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By C. A. Hartnagel, D. H. Newland

Most of the petroleum produced in New York State is obtained by flooding; that is, water drive. No important oil fields have been developed during the past 30 years, nor does there seem much hope that the productive oil areas will be substantially enlarged in the future. There is some prospect that additional supplies may be obtained by deeper drilling, but deep tests for gas to the Oriskany sandstone in some of the oil-producing areas have been without results so far as any discoveries of oil are concerned. Although the flooding method had been made legal in 1919, and some floods had been in operation previous to 1921, that year marks the beginning of a rapid increase in oil production by the new method. The flush production of oil in New York was in 1882, shortly after the discovery of the Richburg pool in Allegany County. The oil production in that year amounted to 6,685,000 bbl. The 1937 production of 5,478,000 bbl. was the largest since the flush production of 55 years ago. The effectiveness of water-flooding for increasing oil production from the old New York fields is shown in Table 1. Table 1.—Production of Oil in New York since 1921 Year Barrels Year Barrela 1921 988,000 1929 3,377,000 1922 1,000,000 1930 3,647,000 1923 1,250,000 1931 3,363,000 1924 1,440,000 1932 3,508,000 1925 1,695,000 1933 3,181,000 1926 2,242,000 1934 3,804,000 1927 2,603,000 1935 4,236,000 1928 3,377,000 1936 4,633,000 1937 5,478,000 The area of the New York oil fields is about 60,000 acres. It has been estimated that not over one-fourth of the area is being flooded. Very little of flooded territory has ceased to produce. Some leases flooded by the early, less scientific methods are being again subjected to the water

Jan 1, 1938

By B. C. Burgess

AFTER many years of close and friendly association with talc and soap-stone, this orthographically distinguished mineral steps forth in this edition, for the first time in a chapter of its own. Pyr, the Greek for fire, and phyllite, a rock or stone, form its name and at the same time refer to the first recorded use of pyrophyllite as firestones or hearthstones. Another derivation of "phyllite" is from the Greek phyllites, "of leaves," alluding to the beautiful white radial crystal aggregates that form when pyrophyllite is heated. Pyrophyllite used by the Chinese for carving is called agalmatolite, from the Greek agolma, meaning an image. COMPOSITION AND PROPERTIES Pyrophyllite has previously been grouped with talc because of the close similarity of the minerals in physical and optical properties. They have the same space group; and chemically they are closely related, pyrophyllite being the aluminum silicate A12Si4010(OH)2 and talc the magnesium silicate Mg3Si4010 (OH) 2. Another arrangement of the pyrophyllite formula is generally given as A12034Si02H20 because it expresses the chemical composition as usually determined (alumina 28.3 pct, silica 66.7 pct, water 5.0 pct). Vanderbilt gives pH values of pyrophyllite 5.6 to 8.4.29 Pyrophyllite usually is white, pale green, cream or pale yellow, buff or light gray. It is found in darker shades and other colors principally due to oxidation of contained iron minerals. It is translucent in thin sections. In hardness it is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. In bulk specific gravity, the powdered mineral ranges from 0.4 to 0.7. Its luster is pearly to dull; it is infusible in the Bunsen burner flame, slightly affected by aqueous solutions of sodium carbonate and hydrochloric acid. It is decomposed by sulphuric acid, with separation of gelatinous silica. It is characterized chiefly by its micaceous structure and cleavage, its softness and greasy feel. Two other varieties occur

