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By F. Julius Fohs

Centrally located with relation to the largest iron- and steel-producing districts of the United States, the fluorspar-deposits of Kentucky possess increasing interest and importance. As typical of the numerous fluorspar-mines of Kentucky and Illinois, I have selected for description the Memphis, because it and others of its immediate group exhibit the conditions characteristic of all. I. The Memphis MiNe. This mine lies 5 miles NW. of Marion, in Crittenden county, Kentucky, a station on the Chicago and Nashville division of .the Illinois Central R. R. For the first mile and a half out of Marion we see only Birdsville or Middle Chester sandstones of Mississippian age. Then we cross a fault of about 850 ft. displacement, and the Ste. Genevieve oolite sets in. Beyond the fault, oolite is the predominant rock, except that the hills to the north have a capping of Cypress or lowest Chester sandstone, 80 ft. below which is an outcrop of from 6 to 10 ft. of Ste. Genevieve (Rosiclare) sandstone. Occasional sink-holes are noticed, and as the mines are approached evidence of faulting is again seen. A line of .crude head-frames and open-cut dumps, extending for more than a quarter of a mile, marks the Klondike vein. The open-cuts are from 15 to 20 ft. deep, and in most of them, from the surface down, was found the reddish gravel which is really fluorspar—some of it white or purple and crystal-clear (if the red clay is washed off), and some carrying iron and silica, and stained by waters from the decaying limestone walls. In one of these cuts, at a depth of 20 ft., white and purplish honey-combed fluorspar was found, in which the larger cavities are due to the leaching of limestone and calcite, and the minute ones to the leaching of zinc-hlende.

Jan 1, 1910

By R. S. Reed, D. L. Ward

This paper is the result of a study, in 1919, to determine how much surplus power could be produced through the proper utilization of the entire gas flow from the two furnace stacks at the Federal Furnace Plant, South Chicago, 111. Obviously, the problem was to measure the flow of gas through the main beyond the point where the amount necessary for stove operation mas rermoved. In all probability, blast-furnace gas is the most difficult gas to measure, because of the high moisture and dust content, and the widely fluctuating flow from the furnaces. This wide fluctuation of flow forbids the acceptance of any one group of flow road-ings as indicative of normal operating conditions. A study of the conditions showed that a recording device on gas flow was necessary. As the gas at the point of measurement had passed through met washers, and accordingly was saturated with water and contained considerable dust carried past the scrubbers in the form of sludge, no form of Pitot tube could be used, for this sludge would quickly plug the dynamic. and static holes, spoiling the gage readings. An even more serious objection to the use of Pitot tubes was the impossibility of accurately measuring the cross-sectional area of the gas main on the plane of Pitot-tube installation. Given an absolutely clean gas and a perfectly circular pipe, it would be safe to assume, through measurements of the pipe diameter, that the gas main was of a certain cross-sectional area. But the continual depositing of sludge and the fact that the main mas fabricated from riveted sheets led us to discard the idea of using Pitot tubes for. this service. The Venturi tube mas then considered, and had there been a sufficiently long straight run of gas main to accommodate a tube of the required size (72 by 28 in.) such an installation would very likely have been made. A plate with a sharp-edged orifice was eventually accepted as it possesses all the characteristics of a Venturi tube, requires less space, and

Jan 1, 1922

By R. S. Reed, D. L. Ward

This paper is the result of a study, in 1919, to determine how much surplus power could be produced through the proper utilization of the entire gas flow from the two furnace stacks at the Federal Furnace Plant, South Chicago, 111. Obviously, the problem was to measure the flow of gas through the main beyond the point where the amount necessary for stove operation mas rermoved. In all probability, blast-furnace gas is the most difficult gas to measure, because of the high moisture and dust content, and the widely fluctuating flow from the furnaces. This wide fluctuation of flow forbids the acceptance of any one group of flow road-ings as indicative of normal operating conditions. A study of the conditions showed that a recording device on gas flow was necessary. As the gas at the point of measurement had passed through met washers, and accordingly was saturated with water and contained considerable dust carried past the scrubbers in the form of sludge, no form of Pitot tube could be used, for this sludge would quickly plug the dynamic. and static holes, spoiling the gage readings. An even more serious objection to the use of Pitot tubes was the impossibility of accurately measuring the cross-sectional area of the gas main on the plane of Pitot-tube installation. Given an absolutely clean gas and a perfectly circular pipe, it would be safe to assume, through measurements of the pipe diameter, that the gas main was of a certain cross-sectional area. But the continual depositing of sludge and the fact that the main mas fabricated from riveted sheets led us to discard the idea of using Pitot tubes for. this service. The Venturi tube mas then considered, and had there been a sufficiently long straight run of gas main to accommodate a tube of the required size (72 by 28 in.) such an installation would very likely have been made. A plate with a sharp-edged orifice was eventually accepted as it possesses all the characteristics of a Venturi tube, requires less space, and

