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By F. Lawson, N. A. Sareyed-Dim

A rotating disk of iron precipitant in a high temperature batch reactor has been used to study the kinetics of precipitation of nickel from low concentration aqueous solutions. Under inert atmosphere conditions, for temperatures up to 150°C, the rate of nickel deposition at pH25°C of 5 to 6 is controlled both by the rate at which nickel ions reach the surface and the rate of chemical reaction at the surface. However, the presence of oxygen in the atmosphere above the reacting system increases the nickel deposition rate dramatically. It is suggested that under the experimental conditions used, hydrogen atoms are adsorbed on both the iron and nickel, thus reducing the number of sites available for the cementation reaction. Oxygen acts as a depolarizer for hydrogen.

Jan 1, 1977

||Abad, Leopoldo F., Min Engr, Div of Mines, Bureau of Science Manila, P I '23 Abadilla, Quirico A, Geol, Lago Pet Corp Box 172, Maracaibo, Venezuela '20 ||Abbey, Robert Graham, The W W Sly Mfg Co Train Ave, Cleveland, Ohio '21 Abbott, A. N., Mines Supt, Mazapil Copper Co, Ltd Concepcion del Oro, Mexico '23 Abbott, Clarence E., Mgr, Mines & Quarries, Tenn Coal, Iron & R R Co, 1242 Brown Marx Bldg, Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr , Consolidation Coal Co , Elkhorn Div Jenkins, Ky. '16 Abbott, Robert R., Met Engr , Peerless Motor Car Co Cleveland, Ohio '12 ||Abbott, Wells Osborn, Ray Consolidated Copper Co Hayden, Ariz. '23 Abeel, George H, Jr., Cons Min Engr 4612 West 17th St , Los Angeles, Cal '18 Abel, Albert E., Asst to Pres, Valley Mould & Iron Corp Sharpsville, Pa. '19 Abernathy, George Elmer, Prof of Geol & Min , Kansas State Teachers College, Pittsburg, Kans. '20 Abey, Hiroshi, Min & Met Engr, Min & Met Dept, The Higher Technical School, Osaka, Japan. '17 ||d'Ablaing, Philip R, Chem , Anaconda Copper Min Co Great Falls, Mont '25 Aborn, Robert H , Research Assoc., Mass Inst of Tech Cambridge, Mass '19 Abouchar, Sylvain Sley, Min. Engi & Geol , care of S H Sekaly, 13 Rue El Nimr, Cairo, Egypt '17

Jan 1, 1923

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By J. E. Tobey, David R. Mitchell, J. H. Kerrick

DETAILED knowledge of purchase specifications established by coal consumers is essential to the successful design and operation of a coal-preparation plant. ANTHRACITE Specifications should be considered by both the consumer and the producer as guide posts outlining a certain path for both to follow. Plants differ, therefore specifications must differ to meet the varied requirements. Specifications are not of themselves a "cure all" or an assurance of complete satisfaction in fuel utilization. Specifications should not be regarded as a license to engage in an orgy of buying any and all coals that may happen to fall within their limits. This would lead to the indiscriminate mixing of coals which may vary in their burning characteristics. Different coals of equal grade tend to be individualistic in their burning characteristics. Rather, specifications should be used to help simplify coal selection, to reduce the actual number of coals used over a given period; in other words, to have a stabilizing influence on coal or customer turnover. In the final analysis, the use of too many coals per year in a plant is costly to both the consumer and the producer. Too many sources usually result in higher operating and maintenance costs for the consumer and higher sales costs for the producer. Finally, the statement included in the report accompanying the com¬prehensive Coal Selection Charts prepared by the Coal Committee of the National Association of Purchasing Agents, and released in 1938, is significant. This Committee worked diligently for a period of 15 years seeking to find a scientific and reliable method for selecting coals. The two following paragraphs are quoted from its report: More important is the fact that no ready-made classification or set of specifications can possibly replace the judgment and resourcefulness of an experienced combustion engineer or fuel technologist, nor the usual need for full scale plant tests under the exact conditions of use before a final decision is made ...

Jan 1, 1943

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By Gerald Edmunds

CASTINGS of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, some-times nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is devel-oped to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and there-fore the position of the grains is more com-plex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicat-ing that thermal contact was better there than in neighboring areas.

Jan 1, 1940

By Leonard A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region com- prises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1 ). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County.

