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By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4'C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

ALEXANDER, JOHN S, M,'74-6,'81-3 *ASHBURNER, C A, M, '85-7 ASMUS, GEORGE, Dl, '78-80 BACON, D H , M, '00-2 BAYLES, JAMES C , M,'80-2,'91-3 P, '84-5, V,'88-9 BIRKINBINE, JOHN, M, '83-5, V, 'S7-J, P, '91-2 BLAIR, THOMAS S , M, '74-43 BLAKE, WILLIAM P , V,'71-4,'76-7,'05-6 *BLANDY, JOHN F, V,'71-3,'78-9 BLOW, A A, C, '05-7 BOWIE, A J , JR, V,'93-4 *BRAMWELL, J H , A1, '89-91 BROOKS, THOS B , M, '72 BRUNTON, D W , V, 97-8 BUCK, STUART M , M, '83-5 *BURDEN, JAMES A, V,'80-1 BURNHAM, WILLIAM, M, '82-4. CAMPBELL, H H, M, '93-5 CHAMBERLAIN, H S , V, '96-7 CHANNING, J PARKE, V,'08 CHRISTY, S B , V. '91-2, '07-8 CHURCH, JOHN A, M, '79-8l,'94-6, V, '07-8 COGSWELL, W B, V, '74-5,'86-7

Jan 1, 1910

ALEXANDER, JOHN S, M,'74-6,'81-3 ASHBURNER, C A, M, '85-7 ASMUS, GEORGE, Dl, '78-80 BACON, D H , M, '00-2 BAYLES, JAMES C , M,'80-2,'91-3 P, '84-5, V,'88-9 BIRKINBINE, JOHN, M, '83-5, V, 'S7-J, P, '91-2 BLAIR, THOMAS S , M, '74-43 BLAKE, WILLIAM P , V,'71-4,'76-7,'05-6 BLANDY, JOHN F, V,'71-3,'78-9 BLOW, A A, C, '05-7 BOWIE, A J , JR, V,'93-4 BRAMWELL, J H , A1, '89-91 BROOKS, THOS B , M, '72 BRUNTON, D W , V, 97-8 BUCK, STUART M , M, '83-5 BURDEN, JAMES A, V,'80-1 BURNHAM, WILLIAM, M, '82-4. CAMPBELL, H H, M, '93-5 CHAMBERLAIN, H S , V, '96-7 CHANNING, J PARKE, V,'08 CHRISTY, S B , V. '91-2, '07-8 CHURCH, JOHN A, M, '79-8l,'94-6, V, '07-8 COGSWELL, W B, V, '74-5,'86-7

Jan 1, 1910

Jan 1, 1881

By GEORGE O. SUMAN

IN THE operation of oil properties there are various difficulties with pumping wells which can often be overcome or greatly lessened if sufficient attention is, directed towards pump and tubing problems. The difficulties referred to are the wearing out of pumps, sanding up of pumps, and the sanding up of the hole. As the perforations in the oil strings are large and the oil and sand loose and unconsolidated considerable trouble is often encountered in pumping wells due to the ease with which' the sand can come into the holes. DETERMINING FLUID LEVEL In determining the proper depth at which to tube a well it is essential to first find out something about the behavior of the fluid in 'the hole: Facts in regard to this natter can be obtained by finding the fluid level on pulling the tubing, by making a pumping test on the well tubed to various depths, and by bailing tests during cleaning out work. In ordinary oil field operations it is customary to take the fluid level at the time of pulling the tubing. This 'can only be done when the pump is not sanded up. There are two methods used in obtaining the fluid level. One method is to note where the outside of the tubing starts, to be covered with fluid when pulling the

Jan 1, 1925

By F. H. Rhines, A. H. Grobe

The constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conven-tional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitu- tion of its alloys desirable. As a part of a program far the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (I43. 5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

By A. H. Grobe, F. H. Rhines

The constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conven-tional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitu- tion of its alloys desirable. As a part of a program far the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (I43. 5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By C. S. Smith, L. H. Beck

