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By E. G. King

Thermodynamic data for the hydrated varieties of alumina are sparse, and those for the common clay minerals are virtually nil. This paper partly fills the vacuum by reporting low-temperature heat-capacity measurements and entropy evaluations of diaspore (A10(OH)) and three clay minerals of the composition A12Si207?2H20 - kaolinite, dickite, and halloysite. The heat-capacity measurements were made in the temperature range 510 to 298.15° K., and the entropies were evaluated at 298.15° K. Diaspore has an unusually low heat capacity and entropy compared with boehmite (another mineral of the same chemical composition). The entropies of the three clay minerals differ too little for entropy to be the important factor relating to differences in the thermal stability of these substances.

Jan 1, 1961

By H. U. Ross

ROASTING is usually thought of as a process in which finely crushed or ground ore is heated with air in a suitable furnace in which the ore is rabbled or agitated in such a way as to insure complete reaction between the oxygen of the air and the oxidisable constituents of the ore. Roasting in this sense is used only to a very limited extent in the iron and steel industry. This is because, in most iron ore deposits mined today, the ore is of a type that does not require roasting. Where this process is used, it is usually because of some special circumstance, such as a peculiar economic condition, that warrants it. If roasting is looked upon in the broader sense as a gas-solid chemical reaction carried out at an elevated temperature in which both gaseous and solid products are formed, then the process is used in the iron and steel industry to a greater extent

Jan 1, 1961

By A. L. Engel

This report describes results of laboratory-scale experimental treatment of nine ores containing gold and silver, including samples of products of previous plant treatment, from ore deposits in California and Nevada. The samples treated were taken by engineers of the Bureau of Mines during investigations of these ore deposits. The information reported is of interest for development of the mining districts represented or in future Investigations of similar ores from other sources. The treatment methods were as simple as possible. More complicated treatments were tried when required, The applicability of the methods and their limitations in treating the ores are shown by the data in this report. The following treatment methods were employed in the experiments described: Screen analyses were made to determine distribution of values in various screened-sized portions of crushed ore, or to determine optimum size to which a particular ore should be crushed or ground to liberate values, and some-times to determine residual values in various-sized portions of treated material.

Jan 1, 1961

By G. Derge, L. D. Kirkbride

In recent years the problem of sulfur elimination in iron and steel-making has been of increasing importance. This interest has been due to the increasing amounts of sulfur coming into the system via raw materials. As a result, many investigations have been directed at obtaining information pertaining to the rate and mechanism of sulfur removal in the blast furnace as well as measuring appropriate thermodynamic quantities. Chang and Goldmanl as well as others2'3 showed that the process of sulfur transfer from molten carbon-saturated iron to blast furnace-type slags could be considered as two opposing first-order chemical reactions. Recently, Ramachandran et al.4 have shown that during desulfurization electrical neutrality is preserved in both phases and iron and silicon are transferred into the slag concurrently with the evolution of carbon monoxide gas. They concluded that the reaction s + c-+ (0)=(S) + CO(g) does not express the stoichiometry of the sulfur transfer process. As in all previous investigations, these authors studied the process of a net transfer of sulfur from metal to slag across a slag-metal interface. However, no experimental data have previously been obtained for the process of sulfurization. It was the purpose of this study to investigate the sulfurization process, i.e., net transfer of sulfur from slag to metal. EXPERIMENTAL PROCEDURE Apparatus—The equipment used in this investiga-tion was typical of that used by others.1-3The furnace was a high-frequency induction unit powered by a 35 kw Hg spark gap converter. Fig. 1 shows a schematic diagram of the apparatus. A two-compartment crucible assembly was employed to melt the slag and metal charges; being similar to that used by Ramachandran,4 in size and design. The atmosphere was that produced by reaction of hot graphite with air. Temperature measurements were made by W-Mo thermocouples which were calibrated against a Bureau of Standards Pt - Pt 10 pct Rh couple. Temperature control was always good to * 5°C and in general was much better than this figure. Raw materials used in the experiments were C. P. reagent grade where possible. The silica used in the preparation of the slags was in the form of highly purified silica flour. Silicon and titanium additions

