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By G. S. Baker, S. H. Carpenter

Langenecker has reported significant reduction in strength of high-strength metals during ultrasonic t'ibration. Decreases in static yield stress an order of magnitude greater than the calculated stress amplitude of vibrations were reported by him for a stainless steel and for tungsten. in the present work, attempts were nzadc to verify such large reductions in yield and flats stresses using resonant librations of measured amplitudes. The results show that both the soft metals (copper and aluminum) and the high-strength metals (sleels) hare reductions in yield and .flow stresses no larger than the stress amplitude of libration. BLAHA and Langenecker,' investigating the effect of vibratory stresses on the deformation of zinc and aluminum, found a decrease in the static yield and flow stresses approximately equal to the vibratory stress imposed. Langenecker later extending this work to high-strength metals such as stainless steels and tungsten2 found a much larger effect. In these metals the static yield and flow stresses decreased by an amount more than an order of magnitude greater than the calculated vibratory stresses. It was suggested that this phenomenon could be a serious hazard to high-strength structures in an acoustic environment, such as a large rocket at launch, or could be used advantageously in the working of hard-to-work materials such as the refractory metals. Langenecker and others3 have investigated the effect of high-amplitude vibrations on many metal-forming operations. The results have been quite favorable with usually a large decrease in the energy necessary for the forming operation. The processes, however, involve large frictional forces and it is not clear whether the decreases in forming forces are to be ascribed to decreased friction or to decreased flow stresses. The present paper reports an attempt to determine the effect of accurately known vibratory stresses on the static yield and flow stresses. I) EXPERIMENTAL TECHNIQUE The standard multicomponent resonator technique for measuring internal friction has been adapted to allow simultaneous high-amplitude vibration, internal-friction measurement, and tensile deformation. This has been described in detail elsewhere.4 Longitudinal oscillations of approximately 50 kc frequency are excited in a multicomponent resonator by a quartz transducer. A second transducer measures the amplitude of vibrations. Fig. 1 shows a schematic drawing of the resonator and grip arrangement and the displacement pattern produced. Since the centers of the dummy bars are at displacement nodes, they represent points where attachments will not materially affect the vibrations. The force is applied by a standard Instron tester. The sample may be deformed while simultaneously vibrating at up to 104 strain amplitude. 11) EXPERIMENTAL RESULTS The effect of high-amplitude vibrations on the yield and flow stresses of copper. aluminum, tantalum. a soft iron, and a stainless steel has been measured. In addition samples of tungsten vibrating at stress levels up to 10' dynes per sq cm have been subjected to static stresses near the static yield stress with no indication of macroscopic deformation. Fig. 2 gives typical results for 99.999 pct polycrys-talline copper. A vibratory stress of 7 x 107 dynes per sq cm is applied at points "a" and removed at points "h". The behavior of aluminum is identical. In agree-

Jan 1, 1967

By John Henry Harden

IN 1874, with Mr. H. Y. Attrill, of Baltimore, Md., I made an examination of some property at Goderich with reference to sinking for and mining salt. With this end in view we visited all the wells in the neighborhood, but the information sought being of so unreliable a character I advised the putting down of a borehole on the property. This has since been done, the result of which has lately been published by Dr. T. Sterry Hunt in the Toronto Globe. From this there appears to have been passed through six beds of salt of an aggregate thickness of 125 feet. Rock-salt was known to exist, for, by the boring of existing wells, small crystals had been brought to the surface in the dirt, but no attempt had before been made to obtain a reliable sample or to prove the number and thickness of the beds. The question now remaining for discussion is, shall the present method of obtaining the salt be continued, or shall the beds be won by a shaft in a regular mining fashion, by which means the salt may be gotten in a condition almost ready for the market? The present mode of obtaining salt is by boreholes from 6 inches to 8 inches in diameter drilled to the beds, into which is inserted a pump. The "feeders" of fresh water intersected in drilling the well are allowed to descend on the outside of the pump-tube to the salt beds and there become saturated, when, on use of the pump, brine is obtained for evaporation. In the beginning brine can only be had in limited quantity, but by the daily application of the pump, and the gradual solution of the salt, a larger surface becomes exposed to the action of the fresh water, and a continuons supply of brine is obtained. It will then be understood that the supply of brine is dependent upon the feeders of fresh water intersected in boring the well, which, we are told, have never shown any sign of diminution, and this is the water that must be encountered in sinking a shaft. There are ten wells in operation at Goderich, the most important one to the present project being known as the Hawley Well, located at an elevation a few feet above Lake Huron at the mouth of the river Maitland, at, a much lower level and nearer to the proposed shaft than any other well in the district. At this well the feeders

