800 Ib. per sq. in. Although the water-white products recovered in the separator sometimes have end points of 650" F. and higher on standard Engler distillation, they occur only in the gas phase in the reservoir. It is entirely possible that even some small amounts of dark colored reservoir components may occur in the gas phase when the temperature is 300" F. and pressures exceed 6000 Ib. per sq. in. Close approaches to these conditions have been encountered in the deepest producing wells. The condensible content of the deep reservoir gases of the many pools that have been tested or produced to date shows a wide variation in both condensible content, per 1000 cu. ft. of gas, and physical character.

Jan 1, 1939

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969

By Alec M. Crowell, Thomas D. Bailey

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By Thomas D. Bailey, Alec M. Crowell

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By George I. Smith

Jan 1, 1985

By W. A. Ver Wiebe

The year 1938, with a production of 58,784,250 bbl. from 18,790 wells shows a slight recession from the high peak of oil production reached the previous year, when slightly over 68 million barrels of oil was marketed. The previous high peak had been reached in 1917 with a total of 45,451,000 bbl. Another still earlier peak was reached in 1904, during which year slightly less than 5 million barrels was produced and sold. The production of gas, on the other hand, probably reached a new peak during 1938 with a total of over 60 billion cubic feet. This peak, however, was not the highest peak, for during the year 1908 over 80 billion cubic feet was produced. Between these two high peaks the production dropped down to 16 billion cubic feet in the year 1921. The number of wells drilled during the year totals 1569. This figure is somewhat lower than the figure given in several trade journals because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly three-fourths (or 1107) of the total number of wells were completed as commercial oil wells (915 in western and 192 wells in eastern Kansas). The commercial gas wells completed number 50, of which 4 are in eastern Kansas and 46 in western Kansas. The remaining 412 completions include 130 dry holes in eastern and 282 dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year accounted for 70,000 bbl. of new oil for eastern and 1,220,000 bbl. of new oil for western Kansas. It is interesting to note in this connection that the number of wells completed in the state rose gradualIy to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918 when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak in 1937, the low point was reached during 1931, with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a new area whether it should be called a new pool or a long extension of an

Jan 1, 1939

By W. A. Ver Wiebe

The year 1938, with a production of 58,784,250 bbl. from 18,790 wells shows a slight recession from the high peak of oil production reached the previous year, when slightly over 68 million barrels of oil was marketed. The previous high peak had been reached in 1917 with a total of 45,451,000 bbl. Another still earlier peak was reached in 1904, during which year slightly less than 5 million barrels was produced and sold. The production of gas, on the other hand, probably reached a new peak during 1938 with a total of over 60 billion cubic feet. This peak, however, was not the highest peak, for during the year 1908 over 80 billion cubic feet was produced. Between these two high peaks the production dropped down to 16 billion cubic feet in the year 1921. The number of wells drilled during the year totals 1569. This figure is somewhat lower than the figure given in several trade journals because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly three-fourths (or 1107) of the total number of wells were completed as commercial oil wells (915 in western and 192 wells in eastern Kansas). The commercial gas wells completed number 50, of which 4 are in eastern Kansas and 46 in western Kansas. The remaining 412 completions include 130 dry holes in eastern and 282 dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year accounted for 70,000 bbl. of new oil for eastern and 1,220,000 bbl. of new oil for western Kansas. It is interesting to note in this connection that the number of wells completed in the state rose gradualIy to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918 when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak in 1937, the low point was reached during 1931, with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a new area whether it should be called a new pool or a long extension of an

Jan 1, 1939

By J. B. Austin, R. L. Rickett

MEASUREMENTS Of the rate of decomposition of austenite at constant temperature are commonly represented by plotting the percentage transformed on linear coordinates against time on either a linear or a logarithmic scale, a method that yields a curve that in shape resembles an integral sign (Fig. 1). A graph of this kind is not always convenient because extrapolation to the beginning or end of the transformation, or even interpolation, may be uncertain unless there are a large number of observations, which seldom happens; furthermore, the degree of consistency of a set of measurements is difficult to judge from such a curve. It is desirable therefore to find some mode of plotting, or even better to find a standard variety of graph paper, that gives a straight line instead of the integral shape. The straight line has many advantages; the number of readings required to fix the position of the curve is greatly reduced, interpolation is easy and rapid, extrapolation can be carried out with greater confidence and, finally, the consistency of the measurements is readily estimated from the scatter of the points. The last advantage is particularly valuable when the data are obtained by direct microscopic examination alone, because they are influenced by the skill of the observer in estimating the relative size of areas, possibly also by undetected inhomogeneity of the specimen. A search for ways of representing the observations as a straight line yielded two methods which are described in this paper. The paper also includes an account of some interesting relations brought to light in applying these methods to the available experimental data. Usually the best way to derive such a method of plotting is to base it on established principles of chemistry and physics, as has been done, for example, for the temperature variation of the equilibrium constant of a chemical reaction. But so little is known of the mechanism of the decomposition of austenite, and so little is available in the way of well established background for changes of this kind, that it is simpler to rely upon purely empirical means. The general plan therefore is to study existing data with a view to finding some function of the direct observations that will