Jan 1, 1922

By Richard W. Lodge

Several methods, both wet and dry, for the assay of zinc-box residues from the cyanide process, have been described in recent years, and each of them has been claimed to be superior to all others. In the year 1901, a paper, entitled "Assay of Zincy Precipitates," was published ill the School of Mines Quarterly to the purport that the scorification method for the assay of zinc-box residues was absolutely unreliable. In order to shed light on this matter, the following experiments were undertaken by Messrs. C.B. Hollis and F. D. Kehew, undergraduate students at the Massachusetts Institute of Technology. The zine-box residues used were obtained through the courtesy of Mr. H. R. Batcheller. The samples were very rich and varied greatly in the fineness of their condition. SCORIFICATION-ASSAYS. In the preliminary tests, the charge, which was weighed on a chemical balance, consisted of 0.1 Assay Ton of residues mixed with from 30 to 35 grammes of test-lead and placed in a 3-in. scorifier, over this an additional quantity of test-lead (from 30 to. 35 grammes) was placed for a cover, and borax-glass, varying in quantity from 3 to 15 grammes, was sprinkled over the top of each charge of the various assays for a cover. The charges were scarified in a muffle-furnace heated to the ordinary temperature which is used in scorification; in some cases the door of the muffle was left open, while in others it remained closed. Generally, the charges spit badly, especially in the assays that were made with door of the muffle left open, or in those in which the door was opened too quickly. The results of the preliminary assays showed: 1. That in order to obtain approxi-

Jan 1, 1904

By A. M. Gaudin, C. S. Chang

IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.1-4 The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods.5-6 In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba140 to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,4 were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand picked quartz, washed free of stains, were reduced in size to -20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This -200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then' was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn,, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.7 The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74 micron quartz particles, using a surface factor of 1.96,8 is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1952

By Ellsworth Daggett

The Berlin gold-quartz mine is situated in Nye county, Nevada, on the west flank of the Shoshone range, about 40 miles south and 30 miles west from the town of Austin, the county-seat of Lander county. The distance from Austin is about 60 miles by stage-road. The outcrop of the vein, at the top of the incline-shaft, is situated just at the base of the mountain proper, almost exactly at the intersection of the mountain-side with the gravelly bench that slopes for about three-quarters of a mile to the flatter sage-brush plain, or desert valley, below. The vein itself consists almost entirely of quartz, with perhaps 2 per cent. of sulphide of iron, copper, lead, zinc and antimony, and perhaps a trace of some of the compounds of tellurium with gold and silver, although none of the latter have been as yet positively identified. The relative proportion, by weight, of silver and gold in the ores, varies in different parts of the vein, from 12 silver for 1 of gold, to 7 silver for 1 of gold. The quartz vein-filling is usually frozen fast to the walls, and is very hard and compact, seldom showing the friable, fissured, or shelly structure often to be found in quartz-veins. Comparatively little evidence of relative motion of one wall of the vein upon the other is to be found—a fact indicating that during the formation of the vein, and prior to the extensive movements herein described, little disturbance had taken place. No evidence whatever of metasomatic origin has been observed. On the other hand, occasional occurrences of comby structure, in which the axes of the quartz-crystals are at right angles to the plane of the vein, rather indicate deposition from solution in a pre-existing fissure. Spurs, or branches, and small parallel veins, while not en-

