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By M. King Hubbert

DURING the past summer the writer was asked by the Illinois State Geological Survey to make a study of some of its economic geological problems with regard to the applicability of geophysical methods of prospecting to their solution. The following four problems were sug-gested for investigation: (1) the fluorspar area of Southern Illinois, (2) oil structures in the south central part of the state, (3) the lead and zinc-bearing area of northwestern Illinois, and (4) the water supply and gravel deposits of the glacial drift. The prime requirements were to find a means of obtaining a maximum of useful information with a fairly modest outlay of expenditure for technical staff and equipment. The method of procedure adopted was that of making a preliminary study of each of the problems named by means of available office data and published reports with supplementary field reconnaissance where necessary.

Jan 1, 1932

By Bruce H. Gardner, Stephen A. Miller, Shosei Serata

The Bryan Mound salt dome in Freeport, Texas, has some of the largest and oldest solution caverns in the U.S. There are a total of five caverns of varying shapes and sizes randomly distributed throughout the salt dome. When the caverns were converted from a brine production to an oil storage operation, the effects on long-term stability of the caverns and inter-cavern behavior were analyzed to evaluate the future safety of the storage operation. The analysis was based on a worst-possible-case scenario, including accidental wellhead pressure loss. The impact of this pressure loss upon the thinnest partition between the two closest caverns was analyzed, using a case example of storing lightest weight LPG, thereby creating maximum differential pressures between these two caverns. The finite element method with the REM computer code was utilized for this analysis. Results of the analysis illustrate the basic mechanisms of the long-term behavior of the multiple caverns in the LPG storage operation.

Jan 1, 1985

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970

By Wayne E. Hall

The Darwin mining district of California, 160 miles north of Los Angeles, has yielded an estimated $45 million in lead, silver, zinc, and copper since 1875. The deposits are in silicated limestone of Pennsylvanian and Permian age close to a stock of horn- blende-biotite-quartz monzonite. Steep left-lateral strike-slip faults that strike N 50" 70" E served as feeder channels for the ore solutions, and minor folds, favorable beds, and faults close to the feeder channels localized the orebodies. The orebodies are irregular, steep, pipe-like replacements that cut across bedding, bedding replacements, and fissure fillings in a calc-silicate country rock consisting mainly of wollastonite, grossularite-andradite garnet, idocrase, and diopside. Near surface the ore consists of a soft, crumbly mass of cerussite, hemimorphite, jarosite, limonite, and some secondary copper minerals. The primary ore consists of galena, sphalerite, pyrite, pyrrhotite, and chalcopyrite with smaller amounts of andorite, matildite, scheelite, tetrahedrite, and a high silver- lead-bismuth-selenium-bearing galena.

Jan 9, 1959

By J. A. Eisele, D. J. Bauer, L. E. Schultze

Approximately 100 million mt of magnetic reject tailings, which contain apatite and about 1% yttrium and rare-earth elements, exist in the eastern U.S. as a result of iron ore mining operations. At the present time, no economic process is available for recovering yttrium from this material. The U.S. Bureau of Mines (USBM) studied the problem to determine if an effective low-cost method could be found, thereby increasing our domestic yttrium reserves. [Fig. 1] is a line drawing of a photograph taken during microprobe analysis of a sample of the tailings, and shows the distribution of yttrium. Typical analysis of this material is 0.14% yttrium and 1.1% rare-earth elements (mainly lanthanum through neodymium). Over half of the yttrium is present as a hydrated Ca-Y silicate deposited along interfaces in the grain structure; whereas, the remainder of the rare-earth elements occur as Ca-Fe-RE silicates. The remaining yttrium and rare-earth elements are in solid solution with the

Jan 1, 1977

By Jonathan S. Jackson, Bayne B. McMillan, W. Joseph Schlitt

Various dump leach models have been developed by Kennecott, and these are reviewed with an eye toward production forecasting. Some of the models have been bated on first principles, utilizing the chemistry and physics of dump leaching. While providing considerable insight into the leaching process, these have proved to be too cumbersome for use in estimating production. Other models have been based on a declining leach rate for a single block of waste. These permit good short-term projections of solution grades and production, but are inflexible with regard to changes in mining parameters because the trends are based only on historical data. Therefore, a simple and flexible computer model has been developed to aid in leach production forecasting and to provide a tool for assessing the impact of different mining plans on leaching. This program, LEACH, is based on annualized blocks of waste; input parameters are described and examples of its use are given.