Jan 1, 1949

By J. E. Lawver, R. R. Beebe, J. L. Wright

This paper describes a separation coefficient Ks useful as a "measure of goodness" to be used in factorial and response surface methodology. The use and limitations of the separation coefficient is discussed, and a computer program for calculating the coefficient is presented (in Fortran). The application of the coefficient is illustrated in terms of electro-dynamic separation of Mesabi semitaconites. Present Mesabi wash ores and gravity concentrates with an iron to silica ratio of only 5 or 6 to 1 are no longer readily salable, for the steel industry now demands concentrates with an iron to silica ratio of at least 10 to 1 and a structure comparable to pellets. THE ELECTRODYNAMIC-FLOTATION PROCESS Wash ores and gravity concentrates consist largely of hematite, goethite, and quartz. Several methods of beneficiation are being tested at the University of Minnesota Mines Experiment Station with a view to improving the salability of these materials. A process that looks particularly promising from an economic view is the combination electrodynamic-flotation process shown in Fig. 1. This process is designed to upgrade gravity concentrates to a 5% silica content and to provide fines — from the flotation circuit —to permit agglomeration. Although electrodynamic concentration of specularite is an established and well-understood process, the electrodynamic concentration of Mesabi goethite-hematite gravity concentrates presents interesting and enigmatic problems. The gravity concentrates are by no means assemblages of clean, free mineral particles. Instead, the concentrates to be retreated consist of a great variety of middlings. More or less complete liberation would require grinding to minus 325 mesh, at which size only flotation could be expected to function, and even then grades and especially recoveries would not be satisfactory. A close examination of the gravity concentrates shows that grinding to 100% minus 48 mesh will produce a product which is approximately 70 weight % plus 325 mesh (see Fig. 1). The remaining 30 weight % can be deslimed and floated by conventional methods, but the resulting iron concentrate is

Jan 1, 1964

By H. R. Hanley

IT is a well-known fact that the solubility of zinc compounds decreases when these compounds are roasted in contact with iron compounds, but descriptions of tests to quantitatively express the fact have not appeared in the literature. Possibly such an expression cannot be uniformly and exactly duplicated by different operators because of the variation in the personal equation. In a general way, however, the reactions between zinc compounds and iron compounds under roasting conditions will show a certain trend with changing conditions and the approximate quantitative expression of this trend appears reasonably well established by experimental work conducted for this purpose. Ferrites and Marmatites The name "ferrite" has been given to the compound of zinc and iron which has the formula Zn0.Fe203. Among the questions pertinent to this subject are those involving inherent or natural ferrite, and also the synthetic or artificial variety. The inherent or natural product is formed when the mineral containing iron and zinc sulfides isomorphously crystallized is subjected to oxidation at roasting temperature. These isomorphously crystallized minerals are known, mineralogically, as marmatites, and contain ZnS and FeS in ratios of 2 to 1 up to 5 to 1 respectively. The zinc and iron sulfides form a definite mineral. They are firmly attached to each other and form common contact planes through which diffusion of the entities occurs during the roasting process. This diffusion of the molecularly intimate entities produces, during roasting, the compound referred to as ferrite, in proportion to the amount of iron originally present in the marmatite. For example, a marmatite from British Columbia containing 9.739 per cent. Fe and 56.87 per cent. Zn corresponds with the mineral having the formula 5ZnS.FeS. The ferrite produced in roasting, which has the formula ZnO.Fe203, contains 27.07 per cent. Zn and 46.40

Jan 1, 1929

By Walter W. Bradley, OLAF P. JENKINS

IN April of this year the California State Division of Mines (formerly known as the State Mining Bureau) observed its 50th anniversary. The Division serves as a bureau of information and, an encyclopaedia of California's economic minerals. Its primary function is to make economic surveys of the mineral resources of California, their development and utilization. Geological studies also constitute a related part of the work as being necessary in tracing and out- lining ore deposits and the most likely areas in which to find them. The results of the Bureau's data-gathering are published in the form of annual reports of the State Mineralogist, and in bulletins on specific substances. The Division is just completing a series of reports on the mineral resources of the State arranged by counties.. It is now starting .a new series of reports arranged according to substances particularly the so-called non- metallic commercial groups. Of these the following are now available: clays, barite, and mineral paint. These will be followed by reports on feldspar and silica, diatomaceous earth, limestone and others

Jan 1, 1930

By Charles Will Wright

THE economy as well as the living standards of a country depends largely upon adequate supplies of raw materials at reasonable prices. Geological and climatic conditions responsible for the occurrence of commercial minerals and the growth of raw agricultural and forest products are so varied in different parts of the world that no country can be self-sufficient. The world is rapidly shrinking because of improvement in transportation facilities, but populations are steadily increasing and so are the needs for a greater production of raw materials and for their more equitable distribution. Too many barriers between nations prevent free access to the main sources of supply of the raw materials vital to neighboring nations and it is just such barriers that are often the cause of friction and even war. The International Trade Organization is doing a commendable job in helping to. break down barriers and to reduce friction, and we should now find ways to facilitate access to these sources of supply and encourage more efficient and greater production of the raw materials so urgently needed throughout the world. This cannot be done by individual selfish governmental agencies, influenced as they are by politics, nor by socialistic governments attempting to nationalize industries. It can be done efficiently only by the free individual through private enterprise properly protected against adverse governmental action. This protection can be supplied by the World Bank.