Jan 10, 1959

By A. W. Hesse

The trend of American construction toward permanence and longevity is noticeable in the more recent coal plant installations; also, the policy of many coal operators has changed from seeking to obtain the desired tonnage from several plants of small capacities to designing a single installation to produce the whole amount. The mine openings and plant of the Nemacolin mine of The Buckeye Coal Co., are located on the Greene County side of the Monongahela River, 73 miles south of Pittsburgh. The map (Fig. 1) shows the general location, also the Lambert syncline. This syncline partly accounts for the selection of the site; the other reasons were the possibilities of rail and river shipments. Two shafts and a slope were sunk to the coal, work starting on all three in the second half of the year 1917. The air shaft was sunk to a depth of 243 ft. and completed in February, 1918; the slope was completed in November, and the skip shaft was stopped at a depth of 21 ft. below the coal, then the concrete lining was stopped 8 ft. above the coal August, 1918. Work on the skip shaft was resumed May, 1923, and sunk to a depth of 60 ft. below the coal by September, but it was not until May, 1924, that the lining was poured. Max. Min. WateR Water during after Sinking, Crouting, Depth or Cu. Yd. Cu. YD. Gal. per GaL. per Opening Size Length Excav. Conc. Min. Min. Air shaft..... 20 ft. diam. 251 ft. 8 in. 4788 1902 475 2 Slope........ 11 it. by 19 it. 1 in. 857 ft. 11500 5200 50 2 Skip shaft.... 32 ft. 8 in. by 12 it. 8 in. 296 ft. 6042 2293 300 3 Fig. 2 shows sections of these openings. The surface plan shows the relative positions of the openings. Coal was first hoisted from the air shaft May 7, 1918, and entry driving was continued; but the coal had to be stored, as the railroad had not been extended from Crucible to Nemacolin. As soon as the slope was driven to the coal and the linings concreted, the entries were driven along projected lines to connect with those advancing from the air shaft, and skip shaft. As soon as the underground connections had been made between the two shafts, the hoisting by buckets was inaugurated at the skip shaft and construction on the fan at the air shaft started.

Jan 1, 1927

Aamot, Olav Crone, Chem. Engr., Norsk Elektrokemisk, Kongensgt. 18, Oslo, Norway. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tennessee Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abel, Raymond L., Prof., Dept. of Pet. Refin., Univ. of Pittsburgh ..Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T R.F.D. 1, Adamsville, Ohio. '31 Abell, Leo M., Ore Dressing Investigator, School of Mines Adelaide, S. Australia. '31 Abenius, Hakan V., Mine Supt., Bolidens Gruvaktiebolag Boliden, Sweden. '37 Aborn, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S.W. 1,, England. '28

Jan 1, 1937

By John B. Myers

VERMICULITE is a name used to describe micaceous material that exfoliates when heated. It is hydrated magnesium-aluminum-iron silicate. The chemical composition, color, physical appearance, and degree of exfoliation vary. COMPOSITION, PROPERTIES, AND ORIGIN Vermiculite has the characteristic micaceous structure of basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. Hardness is 1.5; specific gravity, 2.2-2.7; luster pearly to greasy; colors, amber, bronze, reddish brown, dark green, and black. Feel is soapy, particularly when wet. When heated it exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin veamiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted into steam. Warping of the unit layers may also contribute to the expansion. The increase in bulk volume of commercially prepared material is 8 to 12 times but individual flakes may increase in size more than this. Pure vermiculite is a distinct mineral and has the structural formula (OH), (Mg,Fe)3 (Si,Al,Fe)4 010.4H20. It rarely occurs in this pure form, but generally as a mixed mineral of varying structure. One explanation is that the mixed material is composed of unit layers of inter-stratified pure vermiculite and biotite. The essential difference between the two is that unit cell structure of vermiculite contains a layer of water molecules whereas the biotite cell contains potassium instead of the water. The water content of the mixed vermiculite is less than that of pure vermiculite but more than that of biotite. Pure biotite does not expand when heated. If the proportion of biotite layers in a vermiculite is too high it will adversely affect the degree of exfoliation. Within a given deposit, the great mass of material may approach a definite com-position with local areas of greater biotite content. It is not uncommon to find also small pockets of pure biotite but these are generally segre-