Jan 1, 1980

By R. G. Whittemore, R. Derry

Nickel metal, in powder form, has been produced by pressure reduction, with hydrogen gas, of slurries of nickel hydroxide at temperatures up to 250°C. The nickel hydroxide was obtained by precipitation from nickel chloride and nickel sulphate solutions, using both magnesium oxide and calcium oxide. Rates of reduction and yields were determined as a function of temperature, hydrogen overpressure, seed addition, and the amount of alkali used. The mechanism of reduction of slurries obtained from the sulphate system was studied, and major differences between the sulphate system and the previously examined chloride system investigated. Specifically, in the sulphate system, contra the chloride system, no seeding was necessary, plating and densification were virtually absent and only short induction periods occurred. Grades of product are given and the use of this process in the recovery of nickel from laterites is discussed. The selective reduction of nickel from mixed hydroxide slurries and effluent treatment plant sludge has also been examined.

Jan 1, 1973

By Charles S. Barrett, Frederick N. Rhines, Robert F. Mehl

The solid solutions which aluminum forms with copper, and with magnesium and silicon, are not extensive, and accordingly could not be expected to form Widmanstatten figures profusely nor with great ease. A study of the Widmanstatten figures in these systems seemed desirable, however, because of the interest which these alloys bear towards age-hardening theories resulting from the necessary relationship between the age-hardening phenomena and the atomic processes leading to the formation of Widmanstatten figures.' Alloys of Aluminum with Copper The most accurate determination of the solid solubi1it.y of copper in aluminum seems to be that by Dix and Richardsoq2 whose results are represented in Fig. 1. According to this work, aluminum dissolves 5.6 weight per cent of copper at 548", and less than one per cent at room temperature. Judging from the constitutional diagram, this solid solu-lion on cooling tends to precipitate the compound CuA12, and this conclusion has been confirmed experimentally by Schmid and Wassermann.

Jan 1, 1932

By Nathaniel Arbiter, Arthur F. Taggart

THE fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. EXPERIMENTAL Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,' and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: 1. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. DISCUSSION OF RESULTS Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether

Jan 1, 1943

By H. O. Hofman

(Canal Zone Meeting, November, 1910.) I. INTRODUCTION. IN a previous paper,1 The Behavior of Calcium Sulphate at Elevated Temperatures with Some Fluxes, we published the results of our investigation, into the behavior of calcium sul-phate in air; that, is, under oxidizing conditions. The results as a whole hold good for a neutral atmosphere, or one which has no chemical effect upon calcium sulphate. The present paper deals with the behavior of calcium sulphate under reducing conditions, the reducing-agents employed being carbon monoxide and carbon, and the changes the calcium sulphide formed undergoes when it is subjected to an oxidizing-roast. Technical literature deals very sparingly with the subject. The information furnished by the recent leading chemical manuals is general. Thus Dammer,2 Moissan,3 and Abbegg,4 quote Berthier as having reduced, in 1823, calcium sulphate with carbon, and Stammer as having done the same in 1851 with carbon monoxide; Gmelin Kraut 5 add Leplay and Laurent (1848) as third investigators. Metallurgical authorities confine their statements to the known fact of reduction by carbon. II. PREPARATION OF RAW MATERIALS. 1. Calcium Sulphate.-This salt was prepared in the same manner as described in our previous paper,6 and was found to be chemically pure. * Professor of Metallurgy, Massachusetts Institute of Technology. + Metallurgical Instructor, Imperial Technological Institute. 1 Trans, xxxix., 628 to 653 (1909). 2 Handbuch der anorganischen. Chemie, vol. ii., part 2, p. 309 (1894). 3 Traité de Chimic Minérale, 1904, vol. iii., p. 543. 4 Handbuch der anorganischen Chemie, vol. ii., part ii., p. 116 (1905). 5 Handbuch der anorganischen Chemie, vol. ii., part 2, p. 233 (1909). 6 Trans., xxxix., 630 (1909).