Jan 1, 1961

By J. Lemish

Considerable research has been conducted in Iowa in recent years on carbonate aggregate reactions in concrete. Groups outside the state have become active in the past few years after recognizing that certain carbonate aggregates are reactive in concrete. The paper reviews the nature and extent of the problem and a summary is given of research by the author and his associates. In recent years considerable research has been conducted in Iowa on carbonate aggregate reactions in concrete. The research is part of a general study on the behavior of carbonate rocks as concrete aggregates sponsored by the Iowa State Highway Commission. Research on carbonate aggregates has not been extensive in the past. Laughlin1 published one of the first papers on carbonate aggregates in 1928 and was followed by others, notably H. S. sweet,' B. Mather et al.,3 and K. Mather4 who emphasized the petrographic and physical aspects of carbonate aggregates. The recognition that certain carbonate aggregates are reactive in concrete has led to increased participation in research in the past few years by groups outside of Iowa. Significant contributions have been made by Swenson and Gillot,5 Hadley,6 and Chaiken and Halstead7 in work which emphasizes the expansion of carbonate rocks in alkaline environments and the reaction of carbonate minerals or dedolomitization with alkalies. It is the purpose of this paper to review briefly the nature and extent of the problem and present a summary of the research by the author and his associates. EXTENT AND NATURE OF THE PROBLEM The problem is the deleterious behavior of certain carbonate aggregates in concrete. It was first recognized in Iowa over 20 years ago when poor service records of certain highways were correlated with aggregates produced from the Glory and LeGrand quarries. Deleterious behavior of carbonate aggregates have been reported in Canada and, more recently, in New York and Virginia. As more knowledge is gained concerning the problem, distress in concrete related to carbonate aggregates may be recognized over a widespread area. The problem may potentially exist in the Midwest, the Northeast, and other parts of the country underlain by thick sections of carbonate rocks readily available for utilization as aggregates. The nature of distress in Iowa highways is a general weakening and deterioration of concrete characterized by progressive cracking and spalling away from joints and edges (Fig. 1). The distress generally occurs after 15 years of service and becomes progressively worse. Specimens of such concrete lack the toughness of sound concrete and break easily under the hammer in the manner of a soft brick. The matrix is generally highly carbonated and dark borders, or reaction shells or rims outline the argillaceous carbonate aggregate fragments (Fig. 2). Cracks observed in cores cut across the aggregates and concrete matrix. Although localized volume change (expansion) is associated with spalling, there is no definite field evidence in Iowa that excessive growth of concrete slabs has occurred. The experience with carbonate aggregates in Iowa indicates that the concrete deterioration is not the same as that induced by the alkali-aggregate reaction associated with siliceous aggregates. The principal difference is that in Iowa the distressed concrete is weakened throughout the slab. In concrete affected by the alkali aggregate reaction, the

Jan 1, 1961

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By E. R. Palowitch

A centrifugal float-and-sink test procedure has been developed by the Bureau of Mines to reduce the time for the gravimetric separation of coals finer than l4-mesh from as long as 24 hours to less than 1 hour. Comparative tests indicated that centrifuging a minus 14-mesh Pittsburgh-bed coal for 20 minutes at 1,500 revolutions per minute produced results that compared favorably with static float-and-sink test results. Standard deviations of the mean recovery and ash content of the float obtained centrifugally ranged from 1.31 and 0.04 percent, respectively, at 1.30 specific gravity to 0.21 and 0.05 percent, respectively, at 1.60 specific gravity. As in static separations, retreatment of the products separated at low specific gravities was required.