Jan 1, 1949

By H. W. Becker, C. C. Frye, A. V. Degau, A. Masuda

Natural gas containing 25.65 per cent hydrogen sulfide and 4.75 per cent carbon dioxicle is gathered frorn eight \veih arid tratzsporrcd 26 miles at a flow rate of 160 MMcf/D and at operating pressures of frotrl 1,200 to 1,800 psig. Dry desiccant dehydrators at each wellsite tnaintaitz the dew point of the gas below 17F. Telemetering facililies permit control of field operations from a central instrunlent console. Corrosion control ineasures, design coilsiderations and material specifications pertainitz to these specia1 conditions are cliscussed. INTRODUCTION Natural gas containing 25.65 per cent H2S and 4.75 pcr cent CO, is produced from the Pine Creek field, Alta. It is dehydrated at wellheads, gathered at 2.200 psig and transported 26 miles to the Windfall field where it is delivered to the inlet of injection compressors at 1,800 psig. The daily average volume of gas transported is 160 MMcf. The project is believed to be unique in its combination of percentage of hydrogen sulfide, operating pressure and transportation distance. This paper describes the project and presents details of some of the design features, corrosion control program and centralized automatic operational control. The Pine Creek field project is one phase of a joint operation of two fields—thc other being the Windfall field. The two fields lie about 30 miles north of Edson, Alta. and 20 miles west of Whitecourt, Alta., respectively, as shown on the map (Fig. 1). They are owned by the same interests and operated according to a plan for maximum economic recovery of products. The Windfall Leduc D-3 reservoir contains a rich condensate-bearing gas containing 15.5 per cent HIS. The gas from the Pine Creek field contains only very small quantities of butane and heavier products. The Windfall reservoir is being cycled to obtain maximum condensate recovery using gas from the Pine Creek field as the displacing fluid, while producing the residue sales gas for both fields from the Windfall field. The Pine Creek field development and gas-gathering facilities are shown on the map (Fig. 2). The producing formation is the Leduc D-3 reef at a depth of 11,300 ft. The original reservoir pressure was 4,590 psia at 7,400 ft subsea and the temperature is 245F. Eight wells are equippcd with dry desiccant dehydrators with the following capacity ratings: three at 35 MMcf/D; three at 20 MMcf/D; and two at 10 MMcf/D. WELLHEAD EQUIPMENT Dry desiccant dehydrators were designed to reduce the water content of the saturated wellhead stream to 2.5 lb of water/MMcf at 2,000 psig. This specification was necessary to prevent hydrates and corrosion forming in the pipeline which will operate at temperatures as low as 20F. A typical flow diagram is shown in Fig. 3, and Fig. 4 is a photograph of one of the wellhead installations. Some of the design details given below are subject to modification in the field. The well-stream flowing temperatures range from 135 to 170F. Wellhead flowing pressures up to 3,200 psig are reduced to the dehydrator-operating pressure of about 2,100 psig by throttling through a pressure control valve. The gas is then passed through an aerial cooler where its temperature is reduced to 105F. thus removing over half

