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By George M. Fowler

DURING 1937 the subject of mining geology was probably given more attention and more mining geologists were usefully employed than at any previous time. Of the many contributing factors the most important were: (1) a higher degree of prosperity in many countries, (2) a. better understanding of geologic phenomena, and (3) the apparently diminishing reserves of several important minerals. Mining companies have come to look upon geology with a growing appreciation of its aid in the more effective exploration and exploitation of mineral deposits. Most of the larger and more active companies have one or more geologists permanently attached to their staffs and some have well organized and efficiently managed geological departments. Even the smaller companies, who feel they cannot afford to employ a geologist on a permanent basis, are seeking the advice of competent men in this field with increasing frequency. One of the most significant trends has been the growing tendency to base exploratory work on more thorough geologic studies instead of empirical "hunches,"on which so much off the work in the past has relied. Likewise, mining companies are apparently more willing to expend larger sums on the basis of geologic possibilities in a district.

Jan 1, 1938

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose moulding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956, p. 15). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat, abrasion, corrosion, and oxidation-resistant, and high strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, :hemica1 process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present economic-political conditions, he U.S. and for that matter, North America, has virtually insignificant ore reserves of chromite. There are chromite deposits, as will be described, but they would only be used under highly abnormal conditions if all outside sources were cut off. All chromite used in the U.S. is imported from the eastern hemisphere in which are contained the principal world reserves. As the main suppliers in 1971-72 were the USSR, Turkey, Republic of South Africa, Philippines, and Rhodesia, the strategic nature of chromite is obvious.

Jan 1, 1975

By Bernard Moore

THE last few decades have witnessed the introduction of many new nonmetallic mineral products and changes in the use of many of those already well known. Among these is diatomite, formerly employed as a mild abrasive and, at one time, as the absorbent material in dynamite. Now nearly 100,000 tons a year are mined and milled into such things as filter aids, cement admixtures, insulants, fillers, absorbents, cosmetics, cleansers, etc. Pumice, commonly regarded as only an abrasive, is now also employed as an insulant, as light-weight aggregate and as a concrete admixture. With increasing use of insulants, light-weight aggregates, and acoustic stuccos and plasters in the building trades, both these mate-rials should find increased application. Very large deposits occur in eastern Oregon and have been studied by the U. S. Geological Survey in cooperation with the Oregon State Mining Board.

Jan 1, 1934

By H. A. Kuhn

THE Pittsburg coal field in western Pennsylvania, is conceded to be the most important in the world. To measure its importance it is necessary to understand the extent of its service in the various industries of the country. Probably 90 per cent. of the pig iron manufactured in the United States up to the present time has been made by using coke manufactured from the Pittsburg coal seam in western Pennsylvania. This coal field is the foundation on which the city of Pittsburg rests and is the reason for the great growth of the iron industry in the Pittsburg district. Iron ore is brought to this district, not because Pittsburgh is a. natural location, over other locations, for the iron and steel industry-as its position places the manufacturer at the mercy of the railroads-but the ore is brought 1,100 miles to meet the fuel. It can be said that the illuminating-gas industry in the United States has used this coal exclusively to the same extent that the pig-iron maker has used it. It may be also said that 20 to 25 per cent. of the fuel used on railroads in the United States conies from this coal field. The Pittsburg coal field is unquestionably the center of the industrial population of the United States, for in addition to the industries of the district and those closely adjoining, it has tributary to it all the cities and industries along the Great Lakes and practically all of Canada with the exception of the extreme western and eastern ends. It supplies the industries and population west of Duluth and Superior many hundreds of miles. This coal is floated down the Ohio and Mississippi rivers, supplying the towns en route, and is delivered in New Orleans, a distance of 2,200 miles, for approximately SO to 90 c. per ton transportation cost. It is delivered on the docks of Superior and Duluth at a cost of transportation 50 c. a ton less than the cost of transporting the same coal from Pittsburg to a local consumer in Philadelphia. With other Appalachian coals it has large markets east and along the seaboard, especially for byproduct-coke making and the illuminating-gas industry. It is considered the premier railroad fuel of the world on account of the fact that this coal in a given-sized locomotive will probably haul more cars than any other coal in the