Jan 1, 1961

By Gerald V. Gibbs

Quadratic functions, Q(hkl), are given to six places in increments of 0.01° for 2? from 0° to 90° for CuKa and from 25° to 180° for CuKa1. The wavelengths used for Cu in the computation are those agreed upon by the Editorial Commission of the International Tables for X-ray Crystallography (1950): CuKal 1.54051 A.; CuKa2 1.54433 A. INTRODUCTION At the Federal Bureau of Mines laboratory, Norris, Tenn., X-ray diffraction crystallography using tubes with copper targets revealed a need for a handy reference for the quadratic functions of copper radiation. The tables presented here were prepared to satisfy that need. The quadratic form Q(hkl) may be expressed in terms of the Bragg diffraction angle 2? and of the wavelength ? as

Jan 1, 1961

By Mary S. Esfandiary

This list of organizations that conduct research and development programs on coal has been compiled by the Bureau of Mines with the thought that such a directory may provide a useful guide to worldwide research efforts in the areas designated and may facilitate communication between organizations with similar interests. This list includes government, university, private, and commercial organizations. Many of these groups are conducting comparatively modest but often particularly interesting or specialized investigations. The areas of investigation have been defined in a broad manner--these include analysis and constitution, mining and geology, preparation, combustion, briquetting, high- and low-temperature carbonization, gasification, hydrogenation, Fischer-Tropsch, and health and safety. In some instances such information is not available, but the names of the organizations themselves often indicate immediate arias of interest. Special publications issued by and describing the work of each organization have been cited, when known; almost all of the organizations also publish results of their investigations in the technical press. Several foreign technical and trade publications that include such information and are not published directly by any of the organizations listed are cited in the pages following the list of organizations in each country. This list is not complete. Information that would improve coverage and/or accuracy will be welcomed by the Bureau of Mines.

Jan 1, 1961

By K. Nassau

The Effect of tin and hydrogen on the C0 parameter of a titanium. specimens were capsule cooled in water to eliminate contamination by water. Deybe-Scherrer photograms were obtained in a 114.6 mm camera with CuKa radiation. The parameters shown in Table I and Fig. 1 were calculated from the 213 (8569°) and 302 (8173.5°) reflections? no attempt being made to correct for systematic errors. The principal difference in method of preparation of specimens between this investigation and that of Worner was the use of pickling by the latter to produce X-ray diffraction samples. The possibility that hydrogen introduced by pickling was responsible for the lower a and c-parameters was investigated with the same 80 pct HNO3- 20 pct HF solutions used by Worner. The 6 and 10 at. pct specimens, the parameters of which had already been determined, were pickled and the c-parameters obtained are also shown in Fig. 1. The a-parameters, not shown, are also diminished. The quality of the lines obtained from the unetched and etched samples was unchanged, being quite sharp in both cases. It is quite possible that if corrections for systematic error carried out that the parameters obtained for the unetched samples would approach the data of Worner. In any event, the parameters of the etched samples would be still lower. The data obtained here is evidence that hydrogen in solution has contracted the c and a -parameters. Crystallographic Angles of Calcium Tung-state (Tetragonal, c/a = 2.169) K. Nassau In connection with the preparation and orientation of single crystals of calcium tungstate (Scheelite -CaWO4), the need arose for a stereographic projection for this tetragonal material. There appear to be no tetragonal projections with a c/a ratio above that of indium1 (c/a = 1.522) in the literature. In addition to its use for calcium tungstate, such a projection might find other more general applications and is accordingly presented below. The most recent X-ray diffraction work on CaWO4 is that of Swanson, Gilfrich, and Cook,2 where a summary of previous work is also found. Lattice parameters given are: a = 5.242A, c = 11.372A, and c/a = 2.169. The material is tetragonal with space group Table I, giving angles between crystallographic planes (HKL) and (hkl), was calculated from the formula3

Jan 1, 1961

By Charles Prasky

The objective of this investigation by the Bureau of Mines was to determine the response to sulfatization of diverse low-grade manganiferous materials in the iron formation of the Cuyuna district. In line with this objective a bench-scale sulfatizing procedure was developed that was less expensive and more rapid than pilot-plant methods. Samples from the central and south- western parts of the North range were tested. Results of evaluating a total of 46 pelletized samples, originating in areas with an estimated potential resource of 94 million long tons with a manganese content of 7 percent, indicates that approximately 87 percent of the manganese may be recovered as a synthetic manganese ore. This is equivalent to more than 12 million long tons of a metallurgical-grade ore, containing 46 percent manganese. It is anticipated that a premium product, containing over 50 percent manganese, may be obtained by sulfatizing procedures. This report is part of a continuing investigation5 6 of Cuyuna iron range manganese deposits in Crow Wing County, Minn. Lewis and coworkers describe the manganiferous iron formation in the bedrock of the Cuyuna district and include a description of a high-temperature differential sulfatizing process for recovering a ferrograde manganese product. The low-grade manganiferous