Jan 1, 1908

By C. K. Leith

At the outset I would like to make it clear that I do not enter this discussion in a controversial spirit, but in an attempt to contribute something helpful to an understanding of a difficult problem. I have too high regard for the- sterling quality of the work of the men who have studied this subject in detail to offer anything in the way of essential contradiction to their statements of fact. Difference of opinion arises from differing valuation of the possible alternative hypothesis which these facts suggest. Some degree of recrystallization in limestone contact zones has been recognized by many investigators. Earlier investigators, for the most part, assigned an important, if not the most important, ro1e to recrystallization in development of these zones. With the growing recognition of introduction of ores and gangue materials into the contact zone from igneous rocks through the medium of primary magmatic solutions, there has been a tendency to ascribe to this process most, if not all, of the chemical and mineralogical characteristics of the contact zonc. This has involved a correspondingly diminished emphasis on recrystallization of substances already there as a factor in the process, and in some cases even the complete elimination of this hypothesis. From detailed study of a few contacts, casual observation of others, and a general familiarity with the literature, some of us have been led in recent years to raisc the question whether the pendulum has not swung too far away from recrystallization toward direct introduction from igneous sources, and to argue for more recognition of the part played by recrysta11ization.l The inevitable sequence has been that those of us who have .taken this view have been charged, at least by inference, with emphasizing recrystallization to the total exclusion of the alternative process. Scientists, like other men, like to classify and pigeon-hole views under simple and definite designations, leaving out qualifications which would tend to make the classification more difficult to state. This has made the problem seem more definite and simple, but has tended to obscure the fact that the disagreement is primarily not one relating to essential facts, but one of

Jan 1, 1915

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

By Luther B. Eames

The recovery of dissolved gold from slime pulp in the cyanide process was first accomplished by intermittent decantation. This simple process consists in mixing with the pulp containing the values in solution, a solution of lower gold content, settling the mixture in a tank and decanting the clear supernatant fluid. The thick pulp remaining in the tank is pumped to a second tank together with more barren-solution and again settled and decanted. After several repetitions of this operation, values are so far reduced that further washing is not profitable. The gold recovery of this process is high, but the plant required is bulky, labor cost is high and the amount of solution to be precipitated is excessive. Historical Data As early as 1901, a plant was built in the Black Hills of South Dakota by John Randall, employing the same principles but attempting to make the process continuous by substituting for flat-bottomed tanks, cones which operated continuously, receiving a constant feed and discharging a steady stream of thickened pulp. These cones were operated in series, the thick underflow of the first one forming, with a stream of diluting solution, the feed to the second cone of the series. Barren solution was added to the tank immediately preceding the discharge tank and, after being slightly enriched by the low-grade pulp in this tank, overflowed to form a diluting solution again for the richer feed entering the third tank from the end of the series, and so on back to the richest tank of the series. Clear water was used for the wash in the final tank. This is the principle on which all successful countercurrent decantation plants operate at the present time, but Randall's plant was not successful because of mechanical difficulties in getting a continuous thick discharge from his cone tanks. A similar plant was built in South Africa although there the washes were not repeatedly used, as in Randall's case, but were precipitated after each contact with the ore. This also was abandoned

Jan 1, 1918

By George Otis Smith

In the utilization of natural resources owner, operator, and consumer* should share the attendant benefits. Development needs to be planned under terms recognizing fully the interests of all concerned, for ally undue advantage given to any one of these participants is apt to involve even greater and disproportionate injury to one or both of the others. For this reason it is well to preface any consideration of needed reforms in legislation affecting the disposition of public land with a survey of certain fundamental principles that determine the general conditions of a11 land transfers preliminary to development, utilization, and production. The disposition of any undeveloped natural resource, whether timber, oil, coal, or water power, as a transaction to which land owner and prospective developer are parties, must be based in theory upon a division of expected returns.' Whatever the terms of such disposition, neither party can reasonably ask for anything other than an equitable division of the returns. Under this analysis three and only three questions need to be discussed; namely, what are those profits, how is this division to be accomplished, and what is the equitable basis of division ? The answer to the third question should probably be found by applying to the problem the principles of theoretical sociology, and the question need not be mentioned further at this time, inasmuch as it does not involve the practical considerations to be kept in mind in connection with the other questions, which are concerned with only the measure of returns and their division. That is to say, whether the land owner's equity is to be stated as 95 per cent, ox as 6 per cent, of the profits attending the development of the particular resource, no change would be necessary in the method to be adopted of arriving at the closest approximation of the prospective total profit. If on this basis we now compare the two methods of disposing of