Jan 10, 1914

SLAG composition, slag constitution, reactions in slag, and reactions between slag and metal-in other words, the physical chemistry of slags-are matters of great importance to the open-hearth operator, whether or not he makes use of any detailed knowledge of them. Although this is a relatively young branch of the science of steel- making, much progress has been made; however, much remains to be learned, and many of the statements that can be made at present are probably--or even certainly-subject to future change. Nevertheless, the physical chemistry of slags is sufficiently developed to provide a reasonably secure basis for real understanding of steelmaking reactions. FUNDAMENTALS OF SLAG CONTROL By way of introduction, some time is spent in this chapter on effecting an easy transition from some of the more "practical" manifestations of slag to discussions couched in the more formal language of physical chemistry. This necessitates a certain amount of repetition, but it is felt that the purpose of the chapter is best served in this way. Reactions in the metal phase have products that find their way into the slag and are important components thereof; they are discussed in detail in the preceding chapter. Some substances distribute themselves Between slag and metal in definite fashion, and others are found only in the slag. Their reactions are a large reason for this chapter. Limitations of Slag Control. The open-hearth process is essentially oxidizing and cannot be otherwise operated. (Oxygen gradients in the furnace, the mechanism of oxygen inflow, and similar subjects are discussed in Chapter XIX.) As shown in the calculations of material and heat balances for the charge (see Chapter XV), from 25 to 50 lb. of oxygen will flow from air or combustion gases into the charge or molten bath during the heat for each ton of liquid steel

Jan 1, 1944

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By G. H. Clevenger

THE reagents now used in flotation consist of various acids or salts, which may be either electrolytes or non-electrolytes, dissolved in water and some substance or combination of substances which function as collecting or frothing agents. At times the only dissolved salts present are those naturally occurring in the water used. The general effect of the electrolyte is to greatly sharpen the separation between the gangue and the concentrate. Examples of this are: The use of sulphuric acid with zinc ores; and of sodium carbonate or calcium oxide (line) with silver-gold ores. Crude pyroligneous acid is also sometimes used when available. Various oxidizing agents, such as permanganates, bichromates, etc., are added in the selective flotation of lead-zinc ores. Many other reagents for performing certain specific functions, either real or imaginary, have been proposed, and a number of them have been tried upon a working scale. The wild orgy of experimentation which is now going on in flotation exceeds even that which followed the introduction of the Washoe process for the treatment of Comstock ores, when, among other things, sage-brush tea and tobacco juice were reagents added to the pans. Out of all this will, of course, eventually come a more or less standard practice for the treatment of each class of ore. Omitting a discussion of the functions of frothing and collecting agents, the reagents used in flotation for this purpose may be classified under five general heads: (1) Essential oils; (2) fixed or fatty oils;. (3) alcohols and their combinations with organic acids; (4) coal tar and its refined products; (5) petroleum and its refined products. A flotative agent of some kind is required in flotation as now practiced. A single reagent, as, for example, certain. of the essential oils, may perform the dual function of frothing and collecting agent, or a mixture of substances may be required.

Jan 9, 1916

By Frederick Prime

IN this supplementary list no titles to which an * is prefixed have been seen by the compiler; and he will be most thankful to have any omissions or inaccuracies in the list sent to him to be published as a second supplement in the next volume of the Transactions. The author is indebted to Messrs. Robert Clarke, of Cincinnati ; Thomas Macfarland, of Towanda; Professor F. W. Simouds, of Chapel Hill; and Professor J. J. Stevenson, of New York, for valuable assistance. CEDAR POINT IRON COMPANY, BALTIMORE, July 31st, 1880. ALABAMA. Geological Survey of Alabama. Report of Progress for 1877 and 1878 ; by Eugene A. Smith, State Geologist. Montgomery, 1879. 8vo., 139 pp., and 4 maps.