Jan 1, 1938

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By Junius D. Edwards

WHEN Charles Martin Hall invented the electrolytic process for the production of aluminum, one basic requirement was a supply of pure alumina. Now, more than 50 years later, the same requirement still holds, and there are no technical straws in the wind to indicate that this situation is likely to change. Long ago, Aluminum Company of America took a number of steps to see that this country should not face shortages of alumina and aluminum in time of emergency. As one step to this end, the Company developed and used a supply of bauxite in South America in order to conserve dwindling Arkansas reserves. Another, and more a program than a step, was to investigate every type of process that might bear the possibility of utilizing the low-grade ores of aluminum that are more plentiful than bauxite. It is a long story, but the investigation included electric-furnace processes, acid extraction processes and alkaline extraction processes, with or without preliminary furnace and sinter treatments. Some of the processes developed were operated in commercial production. This work has been continuous since the first World War. The turn of the wheel came sooner than was expected when, in 1942, bauxite shipments through the Caribbean became uncertain and hazardous through the operation of submarines. The tremendous requirements of aluminum for the war effort were consuming high-grade bauxite at an alarming rate and a national search for substitutes began. High-grade bauxites, for technical and economic reasons, have been defined as those containing about 7 per cent or less of silica. While bauxite of this grade was limited in amount in the United States, there was in sight a substantially greater volume of low-grade, high-silica bauxite not amenable to economic treatment by the Bayer process, but richer in alumina than the clays or other available low-grade ores. It was at this point, and after several years of intensive research on this particular phase of the problem, that Aluminum Research Laboratories brought to completion the invention of one of its research staff, which made practical the utilization of large reserves of low-grade bauxite in America. BAYER PROCESS The Bayer process has been almost universally used for the 'production of alumina from bauxite. This process, in outline, comprises the digestion of finely ground bauxite in a solution of caustic soda (NaOH) under pressure and at an elevated temperature. Alumina in the bauxite goes into solution as sodium aluminate and the impurities-oxides of iron, titanium and silicon-remain undissolved. The undissolved residue, known as "red mud," from its color, is separated and run to waste. Aluminum hydrate (A1202.3H20) is precipitated from the solution of sodium aluminate, and the liquor containing the caustic soda and some alumina is returned to the process for digesting more bauxite. The aluminum hydrate, after washing, is calcined at a high temperature to produce

Jan 1, 1945

IN order that you may be expert in every phase of this art of parting, I wish to caution you upon twelve points, all necessary, so that you may know beforehand what may happen to you and what provision you must make to obtain good results. Understand that the gain derived from this art lies in carrying out the work that you wish to do accurately and with profit, which means nothing other than working with certainty and seeing that there is no loss of gold or silver [69v] or substance of anything that is valuable in itself. For, since everything lost is silver or gold, it is valuable however little. it may be, and many little things obviously make one large one; for gain increases gain, and loss, loss. Therefore, you will have as your first task to seek to have the materials that you are to use for making the aqua fortis of as perfect a nature as possible. I tell you this because the saltpeter is often weaker and of worse quality than the alum. For this reason it is necessary to make an effort to have it not only well refined and free from earthiness but also of a nature as powerful as pig [dung] saltpeter, the color of which tends strongly toward yellow. In order to work better, you also refine this again before you put it to use, as I shall tell you in its place. Likewise, see if you can get alum of the red kind that comes from the Levant or from Cartagena, for it costs less and is more powerful. Furthermore; see that you have a good number of well-formed cucurbits of properly purified glass not too large and of, equal content and size. Above all, see that they contain, no indentations, bubbles, folds, or scratches, especially, in the, body or in the bottom, because they break easily and the nature and great force of the acid pierces them by eating away, and makes a little hole. For this reason, cucurbits. are always divided into four grades; one is taken for making aqua fortis, another for drying the waters when they are laden with silver, the third for recovering the acids from the separations, and the fourth are either rejected as useless or dangerous, or are saved for recovering the whites or for some other service. Whoever wishes to practice this art well should remember to keep a large supply of cucurbits, receivers, and alembics. The third is the precaution which one must take in luting them; first, to