Jan 1, 1915

By P. E. McKinney

Developments in engineering during the past decade, particularly as applied to marine construction, mining machinery and other purposes in which corrosion offers a serious problem, have created a large demand for a non-ferrous metal highly resistant to corrosion and at the same time useful in general construction work as a substitute for steel without materially decreasing the factor of safety or increasing the weight of the various parts over that ordinarily used in the case of mild steel. To obtain the combination of desired properties many compositions have been proposed and used with excellent success, but at the present time probably the most popular and most widely used combination is the non-ferrous alloy commonly called manganese bronze. This is nothing more than a high brass to which have been added, by the proper method of alloying, comparatively small percentages of aluminum, iron, or manganese with the definite purpose in view of strengthening the alloy and rendering it more dense and close-grained than the average yellow-brass casting. In the manufacture of manganese bronze a great deal has been said about the importance of using only the highest grades of raw material and the beneficial or detrimental effects, as the case may be, of various impurities, as well as the importance of adding the ingredients according to various formulas proposed; but in most of these cases the literature on the subject has dealt principally with the manufacture of this alloy from virgin metals and raw materials of the highest purity. It is the purpose of this paper to deal particularly with the possibilities that lie in the proper development of methods for manufacturing such an alloy by more economical methods than those which have usually been discussed in other literature on the subject. Shortages have recently existed in raw materials needed for many products entering into the various branches of engineering work, particularly the non-ferrous metals, and during the next few years of reconstruction the country will be flooded with many

Jan 1, 1919

Prof. J. W. Richards, South Bethlehem, Pa. (in reply to several questions):—The cut representing some of the round briquettes which were under test shows that, at the brcaking-stresses, they break into lumps, and do not disintegrate into powder. The process is simplicity itself. I have followed the different processes for sintering iron-ores and flue-dust, am interested in all of them and wish them all success; but this process appealed to me strongly by its simplicity. It is in line with a method which I once tried to work out myself, but which never came to anything, namely, the agglomeration of fine iron-ores by means of Portland cement. As small an amount as 5 or 6 per cent. of Portland cement will enable fine ore to agglomerate and set into a briquette, but when I came to estimate the cost, I found it was a little too high. The Schumacher process, curiously enough, does not work well on iron-ore, but flue-dust thus treated does harden and give a strong briquette. In my attempts to find a reason for this difference, it has occurred to me that possibly the particles of flue-dust had been coated over with some sublimed silica, which might be an agent in the setting. But I found by experiment that neither sublimed silica, nor ordinary silica, nor ordinary alumina, would briquette. Chemically pure iron oxide briquetted quite hard; but the application of pressure is a necessary part of the operation. If simply moistened with the solution and allowed to stand it does not set hard, but the more pressure applied to it the hardcr it sets. Evidently the flue-dust particles must be pressed very close together in order to get the small proportion of active material wet, so that the particles shall act at their points of contact; for it is evident that only at the points of contact does the cementing action take place. The reactions are facilitated by considerable pressure, bringing the acting particles close together, and may go on with