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By Haakon Styri

In discussion of Dr. Fitterer's paper on electrolytic separation of slag inclusions, some results from experiments on electrolyzing high-carbon steels at the SKF Research Laboratory were given. l We had been working for a number of years on chemical methods of separating the inclusions but could not find any solvent that would dissolve the steel without attacking some of the inclusions, particularly the sulfides in which we were mostly interested at the time, nor any that would dissolve all sulfide or silica in filings as fine as 300 mesh without attacking the iron. Electrolytic methods had also been tried without any real progress until we learned from the Bureau of Mines about the use of the collodion membrane around the anode. Our early difficulties were to some extent different from those of the Bureau of Mines, perhaps because of experimenting on steels of higher carbon content, but most of our difficulties were of the same nature as those of the Bureau. Formation of large quantities of basic hydroxides was traced to the use of impure and oxidized ferrous sulfate. To protect from oxidation from the atmosphere during electrolysis, after purer chemicals were obtained, a thin layer, 54 in. or less, of molten paraffin was poured over the surface of the cathode liquid, where it solidified. It was found desirable also to hold the cathode chamber slightly acid by initial addition of 0.1 per cent acid (sulfuric or hydrochloric) to prevent precipitation of the hydroxide. This acidity would decrease gradually and the cathode chamber would become neutral before the end of the electrolyzing. The increase in acidity in the anode chamber during our early experiments had appeared to cause attack of the precipitated sulfides in the residue, which originally was analyzed by volumetric method for sulfur, and for this reason a 10 per cent sodium citrate solution was substituted for the sulfate in the anode chamber. With the use of the more reliable Eschka method for sulfur determination (as in coke), there was however no serious attack on the sulfides in the anode chamber with a variety of different liquids, as shown in Tables 2 and 4. The Eschka method gives a higher sulfur value than

Jan 1, 1933

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By Glenn R. Zellars, J. P. Morris

The carrier gas method was used to measure the vapor pressure of copper over liquid copper and Fe-Cu alloys. From these results, the activity of copper in the alloys was determined at 146°, 1550°, and 1600°C. Calculations of the activity of iron were made from the results for copper. The activities of copper and iron show strong positive deviations from Raoult's law. KNOWLEDGE of vapor pressures of liquid metals has both practical and theoretical value. Fuming of metal baths is directly related to vapor pressure, and the data should bc particularly important to the technology of vacuum metallurgy. Theoretical applications include determinations of heats of vaporization, heats of solution, and activity coefficients in alloys. Methods for measuring vapor pressures of metals have been reviewed by Speiser and Spretnak.' High-vacuum procedures, such as the Langmuir and Knudsen methods, have been used most widely in recent years. However, these methods are not applicable to vapor pressures greater than lo-' mm Hg and often cannot be used in the temperature range of greatest interest. The purpose of this investigation was to develop a procedure for measuring vapor pressures of pure metals and alloys that would be applicable to pressures greater than lo-' mm Hg. The transportation or carrier gas method has been used. Copper was chosen for the initial work because its vapor pressure has been established fairly well and the reliability of the technique could be ascertained. Applicability to alloys was studied by determining the vapor pressure of copper over liquid Fe-Cu alloys. Experimental Procedure The tests were carried out in a graphite-spiral resistance furnace. The charge consisted of 50 g of metal contajned in a covered sintered-alumina crucible 1/2 in. deep and 13/8 in. ID. Two sintered-alumina tubes led from outside the furnace to within the crucible, passing through close-fitting holes in the crucible cover and radiation shield. The arrangement of the crucible and the two alumina tubes is shown in Fig. 1. The small-bore tube (1/16 in. ID by 5/16 in. OD) served as the inlet for the carrier gas. The tip of this tube touched the metal surface and the flow of gas imparted a rippling motion to the metal. In this manner the gas was brought into close contact with the metal and became saturated with metal vapor. In most of the tests the flow rate of the carrier gas was 560 ml per min, measured at room temperature. Approximately half of this saturated gas was allowed to escape from the crucible through the second alumina tube (3/16 in. ID by 5/16 in. OD) and was discharged to the atmosphere through a

