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By H. E. Ellis, O. L. Patterson, Granville Dutton

A large-scale water-injection program for the Holt Bryant reservoir of the Delhi field has been established by means of the new automatic multi-pool analyzer. The objectives of this program were to increase reservoir pressure and eliminate a cross-dip gradient of 200 psi. Pressure increases during the first 15 months of operation have allowed for increased oil production rates of 2,600 BID or 25 per cent. To determine the required water injection it was necessary to predict natural water influx ram. Elimination of the pressure gradients required the water-injection program to account for the fluid migration and pressure interaction between segments of the reservoir. An integral part of the ana1ysis included the determination of in-place volumes of oil and gas. The operation of the automatic multi-pool analyzer in determining the water-injection program is described. New features of the analyzer inc1ude an automatic maferial balance analog and a leart-squares computer for determination of unknown reservoir properties. Operational procedures are sufficiently simple to allow direct use by reservoir engineers on a routine basis. The rapidity and accuracy with which problems may be solved permit repeated ana1yses as a check upon reservoir performance. INTRODUCTION This paper describes the use of a new analog com- puter in determining the optimum injection program for a complex reservoir. The Holt-Bryant (Fig. 1) is the major reservoir in the Delhi field of Louisiana. Production is from the Tuscaloosa at subsea depths of 2,970 to 3,286 ft. The sand dips to the south and southwest from three to five degrees. The reservoir is approximately 12 miles long and varies in width from 1/2 to 2 miles. Various calculations have placed the initial volume of oil in-place in the wide range of 275 to 355 million STB. Two small gas caps were initially present in the reservoir. The Holt-Bryant reservoir was discovered in Dec.. 1944, and was fully developed with 188 producing wells by 1948. After development was completed, an east-west pressure gradient began to establish itself. This

Jan 1, 1957

By L. C. Uren

Field studies and laboratory research have established the fact that the expulsive force which drives petroleum into wells, from the reservoir sands in which it is stored by nature, is primarly an expression of the energy latent within compressed natural gas dissolved or occluded in, or otherwise associated with the oil. Each barrel of oil produced is forced into the recovery well by the expansive energy of a certain volume of compressed gas, originally stored with the oil in the pores of the reservoir rock; and each cubic foot of gas so produced with the oil and expanded to atmospheric pressure reduces by so much the total natural energy available for oil expulsion. This relationship between the volumes of gas and oil produced has seemed so important that petroleum production technolo-gists have come to regard the "gas-oil ratio," or the "gas factor" as it has been more conveniently termed, as a measure of oil-production efficiency. Different methods of oil recovery and production devices are now Com pared on this basis and estimates of ultimate recovery obtainable through their use are considered by many to be inversely proportional to the values of their respective gas factors. The writer has been among those who have given support to a widcspread movement toward a proper recognition of the significance of the gas factor as a guide in the control of producing oil wells, and does not wish to oppose its more extended application. It seems necessary, how-cvcr, in view of the almost elemental faith with which the principle of the gas factor has been received in many quarters, to point out that it is a most complex factor, and one which cannot be regarded as an absolute index of production efficiency without due regard to other contributing factors by which it is influenced to an important degree. Variables Influencing Gas Factor The mere recording of a low gas factor, obtained through the use of some method or device, does not necessarily imply efficient oil production; and conversely, a high gas factor does not always signify inefficient recov-

Jan 1, 1928

THE distinction btween price reduction as a re-sult of lowering of production cost and price re-duction through unrestricted competition cannot be made too clear, because they are often interwoven in actual experience. Take the whole population of a town whose principal industry is shoe manufacturing as a concrete example. If the manufacturer is able to cut his price per pair in half because he has found out how to make a pair at half the cost, he will com-monly let a number of his men go, because reduction in production cost usually results from substituting cheap mechanical energy for expensive human energy. These people will normally find other employment. The workmen who remain employed usually earn more in dollars than they did before, and in spending it give employment where there was less before. Mining companies that initiate considerable enter-prises in foreign lands where the economic level is low, and where most of the people are busily but in-efficiently engaged in raising enough food to support themselves and their families, often find themselves confronted with an acute labor problem. If any con-siderable number of workers leave the land to work in and about the mines, those left on the land cannot raise enough food to keep them all unless they are taught better methods of agriculture and provided with equipment that will enable them to produce more with less expenditure of effort. Add to this the fact that managers commonly find that the "natives," as our British cousins designate them, usually need more food and a better balanced diet than they have been accustomed to in order to show anything above the lowest order of efficiency in industrial work,. and it is clear that to make a new industry possible in what may be termed an economic province involves increas-ing the productivity, not only of those who are em-ployed in it, but of the whole social group. It has already been pointed out that the employ-ment of large numbers of men in automobile manu-facture is only possible because the others have in-creased their productivity enough to turn out every-thing else that is needed without the help of the auto-mobile workers.