Jan 1, 1880

By John R. Wynnyckyj

Results of correlations between strength-development and sintering shrinkage occurring during induration are presented. A mathematical treatment of the shrinkage kinetics is, next, given and is based on the use of semi-empirical equations. The discussion stresses the significance of kinetic constants and activation energies in the assessment of iron ore concentrates for pelletizing and induration. Next, starting with the assumption that there is a need for parameters to characterize the iron-ore concentrates and relate these parameters to shrinkage-kinetic constants and balling behaviour, results of compaction measurements and pore structure characterization (mercury porosimetry) are presented and discussed.

Jan 1, 1977

South Dakota State Geological and Natural History Survey, State University, Vermillion, S D. A list of publications will be sent upon request Many of the publications are out of print A series of Biennial Reports of the State Geologist will be sent upon receipt of three cents for postage on each, and are available as follows: 1918-20, 1920-22, 1922-24, 1924-26, 1926-28, 1928-30 Available Bulletins of greatest interest are: Bulletin 4, Pre¬liminary report of the geology of the Rosebud Reservation (1909), 10 cents; 10, Possibilities of oil in South Dakota (1922), 10 cents A series of Circulars (5 cents each) deals with the possibilities of oil and gas in various parts of the state, as follows¬ Circular 8, Eastern Pennington County (1921), 9, Western Dewey County (1922); 10, Northern Dewey County (1922), 12, Eastern Harding County (1923), 13, Northern Ziebach County (1923); 20, Western Ziebach County (1925), 23, Northeastern Meade County (1925); 27, Western Corson County Other Circulars (5 cents each) are: Circular 16, The natural resources of South Dakota (1924), 22, Structures ,in northern Haakon County (1925); 24, The Ragged Butte structure (1925), 25, The structure of western South Dakota (1925), 28, Structures in western Haakon and eastern Pennington counties (1926)

Jan 1, 1933

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

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

By E. P. Pfleider, W. G. Pariseau

This paper reports the theoretical and experimental results of an analysis of ore pass drawdown as a problem in soil plasticity. The method of analysis developed appears to be a promising technique of investigating the mechanics of fragmented materials. A reconstructed plasticity theory brings experiment and theory into reasonable agreement, and hence may provide the foundation needed for rational ore pass design. The gravity-induced movement of broken rock through ore passes is an economical method of transporting fragmented materials through large vertical distances in underground mines, provided the ore pass is well designed. Unfortunately, the design procedures now followed do not very often result in ore passes that function properly. On the one hand, the huge accumulation of empirical data pertaining to the movement of materials in gravel bunkers, storage bins, deep grain silos and other structures that have features in common with ore passes remains uncorrelated. On the other hand, there is a dearth of experimental data substantiating theoretical models of material behavior. Consequently, reliable generalizations encompassing the broad spectrum of problems involved have not been forthcoming. AS an initial step towards improving the situation, a detailed case study of two-dimensional ore pass drawdown was made. The mechanics of the process were analyzed theoretically as a problem in soil plasticity and tested experimentally through observations of a laboratory ore pass model. THEORY Taylor1 defines a soil as a "mass commonly considered to consist of a network or skeleton of solid particles, enclosing voids of varying size." Broken rock in an ore pass is such a material. In plasticity theory this material is replaced by an idealized substance that deforms elastically up to some state of stress at which slip or yield occurs,2 For com-pressive states of stress, the Mohr-Coulomb criterion is a satisfactory yield condition. After the yield point is reached, the ideal soil deforms in accordance with the concept of plastic potential.4 Under plane strain conditions the governing equations separate into a system of stress equations and a system of velocity equations.' Only stress variables appear in the stress system. The velocity system, however, contains a stress variable. The two systems are, therefore, coupled. Both systems are hyperbolic, and each has two real, distinct families of characteristic curves that coincide according to the classical theory of ideal soil plasticity. The