Jan 1, 1948

By R. E. Wagner

MISSOURI's famous lead area, in what is known as Southeast Missouri, is locally termed the "Lead Belt." These deposits are in the Bonne Terre dolomite of late Cambrian age which has a thickness of nearly 400 ft. Underlying this is the La Motte sandstone which varies in thickness from 0 to 400 ft. The La Motte beds are deposited directly on the ancient erosion surface of Pre-Cambrian porphyries and granites of probably Algonkian age. The buried igneous peaks extend up into the Bonne Terre in several areas within the Lead Belt. Overlying the Bonne Terre are shales and siliceous dolomites of late Cambrian and early Ordovician age. Within the Lead Belt these have a thickness of from 0 to 500 ft. The district is bounded in general on the southwest by the Sims Mountain fault, on the northwest and north by the Big River fault, and on the

Jan 1, 1947

By T. Kilner, A. Plumtree

DURING an investigation of electro-deposited silver structures, samples were prepared for metallographic examination by cold mounting in plastic, grinding on successive grades of emery paper down to 3/0, and chemically polishing by swabbing using the chromic acid solution described by Gilpin and Worzala.1 Attempts to etch these samples using the standard solutions described for silver (e.g., 5 pet KCN-5 pet Na2S2O8, H2O2-NH4OH, and various potassium dichro-mate solutions) all failed to give good results due to staining of the samples and to rapid etching. The staining was caused by the chromic acid polishing solution being trapped in small fissures between the sample and the mounting plastic, and also in small fissures in the sample itself. To overcome these difficulties, an etchant was developed which prevented staining at the same time as it slowly etched the sample. This resulted in a very clean, crisply etched surface as shown in Figs. 1 and 2. This etch consisted of 10 ml of orthophosphoric acid, 10 ml of distilled water, and 2 drops of the polishing solution noted above,' which is made by mixing 100 ml of saturated CrO3 solution, 45 ml of 10 pet HC1 solution, and 800 ml of distilled water. The etching procedure involved taking the final polished sample, either immersing or swabbing in the etchant for a period of 1 to 2 min, rinsing as quickly as possible in distilled water, alcohol, and ethyl ether in that order, and then immediately drying. This etch is easily controlled due to its slow rate of etching, and produces samples with clean, sharp surfaces. Pits due to overetching produced varying contrast effects when viewed under polarized light, and are therefore obviously useful for revealing many structural details within the sample. Another effect of overetching was to produce a height varia-

Jan 1, 1968

By Gilbert P. Moore

Bolivia does not yet have any production which is being marketed. It does have a potential production, however, from wells which have been completed by the Standard Oil Co. of Bolivia, a subsidiary of the Standard Oil Co. of New Jersey. No other company is active in drilling and development work to date. The total potential production from wells now completed is about 6000 bbl, daily. Wells Completed Completions during 1928 and their initial daily productions. if any, were as follows: Camatindi No. 1, 350 to 1000 bbl.: Camiri No. 1, 500 bbl.; Sanandita No. 3, 100 bbl.; Tatarenda No. 1, dry hole, and Bermejo No. 2, deepened 50 ft. made 1000 barrels. The most striking development of the year was the Camiri No. 1 well which, after just entering the sand, made 500 bbl. per day of 52" B. oil. This well is the northernmost good producer which the Standard has brought in to date. Oil from this well is used without refining in the tractors and trucks of the company. A small topping plant has been installed from which high-grade gasoline is obtained for use in motor cars and some is being produced for the use of air plants stationed at Villa Montes. The results for Sanandita No. 13 were somewhat disappointing since Sanandita No. 2 was rated at about 3000 bbl. Tatarenda NO. 1, located on a large unbroken structure, was drilled to 4000 ft. and abandoned as a dry hole. Bermejo No. 2 was deepened 50 ft. to 2085 ft.. and on a 10-day test averaged 1000 bbl. per day. This well is on the border between Bolivia and the Argentine. Wells Drilling The wells drilling are Camiri No. 2, Sanandita No. 5, Machareti No. I and Bermejo No. 5. This is the smallest number of drilling wells which the Standard has had for several years but is principally due to