Jan 1, 1957

By K. Leutwyler, H. L. Bigelow

Jan 1, 1966

By Louis C. McCabe

The control of dusts and fumes of submicron size is involved in many process industries. This paper presents in tabular form the quantitative data from a number of metallurgical operations and discusses allowable discharge in terms of effluent-weight ratio. Typical installations for recovery of stack effluents are cited. THERE are many sources of smoke, fumes, gases, and dusts that may cause undesirable contamination in an industrial area. Fumes and gases are the result of chemical action or volatilization, while dusts are produced in processes of disintegration and dispersion. Commonly, smokes are suspended particles formed by combustion or destructive distillation. Methods for controlling smoke are generally known, and great improvements have been made in equipment for removing fine dusts and fumes from gases. In most of the industrial centers of the country, the chief duty of the air-pollution abatement agency is the elimination or reduction of emissions resulting from improper combustion. Correct methods of firing, proper fuel selection, and installation of properly designed equipment may accomplish this. It is becoming more widely recognized that much of the contamination of an industrial atmosphere is caused by dusts, fumes, and gases that are not related to the process of combustion. As such emissions are usually a functional part of plant operation, they rarely can be prevented even by better design and careful operation. When dusts, fumes, and gases are an integral part of the operation, mechanical equipment must be designed to remove these emissions. Most of the dusts and fumes that should be controlled are less than 1 micron in size. Control of such small particles is largely a new and untried field in many industrial areas. However, where conditions have been critical, effective control equipment for dusts, fumes, and gases has been in operation for many years. The problem is not one of smoke abatement and requires an entirely different set of standards for effective solution. Identical standards need not be applied to all industrial areas because of differences in meteorology, physiography, plant location, plant density, and nature of stack effluents. In this paper, discussion of control of atmospheric contamination by industrial plants refers specifically to the Los Angeles area, but the method of approach is applicable to any area where similar problems are encountered. Quantities of particulate matter reported in analysis of stack effluents indicate the need for standards of emission. Many types of dusts and fumes that contribute materially to the air-pollution problem are discharged into the atmosphere at a lower rate than 0.40 grain per cu ft at standard conditions. On the other hand, some stacks discharge at a higher

Jan 1, 1951

By Louis C. McCabe

The control of dusts and fumes of submicron size is involved in many process industries. This paper presents in tabular form the quantitative data from a number of metallurgical operations and discusses allowable discharge in terms of effluent-weight ratio. Typical installations for recovery of stack effluents are cited. THERE are many sources of smoke, fumes, gases, and dusts that may cause undesirable contamination in an industrial area. Fumes and gases are the result of chemical action or volatilization, while dusts are produced in processes of disintegration and dispersion. Commonly, smokes are suspended particles formed by combustion or destructive distillation. Methods for controlling smoke are generally known, and great improvements have been made in equipment for removing fine dusts and fumes from gases. In most of the industrial centers of the country, the chief duty of the air-pollution abatement agency is the elimination or reduction of emissions resulting from improper combustion. Correct methods of firing, proper fuel selection, and installation of properly designed equipment may accomplish this. It is becoming more widely recognized that much of the contamination of an industrial atmosphere is caused by dusts, fumes, and gases that are not related to the process of combustion. As such emissions are usually a functional part of plant operation, they rarely can be prevented even by better design and careful operation. When dusts, fumes, and gases are an integral part of the operation, mechanical equipment must be designed to remove these emissions. Most of the dusts and fumes that should be controlled are less than 1 micron in size. Control of such small particles is largely a new and untried field in many industrial areas. However, where conditions have been critical, effective control equipment for dusts, fumes, and gases has been in operation for many years. The problem is not one of smoke abatement and requires an entirely different set of standards for effective solution. Identical standards need not be applied to all industrial areas because of differences in meteorology, physiography, plant location, plant density, and nature of stack effluents. In this paper, discussion of control of atmospheric contamination by industrial plants refers specifically to the Los Angeles area, but the method of approach is applicable to any area where similar problems are encountered. Quantities of particulate matter reported in analysis of stack effluents indicate the need for standards of emission. Many types of dusts and fumes that contribute materially to the air-pollution problem are discharged into the atmosphere at a lower rate than 0.40 grain per cu ft at standard conditions. On the other hand, some stacks discharge at a higher