Nov 1, 1910

By Stanford O. Grodd

The Sanford Lake district encompasses an area covering 24 square miles in the central Adirondack Mountains of northern New York State. Discovery of the titaniferous magnetite deposits dates back to 1826. Several attempts to exploit the ores for iron prior to 1942 proved uneconomical because of difficulties with the associated titanium, lack of transportation facilities, and the isolated location. Since 1942, the National Lead Company has produced ilmenite concentrates for the titanium pigment industry, and a magnetite by-product used in the steel and refractory industries. Rocks of the area are Precambrian in age and of igneous origin. The area has a history of erosion, deformation, and metamorphism, subsidence, and finally uplift and glaciation. The resulting topography is extremely rough with drainage patterns controlled by a combination of fault patterns and glacial modifications. The district is within the large anorthosite massif making up the central high peak area of the Adirondacks. All of the various lowsilica rock types associated with the massif are found within the boundaries of the district. These consist of both the Marcy and Whiteface types of anorthosite and of gabbroic anorthosite, gabbro, and different grades of titaniferous magnetite ores. All of the rocks contain the same minerals and differ only in their percentages of these consitituents. Gabbro, and ore associated with it, demonstrate flow structure as both have foliation and lineation. Anorthosite and its associated ores are massive and show very little primary structure. Minor pegmatites and diabase dikes provide evidence of remobilization in selected areas and of late intrusion as well. Faulting is prevalent and follows a regional pattern of major faults trending northeastsouthwest and of minor faults at nearly right angles to them. There are four mineralized areas where an economic grade of ore has been found. Three of these have both gabbroic-type ore and anorthositic-type ore. The fourth has only gabbroic ore. Ores are graded according to their TiO, content, and these range from 9.5 per cent to over 30.0 per cent TiO,. Ore bodies of both types are related to gabbro and conform to the configuration of the gabbro bodies within the anorthosite. At least three distinct theories of ore genesis have been expounded by different investigators. Others propose some variations of one or more of these. Although complete agreement probably never will be reached, it is certain that no one process of ore emplacement can explain the complicated picture as seen today. Further understanding of the ores and their origin will require detailed mapping, sampling, and mineralogical studies of the entire district, and then it may never be understood without qualification.

Jan 1, 1968

By Walter Crafts, C. M. Offenhauer

IN a previous study' of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is a more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about r1to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, 1 per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to 1-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudomartensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously' that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By R. F. Janke, J. F. Bossler

Introduction The commercial use of ion exchange resins to recover uranium evolved in the decade following 1950 when significant efforts were made to recover this vital element economically and efficiently from low grade ores. It was discovered that in both acid and alkaline systems, uranium exists as an anionic complex. This led to the application of anion exchange resins to concentrate and purify the uranium product. While this is the simplest statement of what an ion exchange resin does in the recovery of uranium, it should not be forgotten that the industry is continuing to evolve new methods in mining and processing which affect ion exchange operation. The inception of solution mining, the use of expanded bed ion exchange columns and the development of continuous ion exchange systems represent several examples of this continuing evolution in the industry. Throughout all of the changes in equipment designs and variations in solution compositions, the purpose of the ion exchange resin remains the same - to concentrate and purify uranium. Ion Exchange Resins When evaluating ion exchange resins for a uranium recovery project, the task that faces the chemist or process metallurgist is an assessment of the efficiency and, therefore, the economics of the various candidate resins for a given project. This assessment should include consideration of both physical factors such as particle size, density, hydraulic expansion and pressure drop as well as chemical factors such as the uranium loading and elution characteristics. For any given application, the differences in the physical and chemical behavior of ion exchange resins are a function of the conditions used to manufacture those resins. Therefore, an understanding of the way in which manufacturing variables affect resin behavior is important. Since most uranium recovery projects are concerned with recovery of the anionic complexes of uranium using anion exchange resins, this discussion will be restricted solely to the family of anion resins. The majority of the ion exchange resins used in commercial recovery operations look similar to the resins shown in Figure #1. [ ] Most of these materials are based on a styrene- divinylbenzene copolymer. The liquid monomers, styrene and divinylbenzene, are charged to a co-polymer reactor containing water. The water insoluble monomers are then mixed with the water to suspend oil-like droplets of the monomer mixture in. the water. The entire reaction mixture is then heated causing the monomers to polymerize into sol id thermoset plastic spheres. The spherical nature of the particle, the particle size distribution and the primary crosslinking level are fixed in this step in the production process. Figure 2 is a simplified illustration of this step of the process. [ ]

Jan 1, 1979

By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Ralph W. Marsden

The natural iron ores of the Lake Superior Region in the United States are being replaced by iron-ore concentrates produced from magnetite- or hematite-rich horizons in the Precambrian cherty iron formations. The production of natural ores will soon be less than one-half of the total ore shipped annually. The tonnage of natural ore produced will continue to decline until it is a minor percentage of the ore shipped. The natural ores include (1) soft ore, (2) hard ore, ( 3) conglomerate ore and ( 4) siliceous ore. The soft ores are the important ore type and are sometimes termed "Lake Superior type ore". These ores are in situ deposits of hematite and limonite formed by the leaching of silica and other gangue materials in the iron formations. The leaching is believed to have been done by downward moving surface waters. In deep ore deposits, generally over 1000 feet below the present surface, circulation and leaching action may have been assisted by hydrothermal activity. Hard ore deposits occur on the Vermilion and Marquette ranges where hematite or magnetite has replaced the silica (and possibly some silicates) in cherty iron formation. These ores commonly occur in structural situations favorable for the movement of hydrothermal waters. The ores are believed to be the result of hydrothermal action with iron, possibly from the iron formation, transported by hydrothermal waters to areas favorable for the replacement of silica by iron oxides. Certain stratigraphic horizons of the Lake Superior Precambrian cherty iron formations contain sufficient iron as magnetite or hematite, with a grain size and texture that will give adequate mineral liberation, to yield an ore-quality product after grinding and concentration. The magnetite-rich deposits are termed magnetite taconites. These ores occur on the Mesabi, Gogebic, and Marquette ranges. Magnetite taconite ores are unenriched cherty iron formation and are the result of the sedimentary deposition of the iron formation and the metamorphic history of the rock. The commercial quality hematite-rich iron formations in Michigan are termed jasper ores. The jasper ores are being mined on the Marquette and Menominee ranges. These ores are composed of specular or granular hematite associated with quartz and iron silicates. The jasper ores appear to be recrystallized iron formations in which iron, prior to recrystallization, occurred as hematite.