Jan 1, 1913

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By Maxwell Adams

Considerable interest has recently been developed in sage-brush oil because of its possible utilization as a flotation agent in the mining industry. A list of some of its physical properties, together with the method used in its extraction, may prove of interest at this time. Something over a year ago, a study of the essential oils in desert plants was begun in the Chemical Laboratory of the University of Nevada. None of the oils so far studied possess properties of special interest to engineers, except the oil of sage, Artemisia tridentata, which has exceptional power as a flotation agent. This plant, known as common sage brush, also called black sage, is widely distributed over the semi-arid West, being found quite generally on most of the dry plains and mountains west of Missouri. The method of extracting the oil followed in these experiments is very simple. The leaves, twigs and small branches are placed in an airtight drum, having a capacity of about 27 cu. ft. Steam is admitted through a number of ,small openings at the bottom of the retort, and the pressure maintained at 20 to 25 lb. per sq. in. for 3 hr. The escape of the steam from the retort is regulated by allowing it to pass through a stop-cock into a condenser. The water in the receiver is drawn off from time to time and the oil, which is insoluble and floats upon the water, is thus collected. At the end of 2 hr. most of the oil has been driven out, though traces continue to come over for a much longer time. By raising the pressure, the time required could probably be shortened and the yield increased, but the lack of laboratory equipment has prevented the carrying out of this experiment. The stock wood, bark and branches contain no oil, the distribution of the oil being limited to the leaves and young shoots. There is a seasonal variation in the amount of oil contained. Samples collected on different dates gave the following amount of oil: May 1, 0.42 per cent.; May 27, 0.6 per cent.; June 30, 0.72 per cent.; Aug. 1, 0.9 per cent.; Sept. 10, 1.0 per cent. The increase appears fairly constant from early spring, when the leaves first appear, until light frosts occur in the autumn. When the plant is air-dried there is some loss of oil, as the following data will show: Two 100-lb. samples were collected at the same time. One was distilled when green; the other was air dried for

Jan 1, 1917

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

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

By F. R. Pyne

The following notes are presented in an endeavor to point out the disadvantages attending the use of chrome brick in reverberatory furnaces in which are conducted the treatment of materials of such a nature that absorption by the brick is of too great value to be wasted, and these values must be recovered, if possible, in order to prevent metal losses that can not be tolerated. Several years ago one of the large Eastern copper refineries decided to utilize basic material in place of siliceous material in the walls of their reverberatory furnaces for the treatment of very foul blister copper, as the latter rapidly corroded the siliceous linings. It was also expected that there would be less slag formation, with a consequent decrease in the cost of treatment and a reduction in the metal losses. Magnesite brick were first used, but while the corrosive action of the foul material was greatly reduced, and the amount of slag formed was very much less, the magnesite proved to be unsatisfactory in certain parts of the furnace, because of its tendency to crack and spall badly when subjected to the alternate heating and cooling that takes place in a reverberatory refining furnace. This made many repairs necessary, and consequent frequent interruption in the operation of the furnace, which, together with the high price of the magnesite brick, ran up the cost of maintenance to an unreasonable amount. It was, therefore, decided to substitute chrome brick for magnesite brick in the parts of the furnace affected. The results, as far as the reverberatory furnace was concerned, were very satisfactory. The corrosion due to the action of the foul blister was small and the amount of slag formed was no greater than when using magnesite, and the tendency to crack and spall shown by the magnesite was eliminated. Gradually the use of chrome brick was extended to all furnaces, those treating blister copper as well as those melting cathodes, and the results were so satisfactory that the siliceous roofs were replaced by roofs of chrome brick except in certain places where experience showed a more satisfactory performance on the part of the silica brick. It was immediately recognized, for both the magnesite and the chrome brick, that the metal absorption was very heavy, but it was felt that the