KNOWLEDGE of the Cu-Zn constitution diagram was critically examined in 1944 by G. V. Ray-nor,1 who suggested the diagram reproduced in Fig. 1 as the best evaluation of available data. No pertinent work on the constitution has been published since that time, although a number of authors have discussed transformation kinetics and theory. Despite the large amount of work that has been done on the constitution of these industrially important and scientifically interesting alloys, minor uncertainties still exist. For example, it is still not possible to say definitely whether a two-phase region exists between the ordered and disordered forms of the 8 phase. A careful re-examination of the phase boundaries in this part of the diagram was therefore undertaken. Two methods were selected for the new investigation—quantitative metallography for the higher temperatures and precision lattice parameter measurement for lower temperatures. Because of the relatively narrow two-phase regions flanking the ß phase in these alloys, quantitative metallography is particularly suited for their examination, since the relative amounts of the two phases are very sensitive to their compositions. The method, however, is useless below about 350°C because of the inadequate resolution of the two constituents. Below 400°, however, the X-ray diffraction method is applicable, although it is of somewhat lower sensitivity in this system. The changes of composition that occur during quenching from above about 500°C entirely vitiate X-ray measurements at room temperature though they do not affect metallographic area measurements. The two methods overlap and supplement each other admirably. Both methods depend on the attainment of equilibrium composition of the two phases in a more or less intimate mixture and thus avoid the difficult problems of nucleation and long range diffusion involved in the conventional metallographic bracketing method. The alloys were melted from a master alloy made from re-electrolyzed cathode copper and Horsehead 99.99 pct Zn. Melting was done under a cover of either borax or charcoal and the alloys cast into a 7/8 in. sq graphite mold for the a-ß alloys or a 3/8 in. diam cylindrical graphite mold for the ß-? alloys. The a-ß alloys were rolled at 750°C to 5/8 in. sq; annealed for 24 hr at 800°C and quenched; then rolled and swaged at 200°C to 3/8 in. diam rods, annealed 24 hr at 200°C, quenched and cold rolled 2 pct reduction. This treatment was intended to obtain a small grain size and to produce many nuclei of the minor phase for growth on subsequent heat treatment. The unworkable ß-? alloys were given preliminary treatment by sealing in Vycor tubes in vacuum and annealing for 4 hr at 800°C followed by cooling in air. Samples of homogenized alloys were checked spectrographically for impurities, but the principal components were determined on samples subsequent to heat treatment. The impurities analyzed averaged approximately as follows: Ag, 0.0002 pct; Fe, 0.004; Si, 0.0008; Cd, 0.005; Mg, 0.0002; and Pb, 0.002. For metallography, samples of appropriate composition were cut into rods 5/8 in. long, sealed in pyrex tubes in vacuum and annealed for eight weeks at temperatures of 470°C and below, two weeks at 480°, 500°, and 600°C, and 4 hr at 700°C, followed by quenching in cold water. Temperatures were accurate to ±2°C. The cylinders were then machined to 8.7 mm diam and a slice weighing 1.5 g cut with a thin saw transversely from the center of each. This

Jan 1, 1953

By E. C. Harder

CERTAIN typical characteristics of bauxites, ores of aluminum permit their classification into a number of categories, each of which has special features that enable grouping within it deposits from widely scattered bauxite fields. There may be local variations in conditions that have introduced differences of lesser importance between similar deposits in different fields, resulting perhaps from the influence of factors other than those that have produced the distinguishing features of each of the different groups, but in general the similarity between the deposits in each group is sufficiently striking to make the grouping indicated of interest. Several factors and conditions enter into the decomposition process that results in the development of bauxites and laterites and affects their character. The principal conditions favoring optimum bauxitization are: (1) pres- ence of rocks with easily soluble minerals yielding residues rich in alumina; (2) effective rock porosity, enabling easy access and free circulation of water; (3) normal to abundant rainfall alternating with dry periods; (4) vegetation, including bacteria, advantageously distributed; (5) available sources of appropriate solution and precipitation agencies; (6) a tropical or at least a warm climate; (7) low to moderate topographic relief, allowing free movement of the water table but a minimum of erosion; and (8) long quiet periods in earth history. Assuming that all of these factors are operating to a greater or less degree, it seems that the one that affects most the physical character of the resulting bauxite or laterite deposits is the chemical and mineralogical composition of the rocks that by their decay yield the bauxite deposits. This factor is used in the classification followed in this paper. In the process of weathering of ordinary silicate and carbonate rocks of the earth's crust, whether of igneous or sedimentary origin, it is the minerals of the alkalies that yield most readily to attack. The alkaline earth compounds also offer no great resistance, particularly the carbonates. Thus, among the rock-forming elements, those producing the most insoluble compounds are aluminum, iron, and silicon, together with certain ones of less importance, such as titanium, manganese, and phosphorus. In normal weathering processes such as prevail in temperate regions, the common minerals of rock decay are