By W. G. Lidman, H. J. Hamjian

' I HE fabrication of many materials from powders involves a sintering process. A mass of powder will sinter because of the excess free energy over the same mass in the densified state caused by the higher total surface area of the powder. An understanding of the kinetics and mechanism of sintering should assist in improving the properties of such materials. The present investigation conducted at the NACA Lewis laboratory deals with the sintering of chromium carbide. Dry sintering (sintering at a temperature below the melting point) was divided into two stages by Shaler:' the first stage, during which the particles preserve much of their original shape and the voids are interconnected, and the second stage, during which densification occurs and the pores are isolated. The mechanism of forming interfaces between particles, or welding together of particles, has been investigated by Kuczynski2 and may be described by any one or a combination of the following mechanisms: viscous flow, evaporation and condensation, volume diffusion, or surface diffusion. The mechanism by which pores are closed or eliminated (densification) during sintering, is of interest. Grain growth observed during sintering may be attributed to the variation in the surface energies of individual grains, causing some grains to grow at the expense of others. Grain boundary migration occurs presumably by a diffusion process, therefore the rate of grain growth would be expected to increase exponentially with increasing time and temperature. Thus, for practical sintering times of less than 1 hr, a certain minimum temperature may exist at which major structural and property changes will occur. Densification and kinetics of grain growth during sintering under pressure of chromium carbide were investigated to provide additional information which will aid in describing more accurately the sintering process and the mechanisms involved. This material was selected for this study because of the current interest in high strength, oxidation resistant refractory materials, such as carbides, which are sintered to produce solid, dense materials from powders. Sintering under pressure is a process where the heat and pressure are applied to the compact simultaneously, specimens for this work were prepared by sintering under pressure at different temperatures and for various time periods. Experimental Procedure Preparation of Specimens: Chemical analysis of the commercial chromium carbide used in this investigation was as follows: Cr 86.19 pct, C 12.14 pct, and Fe 0.2 pct. X-ray diffraction powder patterns gave characteristic diffraction lines of Cr3C2 crystal structure. Powder particle size was determined microscopically and the average initial particle size was 6 microns with 85 pct between 2 and 10 microns. Specimens sintered under pressure were formed in graphite dies3 heated by induction. Sintering temperatures were measured with an optical pyrometer by sighting into a 3/8-in. hole drilled 1 in. deep at the midsection of the graphite die. A load of approximately 1 ton per sq in. was applied to the powder. The die assembly was heated in 20 min to the highest temperature (2500°F') at which no increase in grain size could be observed, and less than 2.5 min were required to heat from this temperature to the maximum temperature (3000°F). Sintering temperatures and times for the specimens of this investigation are indicated in Table I. Analysis of Specimens: Specimens polished with diamond abrasives were etched to reveal the grain boundaries with a 1:1 mixture of 20 pct potassium hydroxide and 20 pct potassium ferricyanide heated to 160°F. Representative areas of each sample were photographed at 1000 diameters. The largest diameters of all well-defined grains were measured, but only the measurements of 15 of the largest grains were averaged in order to determine an index of grain size on the assumption that they were among the first to begin growth. Densities were determined from differential weighing of the samples in air and water. The reported density values are considered correct within ±0.01 g per milliliter. Results and Discussion Metal compacts have exhibited grain growth when sintered at temperatures about two-thirds of the absolute temperature of their melting point.' Grain growth also occurs during the sintering of chromium carbide and is illustrated by the micrographs shown in Fig. 1. These micrographs were prepared from specimens sintered for 90 min at temperatures ranging from 1371°C (2500°F) to 1648°C (3000°F). Average grain size and density measurements of specimens investigated are presented in Table I. The relationship between grain size and sintering tem-

Jan 1, 1954

By Joachim J. Hauser

William F. Hosford, Jr. (Massachusetts Institute of Technology)—Dr. Hauser has used a very interesting method to study the interaction of dislocations on different slip systems, but it should be pointed out that the analysis of the experiments is subject to a serious criticism. He states that "the effect of the compression can be adequately described by one slip system." The effect of frictional constraint during the compression makes this quite unlikely. When a block of metal is compressed its lateral expansion requires a sliding of the metal over the compression platens. The role of friction in the interface between the deforming metal and the platens is to increase the normal force required for the compression. Analyses1213 have shown that, in general, the additional force, p, required for the compression is a function of l/h where is the coefficient of friction, I is the length of the speci- men in contact with the platens. For a constant COefficient of friction, isho' shows that P should increase exponentially with pl/h for both plane strain and axially symmetric compression. For a compression specimen, Fig. 7, whose cross section perpendicular to the compression axis is a rectangle whith one dimension L, much larger than the other W, a much larger force would be required for appreciable flow parallel to L than for flow parallel to U7. Therefore lateral strain in the W direction, EW, should be much greater than the lateral strain in the L direction EL. Since L/H = 14.5 for Dr. Hauser's crystals, and since no lubrication was used, it seems questionable that appreciable lengthening of the crystals could occur. Because the theories of frictional constraint have been derived for isotropic polycrystalline materials, it was decided to make experimental measurements on a single crystal. A section 3.590 in. long was sawed from an aluminum single crystal with a square section of 0.249 in., so that L/W= 14.4. This crystal was tested in compression between dry ground steel platens. Fig. 8 shows the orientation of the crystal and the axis of compression. The face for compression was chosen so that the operation of the single-slip system which would be predicted in the absence of friction would lead to a larger strain in the length direction than in the width direction. The dimensional changes of the width and length as well as the height were measured frequently during the compression with micrometers. Width strains were calculated from the average of readings near each end and at the center. A plot of the length strain, EL, against the width strain E w is given in Fig. 9. The slope indicates that the EL amounted to only 2.5 pct of cw. Other compression tests on similar crystals with shorter lengths also showed severely limited elongation. Even for a crystal with L/W = A.0, EL was only about 26 pct of cw. Because of the frequent interruptions of the tests for dimensional measurements should have decreased the frictional constraint by allowing a reseating of the platens, even smaller elongations under continuous testing seem probable. These tests on long narrow crystals show that essentially plane strain conditions prevailed. We may assume that Dr. Hauser's crystals deformed similarly. That the compression can be described by the