Jan 1, 1918

By P. L. Hendricks, J. W. Spretnak

The interstitial atom principally responsible for the yield point and strain aging in electron-beam-melted tantalum is identified by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Two sets of specimens contained two levels of oxygen with very low hydrogen contents and the third set had comparable oxygen and hydrogen contents. The activation energy for the return of the yield point agrees well with that for diffusion of oxygen for the first two sets of specimens. For the third set of specimens, the activation-energy value lies between those for diffusion of hydrogen and for diffusion of oxygen. The advent of the dislocation model of plastic deformation in metals has revitalized interest in the yield point and strain aging in bcc metals containing a certain minimum content of interstitial solute elements. Much theoretical and experimental work has been performed in recent years to elucidate the detailed mechanism of these phenomena. The purpose of this investigation is to attempt to identify the principal interstitial element responsible for the yield-point phenomenon in electron-beam-melted tantalum by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Some of the earlier theories of the yield-point phenomenon proposed a grain boundary film of iron carbide. Such models could not satisfactorily explain all features of strain aging and the yield-point phenomena. The most widely accepted explanation is that of Cottrell,1 later extended by Cottrell and Bilby.2 Strain aging is ascribed to "locking" of dislocations by interstitial solute "atmospheres". The yield-point phenomenon results when the dislocations are torn away from their atmospheres. The strain-aged condition is re-established after sufficient time to allow the interstitial atoms to diffuse to the dislocation lines and re-establish the locking atmospheres. Clearly, the Cottrell-Bilby model is concerned with the bulk of the grain and does not specifically involve the grain boundary. The recent modification of the Cottrell-Bilby model is a redirection of attention to the role of the grain boundary and the possibility of multiplication of a limited number of free dislocations rather than unlocking all of the dislocations. Theories have been advanced by Hahn3 and conrad4 which are modifications of the Cottrell-Bilby theory. The model proposed by Hahn indicates that, although the possibility of un- locking anchored dislocations is not excluded, it implies that unlocking is not necessarily required to explain yield drop. Locking of dislocations during the aging treatment is a necessary part of the theory; however, it assumes that dislocations once locked remain locked. It is suggested that the yield drop observed is a result of the following factors: 1) the presence of a small number of mobile dislocations initially, 2) rapid dislocation multiplication, 3) the stress dependence of dislocation velocity. In the case of bcc metals, locking is considered to be the means by which dislocations are immobilized. Cold working of the metal results in the generation of larger numbers of new dislocations and the stress dependence of the dislocation velocity accounts for yield drop observed. Conrad' has proposed a model similar to the one just described which applies to strain aging of iron and steel and which logically could be extended to other bcc metals. This model also does not require large-scale unlocking of dislocations. It is proposed that, during initial loading of a specimen below the upper yield stress, a few dislocations are torn free of their Cottrell atmospheres at regions of stress concentrations. With an increasing stress, some multiplication of dislocations occurs by a double cross slip mechanism, thus giving a preyield microstrain. At some critical stress represented by the upper yield stress, sudden profuse multiplication of dislocations occurs, enabling plastic flow to proceed at a lower stress. In this model, microstrain, preyielding, and flow represent the movement of free dislocations. It should be noted that this model also requires the locking of dislocations by interstitial solute atoms for the occurrence of a yield point; however, unlocking of large numbers of dislocations is not required. If it is assumed that the yield point will return when some fraction of free dislocations produced during pre-straining are pinned, the number of solute atoms required to pin unit length of a dislocation line can be calculated when prestrain and reloading are done at the same temperature and strain rate. Since the migration of solute atoms back to the stress fields of dislocation lines is controlled by the diffusion rate of interstitial solute atoms, it is to be expected that the activation energy for strain aging would be identical to the activation energy for diffusion. It would also be expected that the strain aging observed will be controlled by the fastest diffusing species capable of producing locking over the temperature range investigated. The rate of yield-point return has been found to be adequately expressed by an empirical rate equation of the form: rate=Ae-Q/RT [1] where A = constant, Q = activation energy, R = gas constant, and T = absolute temperature. Cottrell and Bilby2 have expressed the number of atoms per unit length of dislocation line which arrive

Jan 1, 1967

By Arnold Hague

At the Buffalo meeting, October, 1888, Dr. Raymond presented a paper entitled: "Soaping Geysers" (p. 449 of the present volume), in which he called attention to the use of soap by tourists to cause eruptions of several of the well-known geysers in the Yellowstone Park. Incorporated in this paper appears a communication received from me, written from camp in the Park, in reply to some inquiries on the subject. The letter discussed somewhat briefly the means employed by visitors to the Park to hasten the eruptions from hot springs and reservoirs of hot water, which remain dormant for days, or even weeks or months, at a temperature near the boiling-point, without any display of geyser-action. As the paper has called forth considerable comment, I desire to elucidate one or two points in relation to the temperature of the springs, and to answer some inquiries about the composition of the thermal waters. In the summer of 1885, a Chinaman, employed as a laundryman for the accommodation of the tourists at the Upper Geyser Basin, accidently discovered, much to bis amazement, that soap thrown into the spring from which he was accustomed to draw his supply of water produced an eruption in every way similar to the actual workings of a geyser. Tourists with limited time at their command, who had travelled thousands of miles to look upon the wonders of the Yellowstone, soon fell into the way of coaxing the laundryman's spring into action, to partly compensate them for their sore disappointment in witnessing only the periodical eruptions of Old Faithful. Successful attempts upon this spring soon led to various endeavors to accelerate action in the dormant and more famous geysers. In a short time, so popular became the desire to stimulate geysers in this way, that the Park authorities were compelled to enforce rigidly the rule against throwing objects of any kind into the springs. In connection with a thorough investigation of the thermal waters of the Yellowstone Park and the phenomena of the geysers, I undertook a number of experiments to ascertain the action of soap upon the waters and to determine, if possible, those physical conditions of various pools and reservoirs which permitted the hastening of an