Jan 1, 1951

By H. C. H. Darley

The principal causes of unstable boreholes* have been known for many years. For example, in a paper published in 1938, Halbouty and Kaldenbachl listed nearly all the classes of troublesome shales that we know today. Much progress has been made since then, but we still have difficulty in identifying the cause of hole problems and consequently in selecting the right technique for combatting them. This subject was discussed at length by Kelly2 in a recent paper and much valuable information was provided. In the Shell Laboratory it was felt that there was a need for a better understanding of the basic mechanisms underlying the various forms of hole instability, and accordingly, a study was undertaken. This entailed reviewing the physics and chemistry of shales, developing tests for characterizing shales, and constructing a model to study borehole stability. Full simulation of underground conditions was not attempted; for example, we used reconstituted shale specimens, and often simple solutions or suspensions rather than practical drilling muds. Such procedures are necessary in order to establish mechanisms, but caution must be exercised in applying the results to the more complex conditions in the field. Part I — Compaction Swelling and Dispersion of Shales Compaction of Sediments Shales are formed by the compaction of sediments. Water is expressed as sediments are buried by subsequent layers, and the degree of compaction is proportional to the depth of burial, provided the water is able to escape easily to permeable formations. The younger sediments, when recovered at the surface, soften and disperse when mixed with water; the older shales have undergone diagenesis (alteration of the clay minerals, secondary cementation, etc.), and remain hard and unaffected by water. In this paper we shall apply the term "shale", as the drilling engineer does, to everything from clays, which are highly reactive to water, to completely lithified materials such as claystones and slates, which are completely inert. However, because these materials behave quite differently when encountered in the drilling well, it is desirable to develop a simple means of characterizing them. The feature that distinguishes the various shales is their dispersibility in water —soft clays disperse readily, harder shales disperse slowly when agitated, the lithified materials will not disperse at all unless milled. In the dispersibility test used in our study, a weighed amount of dry shale particles in the 12-to-100-mesh-size range was placed in a tube filled with distilled water and allowed to soak for 16 hours. The

Jan 1, 1970

By C. R. St. John, R. W. Lindsay, Charles R. Austin

Many of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys.l,2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)= and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650" to IOOO °F. as a consequence of additions of 0.40 to 0.60 per cent of this element in carbon steels of the order of 0.25 to 0.35 per cent carbon content. Babcock and Wilcox Tube CO.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or I per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to1000°F. 4

Jan 1, 1945

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.' The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By O. B. Bucklen, J. P. Matoney, P. G. Meikle, R. L. Terry

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also holds true for loading and storage facilities. Where once a 1 million st per yr (910,000 mt/yr) mine was rare, 3-5 million st per yr (2,730,000-4,550,000 mt/yr) mines are not uncommon today in the bituminous industry. This great increase in production, made possible through mechanization, requires greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend to- ward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw-coal storage and blending facilities. The development of the unit train with its attendant economics has contributed more than any other factor to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has added to the need for faster and larger loading facilities. In this climate of rapidly changing technology, any written ac-

Jan 1, 1979

By Radoslav Despotovic

The developed radiometric method of particle system analysis has been applied to investigate the bulk properties of particles precipitated from solutions. The nature and principles of the method applied are described briefly, and some possible models in the field of fine colloid particles precipitation discussed. Changes in radionuclide distribution were followed during the solid phase formation and the data were used to calculate changes in bulk composition of colloid precipitates. The radiometric data show interesting phenomena closely connected with the characteristic of bulk particles. The measured radiometric data are highly reproducible, the applied methods have proved to be sensitive, and the developed techniques have been tested by various standard procedures.