Jan 1, 1961

By T. E. Gray

This report describes the preparation characteristics of the significant coalbeds in Harrison County, W. Va. It is one in a series of Federal Bureau of Mines reports planned to determine coals suitable for the production of metallurgical coke, either as mined or after beneficiation. Over 6.5 million tons of coal was produced in Harrison County, W. Va., in 1958, of which over 3.7 million tons was cleaned mechanically in seven preparation plants. All of the coal cleaned was from the Pittsburgh bed. It has been estimated that more than 1,816 million tons of coal remains in the county in beds 12 inches or more thick. The Pittsburgh and Redstone beds were selected by the Bureau for a study based on current production rates and estimated minable reserves. Sample locations were selected following a study of the literature, conferences with mining engineers and mining company officials in the field, and examination of the available sites. Six samples were collected from the Pittsburgh bed, and three samples came from the Redstone bed, Float-and-sink tests of the samples collected from the Pittsburgh and Redstone beds showed that neither coal could be upgraded to a metallurgical fuel under the standards set up for this study, even after intensive preparation. Finer crushing of the samples moderately increased the yields and slightly reduced both the ash and the sulfur contents in the 1.30-specific-gravity float fractions. Finer crushing slightly decreased the yields in the 1.58-specific-gravity float fractions, whereas it reduced the sulfur content 0.11 percent for the Redstone sample and 0.46 for the Pittsburgh sample.

Jan 1, 1961

By Martin H. Stanczyk

The direct dissolution of a typical zinc sulfide flotation concentrate by elevated temperature and pressure leaching was investigated. The concentrate assayed about 55 percent Zn, 32 percent S, 6 percent Fe, and 1 percent Pb and contained minor quantities of copper and precious metals. The influence of various factors on the dissolution of the zinc in acidic and ammoniacal pulps when using oxygen as the oxidant was determined. The tests revealed that the sphalerite was difficult to oxidize. Complete dissolution of the mineral required vigorous and intimate nixing of the gaseous, liquid, and sold phases. The addition of pyrite or sulfuric acid to water slurries of the concentrate was required to obtain a high zinc extraction when leaching under acidic conditions. The quantity of pyrite and acid used was about 0.125 and 0.25 pound, respectively, per pound of zinc sulfide contained in the leach charge. In tests with acid, about 96 percent of the zinc was extracted from the concentrate in 1 hour at 200° C. when the oxygen partial pressure was 75 pounds per square inch gage or higher. Leaching with a continuous flow of air as the oxidant gave results that were almost as good as those obtained when oxygen was used, In tests with air fed through the autoclave at 320 liters per hour, 95 percent of the zinc was dissolved in 1 hour, Acid leach solutions assaying approximately 58 grams Zn per liter and containing Fe, Ni, Cr, and Cu impurities were produced in the better tests. The leached residue consisted essentially of red iron oxide together with substantially all of the lead and precious metals.