Jan 7, 1928

Following the suggestion of Engineering Council and at the direction of, the President, representatives from each of the Federal Government bureaus interested in map-making were called into a conference for the purpose of coordinating all of the Government's map-making activities. This conference has now reported back to the President the results of its findings, which indicate that Engineering Council's recommendation in this matter was well founded. While the conference report states that its members were of the opinion that little duplication of effort existed, it recommends the formation of a permanent Board of Surveys and Maps. An extended review of the map-making activities, which is given as an appendix to the report, indicates that this recommendation is a logical step. The conference recommendations concerning this Board of Surveys and Maps are as follows: (1) the Board is to he com-posed of representatives of mapping bureaus to be assisted by outside engineering organizations, which have been named above; (2) the estab-lishment of an information office in one of the Government bureaus, preferably the Geological Survey, which is to be under the supervision of the Board and is to be a mapping information clearing house for the Government and outside engineering organizations; (3) copyright laws are to be so changed that copies of all. maps made in the United States and with Governmental authority, will go to the central information office; (4) the Government departments are to receive orders to cooperate, with the Board; (5) future topographic maps of all kinds are to conform with specifications for the standard topographic map; (6) the U. S. Coast and Geodetic Survey to have supervision of final adjustment of all important control data under specifications approved by Board of Surveys and Maps; (7) surveys in the form of maps and publications are to be issued as soon as possible after field work has been completed; (8) program of the Interdepartmental Committee on Aerial Surveying was approved. Outside technical and scientific organizations that are called in for consultation are to operate in an advisory capacity only, responsibility for action on Governmental work is. to rest solely with the Governmental agencies.

Jan 12, 1919

By Lovell Lawrence

MAGNETITE deposits in the Eastern States have been mined uninterruptedly since pre-Revolutionary War days. The industry, thriving in normal times, was given impetus in all periods of tumult, and continued to advance and expand, until the Lake Superior ores came into production. A period of comparative quiet existed until increased freight rates, together with increased mining costs on Lake Region ores, permitted the magnetites again to compete. This, coupled with World War demands, created unpre¬cedented activity. Producing plants were at their peak, new mines were equipped and put in operation and the industry pushed production beyond the absorption point. Ore stocks were tremendous, internal competition severe, and a great increase in import of European ores brought the industry to a low ebb in 1923.

Jan 1, 1933

By Edward W. Parker

THE agreement of September, 1922, between the anthracite operators and the United Mine Workers of America, which followed the 54.5 months strike during the summer of that year, contained the following provision : The parties unite in a recommendation to Congress that legislation be forthwith enacted creating a separate anthracite coal commission with authority to investigate and report promptly on every phase of the industry and the parties hereby ask the President to request the enactment by Congress of the recommended legislation. The continuance of production after Aug. 31, 1923, shall be upon such terms as the parties may agree-upon in the light of the report of the Commission.

Jan 1, 1924

By W. H. Adams

One of the most attractive subjects for technical writers is the gigantic industry of the manufacture of sulphuric acid. This is no doubt, natural when we take into account that it has grown in this country during the past twenty years, from a production of 60,000 tons in the year 1867, to that of nearly 450,000 tons in 1887. We may well excuse much of the literature which but repeats the same old story, as it serves to bring to the public notice, at proper intervals, the hidden resources of our land; and this constant application of essential truths will sooner or later be the means of freeing us from dependence upon the Old World for necessary chemical products. The present increase in manufacture of this acid in the United States is almost wholly from pyrites ores, which we have in unlimited quantities close at hand. The largest consumption of such acid is for treatment of other native products, petroleum, rock-phosphates, etc.; and, considering the knowledge we have gained during the past twenty years, it is safe to say that the industry is but fairly established, and the causes which have operated to place us in our present proud position are but natural incentives for a further growth and an increased consumption of the many other undiscovered or undeveloped resources of our American soi1. In one of his earlier editions Muspratt says: " It would seem that the manufacture of sulphuric acid, though as extensively carried on as any other business, yet seems to be the least understood; and the ignorance of some manufacturers appears to be only equalled by that of writers, who, in their description of the production of this acid, give figures of apparatus, and vaunt as improvements, things which have been exploded for years. It is possible to find in the works of eminent men drawings of apparatus, for the production of sulphuric acid, which never could possibly have worked one day—some, in fact, could never have worked at all."