Jan 1, 1980

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 Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.' This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2'6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7'9 These effects were observed at testing temperatures in the range 100 to 300'. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.' These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180' was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio 'c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By R. A. Deju, R. B. Bhappu

Further information on the surface characteristics of the silicate minerals was obtained by experimentally correlating the oxygen-silicon ratio of the silicates with their electrokinetic properties. Specifically, the behavior of the minerals in an electric field was investigated using zero point of charge as a parameter. A modified electrophoresis cell was used for the determination of electrophoretic mobilities. It was shown that there is an increase in the zero point of charge with increasing oxygen-silicon ratio in the silicates. Finally, a chemical interpretation was presented to describe the surface phenomena observed in the experiments. In recent years great interest in surface chemistry has produced a number of methods to study the surfaces of minerals and to observe the phenomena occurring at their interfaces. One such method is discussed in this paper. A rather complete review of the surface characteristics of the oxide minerals has been undertaken by parks,' but, a similar study has not been made for the silicate minerals. Two previous papers by the authors2'3 attempted to remedy this situation. In these papers it was demonstrated that the reaction between the silicate mineral particles and acidic water involves mainly an exchange of metal ions for hydrogen ions on the surface of the solid, leading to an increase in pH of the aqueous phase. Also, the degree of reaction was found to depend on the oxygen-silicon ratio of the silicate structure, being least for the quartz and greatest for the olivines. A hypothesis was then set forth explaining that upon the fracturing of a silicate mineral, the oxygen-metal bond (which is almost entirely ionic in character) will break more easily than the stronger oxygen-silicon bond. This results in the exposure of unsatisfied oxygen sites on one hand and active, exchangeable cations on the other. These active sites on the fractured surfaces are then available for reaction with the hydrogen ions in acidified aqueous solution. Thus, an increase in degree of adsorption of hydrogen ions occurs as the oxygen-silicon ratio increases due to the presence of a larger number of active sites on such minerals. A correlation between oxygen-silicon ratio and electrokinetic properties will be further pursued in this paper from both the theoretical and experimental points of view. Efforts will then be made to present a chemical interpretation of surface phenomena observed in the experiments. It is believed that this study may supply pertinent information on the behavior of silicate minerals in froth flotation systems. ELECTROKINETIC STUDIES Equipment: In a previous paper,2 Deju and Bhappu described a simple method for determing the zero point of charge using a potential across a cata-phoresis cell and observing particle movement by means of a Rayoscope* optical system. This setup is simple in design and operation and extremely reliable. With care, reproducible results within 1.5% accuracy may be obtained. A new setup has been developed, based partly on the design by Zeta-Meter Corp.4 and partly on previous cells used at the New Mexico Bureau of Mines. This new, modified cell is shown in Fig. 1. Although

Jan 1, 1967

By L. D. Wooddy, W D. Moore

Water drives may be natural or artificial. For the case of a natural water-drive reservoir, the volume of water influx corresponding to reservoir pressuve-production history may be calculated by means of the material bal-ance-unsteady state equation. For the artificial water drive or pattern injection water flood, the material balance equation is sufficient to determine the reservoir pressure-production, injection history. However, for both cases to reliably predict reservoir performance, it is necessary to calculate the saturation distribution of the reservoir fluids at different stages of depletion. This paper consolidates the various equations used to determine the performance of water-drive reservoirs into one approach that is applicable to any reservoir that has a natural water drive or is to be produced by water injection. The numerical procedure has been simplified considerably, and the solution is adaptable to either hand calculations or digital computer operation. INTRODUCTION A water-drive reservoir is one in which the predominant source of energy for production of oil results from the encroachment of water into the oil zone. The water drive may be either natural or artificial. Water invasion takes place by expansion of water in the aquifer as a result of the pressure decline transmitted from the oil reservoir. Because water is practically incompressible, a natural water drive requires an extensive aquifer containing a volume of water many times the volume of oil in the reservoir. Provided the permeability of the formation is reasonably high, a moderate decline of reservoir pressure usually causes adequate water influx. If the reservoir pressure decline becomes excessive because of low permeability or a high rate of production, part of the oil production may result from the liberation of dissolved gas which may cause excessive quantities of free gas to be produced along with the oil. In extreme cases, reservoir pressure may decline so rapidly as to cause the oil to be produced predominantly by dissolved gas drive, leading to abandonment of the reservoir before the advancing water has had a chance to flush the entire reservoir. In reservoirs that are not connected to extensive aquifers, an artificial water drive may be created by injecting water into or around the lower edges of a reservoir. Sometimes water is injected within the reservoir through wells interspersed among the producing wells. When injection is carried out in such fashion, the reservoir is in effect subdivided into a number of separate producing segments, in each of which the displacement of oil is simultaneously taking place, and the shapes of which are fixed by the well patterns employed. Because of the natural tendency of oil and water to segregate according to their relative densities, water will tend to migrate downdip regardless of where injected. Accordingly, the injected fluids can be retained within the intended reservoir segments only when conditions are unfavorable to their migration under the force of gravity. Pattern injections are usually confined, therefore, to reservoirs having low structural relief, or low permeability, or when production and injection rates are such that fluid movements in the reservoir are dominated by the pressure gradients rather than by the force of gravity. In the case of natural water-drive reservoirs and artificial water-drive reservoirs in which the water is in-