Jan 1, 1962

By Robert Keeney

Before the outbreak of the war in 1914, the only electric-furnace smelting plant operating on a commercial basis west of the Mississippi River was an electric pig-iron plant in California; rare metal ores were not smelted, concentrates of molybdenum, tungsten, uranium, and vanadium ores being shipped east for reduction. Practically no- chrome ore was being mined, and only comparatively small amounts of manganese ore. Today there are two electric smelting plants in California, one in Washington, one in Iowa, and four in Colorado; two plants are under construction in California, and one in Montana. Ores of manganese, chromium, molybdenum and tungsten are now smelted in the West, and although uranium and vanadium concentrates are still shipped to the East, they will probably be treated in western plants in a short time. The four electric-furnace plants in Colorado are listed in Table 1. TABLE 1.-Electric Smelting Plants in Colorado Capacity, Company, Location Kilowatts Products . Tungsten Products Co Boulder 800 Ferrotungsten, ferromolybdentun. Boulder Tungsten Production Co. . Boulder 400 Ferrotungsten. Ferro Alloy Co Utah Junction 1200 Ferrochrome, ferrotung-sten. Iron Mountain Alloy Co Utah Junction 3000 Ferromanganese. Power for all of these plants is supplied by the Colorado Power Co.

Jan 8, 1918

By R. W. Ludt, C. C. DeWitt

The use of froth flotation for the separation of minerals has become one of the most important of ore dressing processes. Its particular adaptability to the enrichment of low grade ores has made the process an important factor in the national economy. The methods have been extended to the recovery of a great number of minerals. Among the few minerals which have resisted efforts toward industrial flotation is chrysocolla, a hydrated partly colloidal copper silicate. Chrysocolla, being a product of natural oxidation, has been found to occur in small quantities with many ores which are recovered by flotation methods. In present practice, these small quantities of copper silicate pass off with the tailings and are lost. The advantages to be gained by a satisfactory process for the recovery of chrysocolla is apparent. Any application of principles which points a way toward the satisfactory industrial flotation process for copper silicate would be of advantage. This paper presents an attack on this problem. Two methods for the recovery of chrysocolla have been developed by the United States Bureau of Mines.1,2 They have been successful on a laboratory scale but have been seriously restricted in industrial application by critical requirements in the procedure. In one of the Bureau of Mines methods,' the ore is activated with sodium or hydrogen sulphide in an aqueous solution at a pH of 4. Amy1 xanthate is then used as a collector with pine oil as a frother in the flotation process. An excess of sulphide acts as a depressant and the state of optimum conditions is difficult to control industrially. In the second Bureau of Mines method,2 soap is used as the collector at a pH of between 8 and 9. The diffi- culties with this process are that soap is not a specific collector, that heavy metal or alkaline earth ions cause the formation of insoluble soaps, and that a more acid solution causes the formation of a free acid which does not act as a collector for chrysocolla. The problem of recovering chrysocolla by flotation involves the selection of a suitable collector. The collector molecule must be composed of an active polar group that has an attraction for chrysocolla, and of a hydrocarbon chain. Certain dyes have been shown to have an attraction for certain minerals. Suida3 found that hydrated silicates are colored by basic dyes. Dittler4 showed that chrysocolla, among other colloidal minerals of acid reaction, preferentially takes up such basic dyes as fuchsin B, methylene blue, and methyl green. Endell5 gave information to show that the colloidal material in clay may be determined by its selective adsorption of fuchsin. A simple experiment, likewise, illustrates the difference in the adsorptive power of chrysocolla and of silica for the basic triphenyl methane dyes. When a mixture of chrysocolla and silica is immersed in a very dilute dye solution, less than 5 ppm, the chryso-colla is rapidly dyed and the silica is dyed more slowly. The difference is substantial but one of degree. Dean2 showed that the dyes, crystal violet and toluidine blue, are taken up by quartz in an adsorption type process. The difference in the adsorptive power, however, offers the means by which a new collector may act. To form such a collector, a hydrocarbon chain must be attached to the dye molecule. This involves a process of organic synthesis. Butyl, hexyl, and octyl hydrocarbon chains were selected for substitution in the malachite green molecule. For the purpose of identification, the alkyl-substituted dyes formed are called: butyl-malachite green; hexyl- malachite green; and octyl-malachite green. An outline of the procedure for their synthesis is given in the appendix. It is generally recognized in the preparation of this type of dye that the chemical structure of some of the dye molecules varies. However, a uniform formula is attributed to the dye. Such a procedure has been followed in specifying the structure of these alkyl-substi-tuted malachite green dyes. The structure is given on the basis of their properties as an homologous series of dyes, on their method of preparation, and on the purity of intermediates used. Structure of substituted alkyl malachite green is: C6H4 N(CH3)2 p-R C6H4 CH C6H4 N(CH)2 Procedure The flotation cell is a Bureau of Mines 100-g, batch unit provided with an air inlet at the bottom above which is a variable speed agitator. The agi-