Jan 1, 1968

By P. S. Bagga, P. T. Luckie

Liberation (the process of destroying the interlock between unwanted materials, such as mineral matter and pyrite, and coal) is one of the most important precursors to the benefication of raw coal in order to produce high grade marketable coals at economical recovery levels. Liberation is achieved usually by comminuting the raw coal. However, because of the significant interaction between the production of fine particles to achieve liberation and the cost of separating fine particles, the coal industry needs a method projecting the change in washability with size reduction. Such a projection can be combined with size reduction and separation simulators in order to examine completely beneficiation circuitry to produce coals of stringent specification. This paper presents the development of an appropriate liberation model for coal and its solution by Monte Carlo simulation to predict the expected washability of the raw coal as a function of comminution. It includes model validation with a known binary mixture as well as with a known teritary mixture.

Jan 1, 1983

By Thomas F. Bates

ANALYSIS of the chemical and structural differences in minerals often results in a better understanding of the differences in the geological conditions under which they were formed. The minerals in the kaolinite group differ in the amount of interlayer water and in the nature and amount of ordered and/or random shifting of each 1:1 layer with respect to those above and below it. This paper is a progress report resulting from research on the morphology, structure, and origin of fine-grained minerals, supported by Contract N6onr26914 with the Geophysics Branch of the Office of Naval Research. The purpose of the paper is to present data obtained in the laboratories at The Pennsylvania State College and elsewhere, which reveal some of the details of structure of the minerals in the kaolinite group, and to suggest a number of interpretations that bear upon the conditions of origin of these minerals. Be¬cause most of the work in this investigation thus far has been concerned with the relationships of kaolinite, halloysite (4H2O; endellite), and halloysite (2H2O), must of the discussion deals with these members of the group. The first step in the analysis of the differences in two sets of geological conditions is an evaluation of the differences in the minerals that result. Thus the chemical differences between the montmorillonite and the kaolinite clays corroborate other evidence in support of the view that the montmorillonites are commonly formed when solutions are alkaline and leaching poor, while kaolinite usually is associated with acid solutions and good drainage condi¬tions. It is obvious that the greater the differences in the minerals, the more divergent may be the conditions that give rise to them and the more readily one condition can be distinguished from the other. In the kaolinite group, differences between individual members are small, therefore the differences in condition of origin are presumably subtle and difficult to define. At the same time, the very fact that the minerals differ only slightly makes them more sensitive indicators of the exact conditions under which they and the minerals associated with them were formed. Since clay minerals are being used more and more to evaluate the nature, value, and mode of formation of economic mineral deposits, an attempt to define these subtle differences would appear worth while. For purposes of the present discussion, the minerals nacrite, dickite, kaolinite, the so-called "fireclay mineral," halloysite (4H2O), halloysite

Jan 1, 1952

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

IT was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a. component of the pulp, of a mass solubility of the general order of a fraction of a milligram to 15 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.2 The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. EXPERIMENTAL Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well beyond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipita-

Jan 1, 1943

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By M. C. Leverett

KNOWLEDGE of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum pro-duction, but is as yet incompletely devel-oped. The object of this paper is to show the application of well established thermody-namic and physical principles to these prob-lems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: I. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion of mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. CAPILLARY EQUILIBRIUM IN SANDS Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treat-ment of problems of mixture flow, the con-cepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis-turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predict-able from the theory of capillary equi-librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, of course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is as-sumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reser-voir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems in-volving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately in-vestigated experimentally. Experimental evaluation of the pertinent properties of natural reservoir rocks will permit the ex-tension of the numerical treatment to prob-lems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids; that is, the manner in which the reservoir fluids are distributed vertically when the forces due to capillarity are just balanced by those due to gravitation.

Jan 1, 1940