Jan 1, 1958

By E. S. Anolick, Joseph Singer

The magnetic after-effect, in the form of time decay of permeability (l/µ), has been used to obtain independent data on the solubility of' carbon in pure iron. The results differ slightly from the solubilities obtained through internal -friction experiments. The mechanism of the time decay being the magnetic analogue of internal friction, it appears necessary to explain the observed discrepancies, and some suggestions are made. THE purpose of this work was to establish the reliability of the time decay of permeability as a measure of dissolved interstitial in the body-centered-cubic lattice, and further, to establish techniques suitable for such measurements with samples of a form convenient for various other measurements. This particular sample form was the "epstein" strip, i.e., 25 cm by 3 cm by 0.035 cms. While the general conclusions are not limited by this geometry, there are two aspects of the samples that may be relevant: a) texture, and b) grain size, which ranged generally from 1 to 10 mm. Effects due to these two possible parameters were thought to be small and were not investigated. Calibrating the time decay technique and the other experimental procedures by measuring the solubility of carbon in pure iron suggested itself because of the accumulation of data on this subject through the related technique of the internal friction'; The essentials of this report have been published in a somewhat condensed form.5 Since then some additional data have been taken. It is the purpose of this paper to add these data and to provide more complete description of the experimental techniques than was possible then. The time decay of permeability is a form of the magnetic after-effect.6,7 Permeability is measured immediately after demagnetization (µº) and also long after (µ8). The time decay, ?(l/µ), is the difference 1/µ8 - 1/µ0 and has been considered to be proportional to the concentration of a dissolved interstitial6,8,9,12 The relaxation time! 7, is characteristic of a particular diffusion, and affects the permeability as follows: where he being the activation energy for diffusion of the interstitial. Reference is made to the works of snoek6 and Neel7 for a complete discussion. A brief exposition of the principal ideas may be in order here, as follows. On the basis of the simplest model, resistance against domain wall motion increases with time after demagnetization due to the diffusion of interstitials to preferred sites created by the magnetostrictive tetragonolization under the strong magnetic field. Thus permeability, measured with a small field after the abrupt removal of the large field, will continuously fall with the process of diffusion of the interstitials, and the total "time decay" (or "time decrease") should be proportional to the amount of interstitial in solid solution. In the present report, use is made only of the total time decay rather than of the nature of the progress of the decay; the only problem involved in this approach is the need for assurance that only one interstitial is contributing to the effect as used. It is felt that the special use made here of the total time decay warrants the conclusions. Other work has been going on elsewhere on the detailed study of the nature of the time decay.8'9 EXPERIMENTAL A) Materials—12-lb ingots were made in a vacuum furnace from high-purity iron and by a series of hot and warm reductions were brought down to 14-mil strip. This was cut into 25-cm epsteins. The pure iron was decarburized at 750 °C by hydrogen. The time decay measurement for the decarburized iron (see below) indicated a satisfactorily low starting level of interstitials. Grain growth to grain sizes of 1 to 10 mm was produced in the pure iron by a 700" anneal in hydrogen after a critical reduction of about 7 pct as suggested by previous trials. No measurement of texture in the pure iron was made. The grain size was taken to be large enough to be beyond any sharply critical size regarding solubility. B) Infusion of Carbon—Since the permeability measurement required about two dozen epsteins, a special method of carbon infusion had to be developed to ensure homogeneity of infused carbon. This was accomplished by setting the samples edgewise in a

Jan 1, 1961