Jan 1, 1969

By Paul Queneau

FEW of us who waded ashore on the Norman beaches realized the importance of coal to a successful invasion. General Eisenhower and his staff had been aware of the essential need for coal and an able Solid Fuels Section had been set up under the direction of Colonel Robert P. Koenig, of Indiana. This organization met the requirements of the invading armies on their march to the Rhine. East of the Siegfried Line enemy territory, the Army Engineers were called upon for assistance. When the Engineers were advised that, in addition to their normal duties, they were to occupy and place in operation the coal mines in the Twelfth Army group area, plans were drawn up overnight and action was initiated immediately. The Sixth Engineer Special Brigade, a versatile outfit which made a notable record D-Day on Omaha Beach, was selected to handle the operation. Within 48 hours of the new assignment an advance command post was set up cm the west bank of the Rhine at Homberg, just below German-held Duisburg. The 368th Engineer General Service Regiment was assigned to the Brigade, and the British 44th Pioneer Group, including specialist personnel, was also attached. This large British unit was added because most of the mines would shortly come within the British zone of

Jan 1, 1946

By W. C. Phalen

SALT-MAKING PROCESSES THE production of salt in the United States divides itself at the outset into two distinct classes: (1) The mining of rock salt and its purification and separation into marketable sizes, and (2) the production of salt by evaporation from brines, bitterns, and other solutions. The processes employed at the present time in the manufacture of salt by evaporation may be outlined as follows: 1. Solar evaporation. 2. Direct-heat evaporation (a) in open kettles; (b) in open pans. 3. Steam evaporation, (a) in jacketed kettles, (b) in grainers. 4. Vacuum-pan evaporation. In this paper only the solar-evaporation processes practised in different parts of the United States will be described. SOLAR EVAPORATION Localities In the Eastern States the solar-evaporation process is not generally employed for climatic reasons. In the Western States, particularly in California and Utah, the great bulk of the salt produced originates in the solar-evaporation process. Of the Eastern States producing salt, this process, so far as the writer is aware, is employed in New York State only.

Jan 9, 1914

By Nicholas J. Grant, John Chipman

A FULL understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization; the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag-i.e., equilibrium conditions-and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck :20 [ ] Among others there appear the following:

Jan 1, 1946

By William E. Ford, Edward Salisbury Dana

5. Crystallography. - The subject of Crystallography includes the description of the characters of crystals in general; of the various forms of crystals and their division into classes and systems; of the methods of studying crystals, including the determination of the mathematical relations of their faces, and the measurement of the angles between them; finally, a description of compound or twin crystals, of irregularities in crystals, of crystal- line aggregates, and of pseudomorphous crystals. 6. Definition of a Crystal.- A crystal * is the regular polyhedral form, bounded by smooth surfaces, which is assumed by a chemical compound, under the action of its intermolecular forces, when passing, under suitable conditions, from the state of a liquid or gas to that of a solid. As expressed in the foregoing definition, a crystal is characterized, first, by its definite internal molecular structure, and, second, by its external form. A crystal is the normal form of a mineral species, as of all solid chemical com- pounds; but the conditions suitable for the formation of a crystal of ideal perfection in symmetry of form and smoothness of surface are never fully realized. Further, many species usually occur not in distinct crystals, but in massive form, and in some exceptional cases the definite molecular structure is absent. 7. Molecular Structure in General.- By definite molecular structure is meant the special arrangement which the physical units, called molecules, assume under the action of the forces exerted between them during the formation of the solid. Some remarks are given in a later article (p. 22 et seq.) in regard to the kinds of molecular arrangement theoretically possible, and their relation to the symmetry of the different systems and classes of crystals.