Jan 1, 1929

By John Henry Harden

It appears that in the earlier days of anthracite coal mining, 1824-25, the Lehigh region mined 76 per cent. of all the coal sent to market. During the same period Wyoming sent 12 and 5 per cent. respectively, whilst the Schuylkill sent 11 and 18 per cent., the number of tons marketed being in those days very small indeed. In the year 1828 the Schuylkill region mined over one-half of all the coal sent to market, and continued to do so for thirty years (with the exception of the year 1831), until 1858 ; since that date the production has declined very steadily in comparison with the other regions, until, in 1876, it was only 34 per cent. Wyoming, in the year 1820, was mining 40 per cent., but the production of all the regions was very small; in six years it declined to 5 per cent., increased to 34 per cent. in 1831, declined to 10 per cent. in 1838. Since which time the increase has been gradual, until 1873-75 Wyoming produced over 50 per cent. of all the anthracite coal sent to market. In 1867 the production exceeded that of Schuylkill, and has continued to do so since that time. In the year 1876, during the existence of the "coal combination," Wyoming lost 9 per cent.; during the same time Lehigh gained 7 and Schuylkill 2 per cent. over their relative production of the preceding year, the decrease of Wyoming being two and a half million tons, the increase of the Lehigh one million, the decrease of the Schuylkill nearly three-quarters of a million. The extraordinary production of the Lehigh region at a time of decreased demand and in opposition to an agreement with the other regions to limit the supply to the supposed demand mas the cause of the disagreement which ultimately broke up the combination of the great coal-producing and carrying companies. The Lehigh region produced very steadily, from 1829 to 1854, an average of about 22 per cent. of the whole production. From 1854

By James P. Roe

I. INTRODUCTION. THOSE who deem the subject of this paper an old and super¬seded one may recall with advantage the words of the great proverb-maker, bidding us to seek the new in the ashes of the old. The manufacture of wrought-iron began with the small hearth built upon an eminence, and relying on the wind for blast. Next came, either the hearth about 12 in. in diameter by 2 ft. in height, blown by a man operating two goat-skins for bellows, or, a hearth of greatly varying diameter and about 10 ft. high, depending for its blast upon natural draft. The former appeared in India, the latter in Burmah; and both were in operation until quite recently, though their origin is lost in prehistoric times. The Catalan forge was the evolutionary descendant of the foregoing, and the parent of the Blase-ofen, which in turn led to the high bloomary or " Stückofen," the father of the blast-furnace, as a producer of cast-iron. The production of cast-iron checked the growth of the direct processes; and led to the introduction of various hearths, such as the Walloon, for low-silicon irons; and the South Wales process, combining the run-out fire with the finery, for higher-silicon irons. Some of these are still in operation in localities possessing the necessary raw materials; and their product is used for purposes requiring wrought-iron of exceptional quality, the supply of which is still smaller than the demand. We have to look back but a century and a quarter to see the introduction of the puddling process by Henry Cort; a process which, reinforced by the iron-oxide bottoms and fettling of Hall, was not less revolutionary in character, and more revo-

Jul 1, 1905

Alexander N. Winchell, Butte, Mont. (communication to the Secretary): Mr. Spurr calls attention to the fact that an ore-deposit may be due to a succession of concentrations at different geological epochs. He cites an example of such a condition on Napoleon creek, a branch of Forty-Mile creek, Alaska. It will perhaps be of interest to call attention to another example of the same general character, not so remotely situated. The example referred to is located on Pole creek, a tributary of Cherry creek, in the extreme northeastern part of Madison county, Montana. An excellent geological map of this region is to be found in the Three Forks folio (No. 24) of the United States Geological Survey. According to this map, Pole creek, in its upper course, occupies the contact between the " Flathead " formation, which Peale correlates with the Middle and Lower Cambrian, and an area of gneisses and schists supposed