Jan 1, 1888

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.' Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By Clyde E. Williams

DESPITE the confusion resulting from the depression and the beginnings of recovery, important progress in all branches of iron and steel metallurgy has been accomplished during the year 1933. Research work has been intensive and highly technical, with increasing attention paid to fundamentals. Plant application of research developments has been rapid. Highly specialized laboratory methods were used for the study of iron-ore concentration methods. More attention has been given by the blast-furnace operator to the sizing of ore and the elimination of fines from the charge by the use of sinter. Combustion in the open-hearth has been placed under better control and the insulation of open-hearth furnaces has spread rapidly, with resultant higher fuel efficiency and better control of the melting and refining operations. Control of iron oxide content in the slag and the determination of iron oxide and other inclusions in steel received great attention during the year.

Jan 1, 1934

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors' conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors' article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.'); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors' reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

By AIME AIME

THE meeting" of the Rare Minerals and Metals Committee was held Monday afternoon, Feb. 17; Donald M. Lidclell, chairman, presiding. The first paper (T. P. 279), "Progress in the Use of Tantalum," by George W. Sears, was read by Mr. Smyth. Dr. Sears' paper contains an interesting summary of the uses, alloys and ores of tantalum and a resume of present method of reduction. The uses of tantalum is based on its extreme rise to the reaction of even the strong mineral acids, its great avidity for the common gases and its capacity for transforming alternating to direct current. Tantalum, as an alloy material, has received considerable study and many alloys have been reported. Among them three types appear to .be most prominent, alloys of high melting point, hard alloys and acid rising alloys. As the estimated quantity of tantalum in the earth's crust is less than that of gold, it must be looked upon as n rare metal. Australia is the greatest producer and the Black Hills of South Dakota produce minor amounts. As the one type of mineral available contains both tantalum and columbium, the extracting and metallurgy of tantalum are difficult chemical processes. Greater simplicity in this and the development of a market for columbium would undoubtedly be of great benefit to the tantalum industry, andl make for a greater use of tantalum produced.

Jan 1, 1930

By Franklin G. Pardee

IN 1920 the Minnesota Tax Commission estimated a reserve of 1,341,674,538 long tons of iron ore in Minnesota, the Michigan State Tax Commission report showed 199,092,855 long tons in reserve in that state, and the Wisconsin Geological Survey set the Wisconsin reserves at 21,500,000 long tons. The total reserve that year for the Lake Superior District amounted to 1,562,267,393 long tons. Ten years later the reserves of iron ore in these same districts were Minnesota 1,235,227,510, Michigan 168,349,823, and Wisconsin 23,000,000, or a total of 1,426,577,333 long tons. The decrease in ore reserves in this ten-year period was 135,690,060 long tons, but the shipments were 520,746,975 long tons. In other words, the ten-year depletion in reserves was only 8.68 per cent. If similar conditions carry into the future this calculation would indicate a life for the ore reserves of the Lake Superior region of over 100 years.

Jan 1, 1933

By William L. Batt

FROM the time the Japs overran the Far East, the United Nations faced a serious military problem in the critical shortage of many raw materials desperately needed to prose¬cute the war on two fronts. For many months this critical shortage threatened substantially to limit the gigantic effort to get shooting equipment into the hands of the fighting men on the far-flung battle lines. Now this crisis has been met. Solvency in raw materials has been achieved. Simply stated, this job of producing solvency has been done by "cutting cloth to fit the garment." This does not mean that we have all the raw materials we need. Unfortunately, a few raw materials are still short, thereby limiting the total production of certain war goods, or making these goods less effective. Where the supply of raw materials is known to be limited, however, substitutions have been made or production schedules have been geared to the amounts available, and an over-all balance has been achieved between various parts of the war-production program.

Jan 1, 1943

E. E. Olcott, New York City: Prof. Kemp's valuable description of the Lancaster Gap mine is in line with many other able contributions on the origin of mineral deposits that the Institute has lately brought forward. The splendid contribution that Prof.