Jan 1, 1950

By Fred D. Gustafson

With the postwar emergency for new housing and for new industrial buildings, much research has been done on lightweight aggregates for use in concrete and plaster. The trend toward lighter weight aggregates to relieve the dead load on the higher, steel frame- work buildings started toward the end of the last century. Progressively the requirements be- came more stringent, crushed bank slag, weighing 80 lb per cu ft as com- pared to 100 lb for crushed rock, was supplemented in some sections by foamed slags and expanded shales weighing from 40 to 60 lb per cu ft. In other sections cinders were used weighing from 40 to 50 lb, including sand. Sections favored with more recent vulcanism turned to pumice weighing from 30 to 60 lb, whereas other localities made use of diatomite, from 28 to 40 lb. Exfoliated vermiculite weighing from only 6 to 10 lb per cu ft came into use. As the search for lighter weights in aggregates continued so did the search for other desirable properties such as nailability, ease of cutting or channeling, and good insulation to both sound and heat. This search eventually led to a widespread interest in the expansion of perlite, or similar volcanic glasses, with the result that in 1946, the Office of the Housing Expediter' listed eleven firms reporting the operation of processing plants either on pilot or commercial scale producing aggregates weighing from 2 to 16 lb per cu ft.

Jan 1, 1949

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author's reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer's decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry's law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

By J. Brian Eby

As is generally understood, the word geophysics means literally ?the physics of the Earth? and the science of geophysics is therefore that which treats of the study and measurements of the various physical properties of the Earth. The broad and general study of the elastic, the gravimetric. or the magnetic properties of the Earth as a whole belongs to the general science of geophysics. The detailed application of this science to rocks of shallow depth and in small areas for the purposes of ascertaining data on their character and structural attitude gave rise to the present well-known science of ?applied geophysics.? Since the discovery of enormous new quantities of oil, gas, and sulphur has been by far and wide the principal benefaction of geo-physics in the United States, this paper will refer only to geophysical methods employed in the search for these particular minerals. The application of methods and appliances originally used for geophysical research to the solution of the practical problems of finding new oil-fields, plus the counterflow or new and highly refined techniques and Instruments from the company and consulting geophysical research laboratories and into non-economic geophysical research, has provided another case of that gen-eral cycle of events which is familiar to all scientists. That this closed-circuit flow or scientific current has been tremendously important to the whole science of geophysics is probably well known to all members of this audience, but the gen-eral status of the exploratory geophysical arts as now used In the search for new oil-fields, the scales on which different methods are being used, the magnitude of the costs involved, and the far greater magnitude of the practical results achieved may not necessarily have come so directly to your attention. It is, I understand, for this reason that this paper has been sug-gested, and I shall seek to provide the information requested by using as case-illustrations those changes in the oil-reserve picture for the United States as a whole, and for the Gulf Coast, California, and Illinois Basin regions in particular, which have occurred in the period of the past 17 years, during which time oil-field discoveries have proceeded at a rate which served to build up known and readily-available (or proven) oil supplies to a reasonable figure, and have dispelled the fears of a serious oil shortage during any period for which valid fore-casts can be made. Not that geophysical-prospecting methods have alone been responsible for this transformation, but they have an indispensable and leading part in the picture of exploration and production-to which geophysics, geology, engineering, and general technical progress have jointly made contribution. So far as the United States as a whole is concerned, its total proven, probable, and possible oil reserves (discoverable and recoverable by then-known methods) were estimated at about nine billion barrels in 1920, whereas proven reserves alone are now com-puted at about 16 billion. In 1920 the driller in ?wild-cat? territory was faced with the knowledge that for every new oil-field opened by a successful well, from 20 to 100 unsuccessful wells would have to be drilled and, in some territories, that the chances for a discovery were really less than one in 100 for new drilling, in contrast to which may be cited the record for the past year in parts of Louisiana where the 67 wells drilled opened 16 new oil-fields, that is to say, where the score of hits to misses was increased to approximately one out of four.

Jan 1, 1940