Jan 1, 1889

By B. A. Eaton, K. E. Brown, C. R. Knowles, D. E. Andrews, I. H. Silberberg

This paper presents the resitlts of an investigation of two-phase, gm-liquid flow in horizontal pipelines. Experimental data were taken in three field-size, horizontal pipelines, two of which were constructed for this purpose. The data were obtained using water, distillate and crude oil separately as the liquid phase, and natural gas as the second phase. Experimental pressure-length traverse, liquid holdup and flow-pattern data were collected for each set of flow rates. These data were used to develop three correlations that are presented herein. The liquid-holdup values correlated with various flow parameters without regard to the existing flow pattern. The same was true for the energy-loss factors. A new flow-pattern map is presented that appears to be quite reliable, but not required for the pressure-loss calculations. The liquid-holdup correlation and the energy-loss factor correlation are used in conjunction with a two-phase flow power balance, developed during this study, to predict the pressure losses that occur during gas-liquid flow in horizontal pipelines. A recommended calculational procedure is given, as well as a statistical analysis of the results. This procedure lends itself to computer application, since several small pressure decrements are needed to calculate a pressure-length traverse. The correlations are shown graphically, but may be curve fitted with existing curve-fitring computer programs. INTRODUCTION Due to the frequent occurrence of gas-liquid flow in pipelines and the desire to accurately calculate the pressure losses that occur in these lines, two-phase flow is of considerable interest to the petroleum, chemical and nuclear industries. In the petroleum industry, gas-liquid mixtures have been transported over relatively long distances in a common line due to the advent of centralized gathering and separation systems. Long two-phase flowlines are usually accompanied by large pressure drops which influence the design of the system. Gas-lift installations are designed on the basis of known tubing pressures at the wellheads. The horizontal flowline connecting the wellhead and the separator system must be correctly sized in order to minimize the horizontal flowline pressure losses and the wellhead tubing pressure. Practically all oilwell production design involves horizontal two-phase flow in pipeknes. All of the flow processes of oil and gas production must be studied simultaneously to insure good well design. Since the beginning of offshore oilfield development, long horizontal flowlines have been constructed. Because pressure losses greatly influence the performance of producing wells, a method is desired that can be used to predict such pressure losses and select optimum flowline size. Several types of gas-liquid flow exist, and many of these are discussed by Gouse The study of pressure gradients, fluid distributions and flow patterns that occur in horizontaI multiphase flow is made difficult by the great number of variables involved. The various flow regimes give rise to changing velocities of the fluid particles in all directions. These instabilities of the interface between the gas and liquid prohibit the determination of actual vector velocities of fluid particles in each phase. Also, it is practically impossible to arrive at correct sets of boundary conditions. Therefore, most investigators have concluded that a solution to the problem by the classical fluid dynamics approach, whereby the Navier-Stokes equationsM are formulated and solved, is far too complex. Other methods must be utilized to develop general correlations that will predict the behavior of gas-liquid horizontal flow systems. Multiphase flow studies have sought to develop a technique with which the pressure drop can be calculated. Pressure losses in two-phase, gas-liquid flow are quite different from those encountered in single-phase flow; in most cases an interface exists and the gas slips past the liquid. The interface may be smooth or have varying degrees of roughness, depending on the flow pattern. Therefore, a transfer of energy from the gaseous phase to the liquid phase may take place while energy is lost from the system through the wetting phase at the pipe wall. Such an energy transfer may be either in the form of heat exchange or of acceleration. Since each phase must flow through a smaller area than if it flowed alone, amazingly high pressure losses occur when compared to single-phase flow. Most investigators of horizontal two-phase flow phenomena have chosen to separate their experimental data into several groups of observed flow patterns or regimes.