Jan 1, 1903

By D. J. Blickwede

PRESENT knowledge of the effects of time and temperature upon stabilization of the austenite-martensite reaction in steel is fairly complete,1-3 but at the time the work described herein was initiated there was no information about the effects of alloy elements on the phenomenon. However, it has been assumed on theoretical grounds that alloy elements, particularly carbide formers, may have a significant effect on stabilization.' The present work was undertaken to provide information about the effect of two common elements, nickel and molybdenum, on stabilization in hypereutectoid and hypoeutectoid steels. Seven induction-furnace melted, 1.2 pct C steels ' with a variation of nickel from 0 to 6 pct and of molybdenum from 0 to 1.0 pct were used for most of the experiments. Along with these a series of 0.4 pct C steels containing 0 to 6 pct Ni were also studied. The chemical compositions of the steels are listed in Table I. Stabilization in these forged, hot-rolled, annealed, and centerless ground steels was measured by aging brine-quenched specimens (aus-tenite temperature, 1800°F) at 95" and 150°F and then determining the change in specific volume produced by subsequent cooling from room temperature to —320°F.³ In presenting the results the decrease in the change in specific volume, ?V, after various stabilization times is used. This is given by ?V -= ?VO - ?V1 where AVO is the change in specific volume on quenching directly to —320°F and aV, is the change in specific volume on quenching to —320°F after stabilizing for time t. In other words, ?V is a direct measure of the amount of martensite that is lost to the subzero quench as a result of stabilization and hence is greater, the longer the aging time or the higher the aging temperature. The results are shown in Fig. 1. The scatter of the data, which are not shown for clarity and brevity, was sufficient to make the relative location of the curves on the ?V axis inaccurate within ±2x10-5 cc per g. However, some generalities appear which are of interest. Effect of Nickel In the 0.4 pct C steels, up to 3 pct Ni has little, if any, effect on the rate or amount of austenite stabilized at 95°F, Fig. la. Increasing nickel from 3 to 6 pct almost doubles the amount of austenite stabilized in a given time. In the 1.2 pct C steels aged at 95°F, increasing the nickel from 1 to 3 pct appears to decrease the amount of stabilization, and a further increase to 6 pct Ni completely eliminates stabilization as shown in Fig. lb (M, of 6 pct Ni steel was below room temperature). The same behavior was exhibited by these steels stabilized at 1500°F, especially after aging for periods longer than 5 hr, Fig. lc. Thus it appears that up to 1 pct Ni has little effect on stabilization at low or high carbon levels. More than 1 pct Ni increases stabilization at low carbon contents and decreases it at high carbon contents. Ward, Jepson, and Rait5 have found that at inter-