Jan 1, 1942

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By A. L. Holley

THE general usage of engineers, manufacturers, and merchants, is gradually, but surely, fixing the answer to this question. In every country rails, boiler-plates, and machinery bars, whether hard or soft, are almost universally called steel, when they are made from cast ingots. Other names for the softer steels, such as " homogeneous metal," " Bessemer iron," " Martin iron," and the like, have failed to obtain general recognition. The meaning of the term steel, before it was enlarged to cover newly developing varieties, has been traced, by a recent writer, down through Percy, Shakspeare, and the Bible, in a most interesting manner, from an archaeological point of view. Undoubtedly, it did characterize hardness and other qualities imparted by carbon. It is within the memory of most of us, that all steels were tool steels, and that the soft, structural varieties were introduced-varieties which harden but little, which bend cold, and which, in many physical properties, are akin rather to wrought-iron than to tool-steel. But, since both the hard and the soft steels are made by the same processes, and have their great, distinguishing structural feature in common, viz., homogeneity resulting from fluidity, it has come to pass, despite every other proposed nomenclature, that all the compounds of iron which have been cast in malleable masses, are called steel, the term wrought-iron being still confined to malleable iron made from pasty masses, and hence laminated in structure. No inconvenience has been found, so far, in distinguishing between the more or less carburized products, in general, by the terms " high-steel," " low-steel," " tool-steel," etc., and, in particular, by prefixing the percentage of carbon and other ingredients, to the terra steel. Steels which contain distinguishing ingredients other than carbon, are called "chrome-steel," " titanium-steel," and the like, just as variously compounded bronzes are called "phosphor bronze," "alu¬minium bronze," etc. Thus the combination of several words or symbols, and figures, may completely disclose the characters of the metal, in terms that are subject to no misunderstanding. But inasmuch as several high metallurgical authorities and clever writers have of late proposed to disturb this natural and somewhat settled nomenclature, it seems important to consider the claims of the various classifications. I shall attempt, in this paper, to show

Jan 1, 1876

By A. L. Holley

The general usage of engineers, manufacturers, and merchants, is gradually, bat surely, fixing the answer to this question. In every country rails, boiler-plates, and machinery bars, whether hard or soft, are almost universally called steel, when they are made from cast ingots. Other names for the softer steels, such as " homogeneous metal,'' "Bessemer iron," " Martin iron," and the like, have failed to obtain general recognition. The meaning of the term steel, before it was enlarged to cover newly developing varieties, has been traced, by a recent writer, down through Percy, Shakspeare, and the Bible, in a most interesting manner, from an archœological point of view. Undoubtedly, it did characterize hardness arid other qualities imparted by carbon. It is within the memory of most of us, that all steels were tool steels, and that the soft, structural varieties were introduced—varieties which harden but little, which bend cold, and which, in many physical properties, are akin rather to wrought-iron than to tool-steel. But, since both the hard and the soft steels are made by the same processes, and have their great, distinguishing structural feature in common, viz., homogeneity resulting from fluidity, it has come to pass, despite every other proposed nomenclature, that all the compounds of iron which have been cast in malleable masses, are called steel, the term wrought-iron being still confined to malleable iron made from pasty masses, and hence laminated in structure. No inconvenience has been found, so far, in distinguishing between the more or less carburized products, in general, by the terms " highsteel," "low-steel," "tool-steel," etc., and, in particular, by prefixing the percentage of carbon and other ingredients, to the terra steel. Steels which contain distinguishing ingredients other than carbon, are called "chrome-steel," "titanium-steel," and the like, just as variously compounded bronzes are called " phosphor bronze," " aluminium bronze," etc. Thus the combination of several words or symbols, and figures, may completely disclose the characters of the metal, in terms that are subject to no misunderstanding. But inasmuch as several high metallurgical authorities and clever writers have of late proposed to disturb this natural and somewhat settled nomenclature, it seems important to consider the claims of the various classifications. I shall attempt, in this paper, to show