Jan 1, 1961

By C. S. Finney, John Mitchell

On December 31, 1959, there existed in the United States 15,993 slot-type coke ovens capable of producing 81,447,700 net tons of coke. These ovens were concentrated in 74 coke plants in 21 different states. As of the same date, there were 7448 beehive ovens in existence at 45 plants in the states of Pennsylvania, Virginia, West Virginia, and Kentucky. Total annual capacity of the existing beehive ovens was 4,368,800 net tons, but only 5148 ovens with a capacity of 3,131,600 tons were in operating condition. It is interesting to compare the average dimensions of slot-type ovens built during recent years with the 30 ft x 5 ½ ft x 16 ½ in. ovens erected at Syracuse, N. Y. in 1892. A composite oven built according to the average dimensions of all those erected between 1954 and 1958, for instance, would be 39 ft long. 12 ft high, and 18 in. in width. The coal capacity would be 16 tons as against the 4.4 tons which could be charged to the Syracuse ovens. Of the 15.993 slot- type ovens in existence at the end of 1959, by far the greater number were built by the Koppers Co. whose total of 11,280 ovens included 7891 Koppers- Becker and 3389 Koppers ovens. Of the remainder, there were 3260 Wilputte, 1350 Semet-Solvay, 63 Otto, and 40 Simon Carves ovens. By-product coke oven plants are usually classified either as furnace or merchant plants. According to the definitions used by the US Bureau of Mines, the former are "those that are owned by or financially affiliated with iron and steel companies whose main business is producing coke for use in their own blast furnaces. All other coke plants are classified as merchant. They include those that manufacture metallurgical, industrial, and residential heating grades of coke for sale on the open market; coke plants associated with chemical companies or gas utilities; and those affiliated with local iron works, where only a small part (less than 50 pct of their output) is used in affiliated blast furnaces." The annual coke capacity of the merchant plants during 1959 was 10,393,000 tons. However, the by-product oven of today is essentially an appurtenance of the iron and steel industry, rather more than 87 pct of total by- product coking capacity being concentrated at furnace plants. This was not always so. There was a time when the merchant plants played a much greater part in meeting the US demand for coke and gas. High noon for the merchant plants was reached during the early 1930's. By 1932 there were as many by- product oven installations being operated by the merchant sector of the industry as by the coke divisions of the iron and steel industry (44 of each), and in the same year the merchant plants produced 46.5 pct of all by-product coke made in the country. Since that time their contribution has drastically declined. In 1940 merchant plants were responsible for only 23.2 pct of total US production, and by 1950 their number had decreased to 30 plants which turned out 18.5 pct of the total by-product coke made. At the end of 1959 only 20 of the 74 existing by-product oven installations were merchant plants. They ac- counted for 12.5 pct of the year's production, or 6,849,786 net tons. This percentage has remained fairly constant since 1954. There are several reasons for the decline of the merchant coking industry. For example. On the grounds of economy, quality control, continuity of supply, and so on, the iron and steel industry usually prefers to control its own mines and carbonize its own coal at or near to the blast furnace rather than rely on independent operators for metallurgical coke. As the steel companies have enlarged their own coking facilities, so has the need for coke obtained from other sources declined. Furthermore, not only has the steel industry increased in self-sufficiency by building mare coke ovens during recent years, but it has also progressively improved the fuel efficiency of its blast furnaces. During the years 1947-49 the average coke consumption per ton of pig iron was 1892.8 lb. During 1958 the corresponding figure was 1613.4 lb. There are many individual furnaces where still better results are being obtained, and further reductions in the average may be expected. Perhaps the greatest threat to the merchant coking plant has been the fantastic increase in the use of natural gas and petroleum products for purposes which manufactured gas once served. So deadly has the com- petition from natural gas and oil been that it has almost eliminated by-product oven installations owned by public utilities. In the peak years of the early 1930's there were 23 such public utility plants. In 1960 only two were left. One of these, owned by the Citizens Gas and Coke Utility, was at Indianapolis, Ind.; the other was the plant operated by the Philadelphia Electric Co. at Chester, Pa. The non-utility merchant plants have also been sorely hit. With gas sales revenues reduced, domestic

Jan 1, 1961

James Westfield, Assistant Director, United States Bureau of Mines, Washing- ton, D. C., called the second morning session of the Rocky Mountain Coal Mining Institute to order, and promptly introduced John Peperakis, Manager of the Sunnyside Operations, Kaiser Steel Corporation. Sunnyside, Utah, who spoke on "Ground Control Developments, Sunnyside Mines, Kaiser Steel Corporation." Mr. Peperakis illustrated his talk with a number of slides which were not reproduced with the printed text. (For the printed text of Mr. Peperakis' paper see index.) James J. Diamanti, President of the Car- bon Fuel Company, Helper, Utah, was introduced by Mr. Westfield, and he spoke on "Small Mine Operators Help Themselves." Questions from the floor followed Mr. Diamanti's talk.