Jan 1, 1895

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983

By Walter B. Lenhart

Introduction and Importance of the Industry Sand, as described in this chapter, is a crude product used for ballast on railroads and highways, and as the fine aggregate in concrete, mortar, plaster and in asphalt paving materials. The sand used in glass, as a molding sand, and as a source of silica is described in Chapter 43. Sand and gravel together constitute the mineral raw materials of largest volume produced from the earth. In 1958, as reported by the U.S. Bureau of Mines,21 680,080,000 tons of sand and gravel (including industrial sand) were produced in the United States. The nearest competitor was crushed rock of which 532,818,000 tons were produced. Coal, both bituminous and anthracite accounted for only 431,616,689 tons in the same year. In dollar value, sand and gravel were exceeded only by cement, crushed rock and fuels. Hence it is a major unit of the mineral-producing industry. As an example, one plant in California operates around the clock at an average rate of 1,500 tons per hour, and at peak intervals has shipped over 4,000 tons per hour, all by trucks. Nevertheless, it is controlled by one man through a panel of push buttons that control the crushing, screening, washing, grading, stock piling, and reclaiming of the products. Because sand and gravel are low-valued commodities, but are used in every construction undertaking in every city, village, farm, dam and highway, they are produced in almost every county in the United States and southern Canada, by thousands of individual operators, very few of whom operate in more than one community. Many operations, particularly those established to supply the needs of major dams that are under construction, or of major segments of new highways, are temporary in nature, and the equipment installed is more or less portable. Because of the bulky nature of sand and gravel, there is very little interstate movement, and almost no exports or imports, except a little movement back and forth across the border of the United States and Canada. First, the material needs definition. Definitions Sand and gravel have been defined as continuously graded unconsolidated materials that appear in the earth's surface as a result of the natural disintegration of rocks. Both normally appear together, but in a wide variety of sizes, types and range of size classification. The American Society for Testing Materials has tentatively revised its definition of "sand" as: granular material passing the 3/8-in. sieve and almost entirely passing the No. 4 (4760-micron) sieve and predominantly retained on the No. 200 (74-micron) sieve, and resulting from natural disintegration and abrasion of rock or processing of completely friable sandstone (ASTM Designation C 58-55T). The Society's tentative revision of its definition of "gravel" is: granular material predominantly retained on the No. 4 (4760-micron) sieve and resulting from natural disintegration and abrasion of rock or processing of weakly bound conglomerate (ASTM 125-55T). Sand and gravel deposits contain materials from the finest silt to the largest boulders. Chemical definition of the two materials is nearly impossible. Sand and gravel always are

Jan 1, 1960

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By B. Fazan, O. D. Sherby, J. E. Dorn

McLean&apos;s technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-&apos; have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By A. H. Daane, J. F. Haefling

BECAUSE of the wide use of platinum in industry and research, the physical properties of this metal, including its vapor pressure, have been studied in some detail.&apos; The other members of the palladium-platinum group of metals have not been studied as extensively, and only qualitative information is available on the vapor pressure of palladium. Data given in literature by Vines1 and Brewer2 on the vapor pressure of palladium are based on the qualitative observations by Holborn and Austin3 and Crookes4 on the rate of volatilization of palladium filaments in various atmospheres. The general observation that palladium is the most volatile metal of the palladium-platinum metal group was corroborated by Bell, Love and Normand who studied the separation of isotopes of the platinum-group metals by a mass spectrometric method. We have measured the vapor pressure of palladium using the Knudsen effusion technique. In this work, the effusion vessel was suspended from a quartz-fiber microbalance into an induction furnace, and the amount of vapor effusing from the vessel was determined by direct weighing of the vessel during the measured heating times. This technique has been described in a report from this laboratory." The vapor pressure of palladium was calculated from these measurements using the equation P...... = 17.14 -W- (77m)&apos;u [1] a t where ? is the weight loss in grams of vapor of molecular weight m from a vessel having an orifice of a sq cm, during t sec. The derivation of this equation from kinetic theory has been described in a previous report from this laboratory: as well as in texts discussing the kinetic theory of gases.%" Test Vessel—In the search for a suitable material for the effusion vessel, it was found that tantalum reacted with palladium metal to form intermetallic compounds, and graphite was readily dissolved in palladium metal to form what appeared to be a liquid phase at a temperature several hundred degrees below the melting point of palladium. On cooling, the graphite gathered into spherical balls in the palladium, with crystals extending radially from the center of these balls, some of which were a millimeter or more in diameter. However, palladium metal vapor did not attack the graphite vessel, so graphite could be used where it did not contact condensed palladium. Tungsten did not appear to react with palladium vapor or molten palladium at its melting point, but it was not convenient to use a tungsten-vapor pressure vessel because of the difficulty of fabricating this metal. Since the vapor-pressure range to be studied (10 2 to 10 &apos; mm) did not appear to extend above the melting point of palladium, a combination of tungsten and graphite served to provide a very satisfactory effusion vessel. The lower half of the graphite vessel was lined with some strips of tungsten foil and the sample of palladium consisting of a coil of sheet was placed in the tungsten liner; in this way, no contamination of the palladium by carbon occurred. Procedure After outgassing at 1500C, the tungsten-lined graphite effusion vessel was loaded with 300 mg of

Jan 1, 1959

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965