By H. J. Stehli

The first sintering of zinc ores was done at the Bartlesville plant of the National Zinc Co., under the auspices of the late Otto Rissman. Mr. Rissman, who had had a long experience in the treatment of zinc ores, well realized all the difficulties of satisfactorily roasting zinc concentrates, which were becoming finer and dustier as each year went by—thus increasing the difficulties of roasting them in the existing forms of roasters, which were furnaces of the Ropp, Hegeler or similar types. Mr. Rissman's idea of the advantages of sinter was expressed in this way: in a zinc ore dead-roasted in a mechanical furnace there are many particles that are just like an egg; that is, they have a hard and impervious film of fused material on the outside, and in the retorting this completely cuts off access of the reducing gases to the center of the egg until a temperature has been reached at which this shell of the egg can be broken down through fusion. A particle of sintered zinc sulphide, on the contrary, is exactly like a piece of sponge. The moment the retort reaches the temperature at which the reactions can take place, they begin, because the reducing gases have ready access to the interior of the particles by means of the pores of the '" sponge." His faith in the advantages of sinter was amply borne out by the results obtained at the pioneer sintering plant for zinc ores installed by the National Zinc Company. Early Method of Sintering The method of procedure at Bartlesville was to roast the zinc concentrates down to somewhere in the neighborhood of 8 per cent residual sulphide sulphur; to cool these, then to wet them down to the proper moisture and mix them in the mixer of the sintering plant; then to sinter them by means of the heat available from the residual sulphides. The sulphur contents of the roast varied considerably, of course, as it was difficult with the furnaces in use to control the roasting exactly at any point short of dead roast. Hence at times the concentrates were roasted a little too low to sinter readily, and at such times the lack of sulphur was made up by the addition of raw concentrates to the sintering-machine charge in suitable amount.

Jan 1, 1937

By W. E. Bearce

The recent concern for the recovery of even the finest fractions of coal preparation plant feeds has created needs for new equipment. Thermal dryers currently available have difficulty reducing the filter cake moisture on down to the desired point. This difficulty involves 1) the physical problem of handling this wet, sticky material and making each particle accessible to the hot gases, and 2) removing the extremely fine dried particles from the cooled gases. The dryer described in this paper handles the first of these problems, and eliminates the second by the substitution of steel balls for air as the heat transfer medium. As a general statement, the cost of preparing coal for market is inversely proportional to the size of the lumps or particles. In the not too distant past the finer sizes were discarded as being uneconomical to treat and this practice might be still continuing if it were not for the insistence of the public that this material be kept out of our streams. This being the only cost-free outlet, the disposal of fine refuse became a significant item of expense in every preparation plant. When this happened it was only reasonable to look to the recovery of the values in this material, not only to defray this expense, but to reduce the tonnage which had to be wasted. There seemed to be no device available suited to reducing the moisture in this material to what the market requires. All of the fine coal dryers commonly employed make use of air to bring the heat of combustion into contact with the coal particles. Any device employing air as a heat transfer medium, has the following two strikes against it in attempting to handle 28 mesh by 0 filter cake: 1) It is practically impossible to bring the hot air into intimate contact with the enormous number of fine particles stuck together in the cake. 2) Even if this can be effected, it is impossible to remove the dried coal from the air. A wet scrubber must be employed, the discharge of which must go back to the filter and dryer as a circulating load of the most objectionable sort, being the extreme fines. Various compromises have been used to cope with the problem of drying this relatively small tonnage of high moisture coal. Often some of the dried coal is mixed back with the feed to the dryer in an attempt to make the mixture more handleable and more available to contact with the hot air than the filter cake alone would be. This may help to some extent with the first problem but it does nothing about the second and a dryer operated in this way has to be oversized. Sometimes the filter cake is mixed with a coarser fraction for the same reason. Here again, while this may make a mixture (the particles of which are more readily brought into contact with the hot air), the problem of getting the fine coal out of the air remains and a larger percentage of the total coal to be dried is handled by the most expensive means. Mechanical dewatering has accounted for more and more of total coal drying lately and in many cases would satisfactorily handle the whole load, down to 28 mesh, if there were a means available for doing a good job on the —28 mesh by itself. The dryer which is the subject of this paper was designed expressly for doing this job — drying fine material by itself regardless of how wet it may be to start with, how fine it may be, or how gummy and sticky these properties in combination may make it. The essential features are depicted in Fig. 1. A rotating cylinder is supported on a frame in such a way that one end may be raised or lowered by hy-

Jan 1, 1968