Jan 1, 1961

By H. E. Rowen

As high grade iron ore deposits dwindle and costs rise, sintering becomes more and more important. The steel industry is now faced with beneficiation problems once peculiar to nonferrous work. Succeeding articles describe recent advances in this field. Here is presented the first chapter of a history still being written. SINTERING, for the purpose of this discussion, is defined as the art of burning a solid fuel with 90 to 95 pct ash content. Considering problems of combustion involved in keeping a home furnace burning properly with 12 to 20 pct ash in the fuel, it is evident that combustion represented by the definition has to be right or nothing is going to happen. Our forefathers discovered that many ores containing metals essential to the steadily rising standards of living were associated with elements such as sulfur and arsenic, which had to be removed before refining. This they did by utilizing the solid fuels they had available-the sulfur or other readily combustible components-to create roasting heat. One of the early methods is demonstrated in an old woodcut of the roast heap, Fig. 2. Ore was broken into chunks, piled on an ignition layer of solid fuel-logs in this case-and then. ignited. The sulfide ores roasted as the sulfur burned out. As shown in the background, the countryside was rapidly denuded of all vegetation by the great quantities of SO2 and other liberated gases.

Jan 1, 1961

A statistical investigation of folding at Mount Isa disclosed similar patterns in both the shales and the "silica dolomite" zones. Analysis of these patterns yields 3 groups of folds fully developed north plunging folds, fully developed south plunging folds, and flexuresrepresenting stages of development of folds. Interpretation of results indicates that a regional force from a southerly direction was responsible for the folding.The general pattern of shearing is allied to that of folding, with the exception of bedding-plane shearing. Many shears resulted from continued application of force on folds which ruptured after overthrusting. Other shears resulted from rupture of the more incompetent shale members, without associated folding. The shear pattern is consistent with the theory of a regional force from a southerly direction.INTRODUCTIONThe notes on folding and shearing presented in this paper are part of a current study of the structural geology of Mount Isa.FOLDING 1Measurement of FoldsInvestigation of folding underground involved the measurement of plunge, strike and dip of the axial plane, and the order of magnitude of each fold, together with its location and the rock type. The total number of folds measured was 701, of which 411 occurred in shale areas and 290 within the "silica dolomite" zones. All folds measured are located on main levels, from 7 level to 13 level inclusive. The sections of the mine involved are the Black Star, Black Rock and Racecourse. Detailed investigation of folds on the upper levels (4, 5 and 6) has not yet been done, but observations there suggest...

Jan 1, 1961

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

[NORTH AMERICA UNITED STATES ALABAMA AUBURN Sturm & O'Brien, Consult. Engrs. °Sturm, Rolland G. BESSEMER Granger, W. C. BIRMINGHAM Air Reduction Sales Crockett, John M. Amer. Cast Iron Pipe Co. Carter, Sam F., Jr. Donoho, C. K. Anderson Elec. Corp. Davis, Moss V. J. B. Clow & Sons Neptune, Maurice D. Connors Steel Div. °Sandelin, Robert W. Hayes Aircraft Corp. Ricketts, W. E., Jr. Willhelm, A. Clyde, Jr. McWaine Cast Iron King, O. H. Worthington, B. W. Shook & Fletcher Sup. Co. Gearhart, Thomas A. Southern Res. Inst. Dismukes, Edward B., Wheelahan, Edmund J. Thomas Foys Miller, Ralph M. Union Carbide Metals, Co. Brandler, Edgar A. U. S. Pipe & Fdry. Co. Clay, Donald H. Unaffiliated Berg, H. A. Caldwell, H. A. Gilmer, H. U. Harris, Thomas H. Templeton, J. B.]

Jan 1, 1961