Jan 1, 1954

By D. F. Kaufman, E. D. Levine, L. R. Aronin

ThE primary slip plane in hcp metal crystals can usually be inferred from the c/a ratio. Basal slip is the primary system at room temperature for zinc, cadmium, magnesium, cobalt, and rhenium, all of which have a c/a ratio greater than 1.60. Zirconium and titanium, on the other hand, each with a c/a ratio of 1.59, deform primarily by (1010) [ll20] prismatic slip. The increasing tendency toward prismatic slip in these materials is generally thought to be associated with the increase in atomic density on (10i0) as c/a is reduced. Beryllium, with a c/a ratio of 1.57, would, according to the above scheme, be expected to exhibit prismatic slip. However, in beryllium of commercial purity, the primary deformation mode at room temperature is basal slip.' The ratio of critical shear stress for prismatic to that for basal slip at room temperature is approximately 5:l. The critical shear stress for prismatic slip decreases quite rapidly with increasing temperature, however, and at 500°C the ratio is approximately unity. The apparently anomalous behavior of beryllium has led to speculation that prismatic slip in this material may be restricted by an anisotropic effect of impurities,' and that, if beryllium could be purified to a sufficient extent, prismatic slip might predominate at room temperature. In such a case, the conditions under which basal cleavage can occur would be suppressed, and enhanced low-temperature ductility might result. With the advent of the floating-zone method for purification of beryllium,3 it has become possible to determine experimentally the effects of purification on basal and prismatic slip. Tensile tests were performed at room temperature on single crystals oriented favorably either for basal or prismatic slip. The crystals had been purified to various extents by zone-refining, employing procedures that have been described elsewhere.4 Relative purities of the crystals were estimated by measuring the ratio of electrical resistance at 4.2"K to that at 298°K. Typical values ranged from 0.40 for commercial-purity material to 7.7 X 10"4 for crystals prepared from vacuum-distilled beryllium and subjected to six zone-refining passes. The purity dependence of the critical shear stresses for basal and prismatic slip is shown in Fig. 1. In the purity range studied, the critical shear stress for basal slip is decreased from 1.4 to 0.14 kg per sq mm. The critical shear stress for prismatic slip is decreased from 6.7 to 5.3 kg per sq mm. The decreases in critical shear stress for each deformation mode, therefore, are approximately equivalent. No purification anisotropy is observed. Because of the absolute magnitudes of the critical stresses, the ratio of the critical shear stress for prismatic slip to that for basal slip actually increases from 5:l to 38:l at the highest purity level studied. It is evident, therefore, that basal slip is the primary deformation mode in high-purity beryllium. This fact must be accounted for in any rationalization of the deformation behavior of hcp metals. This work was performed at Nuclear Metals, Inc., under the sponsorship of the U.S. Atomic Energy Commission.

Jan 1, 1964

By Louis Moyd

In the preparation of illustrations to accompany reports of investigations concerning particle shapes of various natural and manufactured materials proposed for use as he aggretates in concrete structures, it was found that stereoscopic views of such materials presented the information much more effectively than the usual two-dimensional photographs. With the whole-hearted cooperation of the Photographic Section, a technique was developed in the petro-graphic laboratory of the Concrete Research Division, U.S. Corps of Engineers, at Clinton, Miss., for simple and rapid preparation of paired stereoscopic photographs and micrographs. The method requires only equipment which is usually part of the general stock of any laboratory, and it is adaptable for all purposes in which three-dimensional views would be found superior to ordinary photographs. Stereoscopic Photographs Where the subject or subjects to be photographed are small but not of microscopic size, an ordinary camera having a ground-glass focusing screen is set up vertically over the field. The material to be photographed is placed on a card, the surface of which is suitable as a background. The card is mounted so that it can be tilted about 5' above and below the horizontal plane, on an axis that coincides with the north-south diameter of the viewing screen. A simple way of achieving this is to mount the card on an object having a convex lower surface. In our laboratory, a watch-glass has been used, with plasticene as the mounting medium. The convex surface should be mounted on a support having a round opening on top and a flat bottom. A roll of tape, a petri dish, a beaker, or any other piece of equipment having the proper shape to give stability to the setup will be satisfactory. The arrangement of the required equipment is shown in Fig 1. For the best results, the subject to be photographed should be mounted in the plane of the axis of rotation. To achieve this effect, the depth of the mass of plasticene between the background and the watch-glass is varied so that when the watch-glass is tilted back and forth on the axis, the subject to be photographed does not appear to move back and forth across the viewing screen. A permanent piece of equipment, embodying an adjustable vertical screw, with lock-nuts, could be made for this purpose. The subject may be illuminated in any manner desired. It was found that the presence of shadows intensifies the effect of depth. In taking the photographs, the concave surface is mounted so that one side of the background card is about 5' below the horizontal, while the axis remains in the horizontal plane. The subject is focused carefully on the ground glass and a picture is taken. The card is then tilted so that the opposite side is about 5' below the horizontal, while the axis still remains in the horizontal plane. The subject is again put in focus and another picture is taken. After both pictures are developed and printed, they are placed side by side in the same orientation and examined with a stereoscopic viewer. If depressions appear where there ought