Jan 1, 1952

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.' In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.' Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.',' It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.' In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By Arthur C. Green

A group of 13 cities situated in Los Angeles and Orange counties in Southern California is engaged in constructing an aqueduct to carry water from the Colorado River at a point near Parker, Arizona, to a distribution point near Riverside, California. The aqueduct will have a total length of approximately 241 miles, and is designed to deliver 1605 cu. ft. of water per second, or a little more than one billion gallons per day. The aqueduct crosses a barren, desert waste and the project includes approximately 91 miles of 16-ft. tunnel. The large amount of tunnel driving that has been done in this country in the past few years has resulted in some remarkable developments in equipment and methods. The building of the Colorado River Aqueduct,, with its 91 miles of tunnels, has called on the best engineering knowledge in the country. New and better equipment has been designed for all phases of the work, and this equipment has been coordinated and adapted to the various conditions with a high degree of efficiency. The result has been that records for tunnel driving have been set under adverse natural conditions that exceed the estimates for progress under good conditions. All of the tunnels in the main aqueduct, except the Valverde and Bernasconi at the western end, have a finished diameter, inside the concrete lining, of 16 ft. Fig. 4 shows a section of the tunnel with the concrete lining in place. Fig. 5 illustrates the finished tunnel in three typical sections. The standard tunnel grade is 3.432 ft. per mile in the 16-ft. tunnels, but the Valverde and Bernasconi tunnels have a steeper grade and a finished diameter of 15 ft. 3 in. The rough bore of the large main aqueduct tunnels averages 12.95 solid cubic yards of material per foot of advance in timbered sections and 10.76 solid cubic yards per foot in unsupported sections. Tunnel Driving While the Conway mucker has been used on tunnel work for years, a larger and more powerful Conway was designed to meet the require-

Jan 1, 1937

By Robert W. Hunt

(Cleveland meeting, October, 1912.) PERHAPS of all the scientific economic questions which have been claiming the attention of capitalists, metallurgists, manu-facturers, directors of public utilities, and the general public of America, during the last few years, none have been of more importance than the one relating to the wear and safety of steel rails. The discovery of the Bessemer process made possible modern railway development. In that growth, as has generally happened in all progressive movements, ill its department have not remained equally balanced. Iron rails permitted the construction of roadways for the passage of power-driven vehicles. In time the speed and weight of such carriages proved too much for the wearing-qualities of the rails, and the limit of railway capacity seemed to have been reached. Bessemer made his invention, which was soon perfected and developed, especially as related to steel rails, and thereby increased the limit of capacity, acid vastly greater railway progress was, made possible. The Siemens-Martin open-hearth process followed, and was later supplemented by the Thomas-Gilchrist basic improvement. For a time the Bessemer steel rails of commerce Were, more than equal to all that was asked of them, but this did not long continue, as evidenced by the records in our Transactions. Revolutionary changes occurred in the industrial world, and in no part of it more than in steel-rail manufacture. Great and powerful commercial combinations were made, whose financial resources made possible the supplanting of the then most efficient blast-furnaces, steel-works, mid mills, by others of theretofore unimagined capacity. Old traditions and practices of steel-making were wiped away, and, in too many cases, output was apparently the chief aim, with the result that much dissatisfaction with the wear and safety of rails was felt by railway officials, and the general public was concerned as to its safety when traveling. The climatic conditions of the winter

Dec 1, 1912

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By A. C. Heath, E. H. Dix

The importance of aluminum-silicon alloys in thc light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and likc silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminurn and alurninum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. Part I.—Aluminum-silicon Alloys The early work on this system was largely confined to determining the general form of thc diagram and in this respect the results are in good agreement. Briefly, alulninunl and silicon form a simple eutectifcrous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Ipraenkell (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solu-t'ion. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility docs not appear