Jan 1, 1950

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

By R. C. Amero

FULLERS earth is a general name applied to claylike minerals that have high natural ad-sorptive powers. They are usually distinguished from ordinary clays by a higher content of combined moisture and a lower apparent density. The definition is based on the ancient use of the material for fulling, or cleansing woolen cloth of oil and grease; a more modern definition should mention the ability to decolorize oil and should differentiate between fullers earth, which is naturally active, and certain bentonites which only develop decolorizing power after being leached with strong mineral acids. The distinction between fullers earth and activable bentonite is not a sharp one, since all types of intermediate clays can be found that are more or less naturally active, yet more or less responsive to acid treatment. The differences seem to depend somewhat on the amount of leaching that has been effected by natural ground waters. Physical Properties The principal mineral constituent of activable bentonite is montmorillonite, a hydrous aluminum silicate to which the following formula is generally assigned: Al,Si,O,, (OH), • 12H,O Fullers earth, as well as bentonite, is usually composed of some variety of montmorillonite, but in the United States the largest tonnage of fullers earth is mined from deposits of attapulgite. Attapul- gite is a clay mineral composed of monoclinic crystals of colloidal size, having a fibrous shape similar to that of asbestos. A sectional model of the attapulgite "molecule" is shown in Fig. 1. A single unit is about 18.0 A wide and 12.9 A high. The length of the molecule is variable, but this same molecular pattern is repeated to form needlework crystals, rather than flakes, as is characteristic of the montmorillonite crystals. Attapulgite has been assigned the following formula,' although actually, the magnesia has been largely replaced by alumina: (0%) . (OH), • Mg, . Si, • Olp . 4H20. The fibrous nature of the mineral is clearly shown in the electron micrograph, Fig. 2. Although the deposits contain 5 to 30 pct quartz and carbonate minerals, impurities in the commercial products are held at a low level, principally by selective mining on the basis of oil decolorizing efficiency. The particle size distribution of this fullers earth has been estimated from settling rates, using sodium citrate as a dispersing agent.' Since Stokes' law only applies to spherical particles, the equivalent particle diameter calculated below is probably more nearly an index of diameter rather than length of the needlelike crystals: Eqnivalent Arbitrary Particle Distribution, Size Diameter Pci Classil3catian 0.05 mm 0.80 0.80 pct sand 0.05-0.02 mm 10.96 0.02-0.01 mm 9.65 42.10 pct silt 0.01-0.005 mm 11.40 0.005-0.002 mm 10.09 2-0.5 micron 10.61 0.5-0.2 micron 29.09 56.58 pct clay 0.2-0.05 micron 14.86 0.05 micron 1.96 The differential thermal analysis shown in Fig. 3 is unique and supports the theory that this is a distinct mineral species.' ~ Other general properties of the mineral as shown in Table I.

Jan 1, 1952

William Metcalf, Pittsburg, Pa. (communication to the Secretary*): I am greatly pleased that some one has at last reached what I have long regarded as the only rational explanation yet given of the reasons why steel hardens. Mr. Field claims originality; and doubtless he is entitled to it, but not to priority, mhich must be granted to Prof. John W. Langley.' The difference between them is that Langley says " Tension, probably molecular," and Field says " Tension, probably atomic "; in either case the vital thing after solution is tension. Mr. Field's argument carries with it the idea of increase of density with hardness; if he mill study the facts farther he will observe that the case is just the reverse; that is, the greater the hardness the less the specific gravity; it was just this fact that led Langley to his conclusion, in mhich I have always concurred. Field agrees with Langley that the first requisite for perfect hardening is complete solution of the carbon, not combination; and all of the facts agree with this conclusion. The fact that increase of hardness causes reduction of density was first brought to my notice some 40 years ago, when Major William Wade was testing Jones & Laughlin's cold-rolled iron, and I mas his assistant. We found the well-known increase of tenacity, compressive strength, torsional resistance, and hardness. Specific-gravity tests showed that the cold-rolled iron was less dense than the hot-rolled bars. Major Wade was so surprised at this result that he gave me a lot of samples to weigh, saying that he was not satisfied with

Jan 1, 1904

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949