Jan 1, 1922

By Paul M. Tyler

The term "milling" as applied to nonmetallic minerals often refers merely to pulverizing without preliminary beneficiation. As applied to dimension stone, it embraces all the gteps involved in shaping and giving the desired finish to blocks. Processes such as sawing, planing, rubbing and polishing seem far removed from milling as the term is used in ore dressing, nevertheless they involve the element of concentration, for only 25 to 50 per cent of the gross quarry output may leave the mill as finished products after imperfect stone has been culled and the rough blocks trimmed. On the other hand, numerous nonmetallic minerals have to be concentrated in much the same manner as low-grade ores. Engineers and machinery manufacturers have begun to recognize more clearly the opportunities awaiting them in the nonmetallic field and have brought with them the methods and equipment developed in metal-mining camps, occasionally with little modification. General Economic Considerations Approximately one-half of the total value of the mineral production of the United States represents mineral fuels, and the other half is about equally divided between metals and nonmetals, the nonmetals recently having become relatively more important. In terms of volume the domestic output of nonmetallic minerals other than fuels is more than 10 times the annual output of metals. Considered on the basis of industrial utility and general commercial and military significance, moreover, the flow of nonmetallic mineral products is quite as needful to our national integrity and well-being as is that of metals, fuels, or other basic materials. Despite their importance individually and as a group, the nonmetallic mineral industries differ so widely in essential characters and economic environment that producers thereof have been slow to develop a community of interest among themselves or with the metal-mining fraternity. A spirit of change is in the air, rule-of-thumb methods soon may be relegated to limbo, and new methods—especially time-tested ideas borrowed from ore-dressing practice—are being introduced. A faithful record of plant practice in certain of these fields, however, must register

Jan 1, 1935

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By J. E. Hilliard, J. W. Cahn

calculation has been made of the standard deviations to be expected in the measurement of volume fractions by areal analysis, lineal analysis and four point-counting Procedures. The effect of experimetztal errors is not included. Our conclusion is that a point count using a two-dimensional grid will be the most efficient method of volume fraction analvsis providing the grid spacing IS coarse enough. The predicted standard deviation for such an analysis is shown to he in good agreement with that determined experimentally. A metallurgist wishing to estimate a structural property by means of quantitative metallography is often faced with a choice between several different procedures. In such a case, he will naturally wish to know: a) Which procedure is the most efficient in the sense of requiring the least effort for a given precision? b) For a given procedure, what are the conditions for maximum efficiency? c) Under these conditions, how many measurements are required to attain a given precision? It is our aim in this paper to provide at least partial answers to these queries as they relate to the estimation of volume fractions from measurements on a random two-dimensional section of an opaque specimen. The commonly used techniques1,2 for volume-fraction analyses are based on one or more of the following principles: i) For an areal or Delesse3 analysis: That the areal fraction of a three-dimensional feature intercepted by a random plane provides an unbiased estimate of the volume fraction of that feature. ii) For a lineal or Rosiwal4 analysis: That the fractional intercept on a line passing at random through a two-or three-dimensional feature provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. iii) For a point-count analysis: That the fractional number of randomly or regularly dispersed points falling within the boundaries of a two-dimensional feature on a plane, or within the boundaries of a three-dimensional feature in a volume, provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. The absence of bias referred to in these principles does not, of course, imply that the results of an analysis will be free of error, but only that the expected result is equal to the true one. Application of the foregoing principles provide the following six possible experimental procedures: a) An Areal Analysis—This involves the measurement with a planimeter (or other means) of the area of a constitutent intercepted by the plane of polish b) A Two-Dimensional Random Point Count—Apos-sible experimental procedure for this analysis is to superimpose a sheet of transparent graph paper on a micrograph, and then use a table of random numbers to select coordinates for the points. c) A Two-Dimensiotuzl Systematic Point Count-Similar to b) except that the points are distributed in a prescribed manner, usually at the corners of a lattice superimposed on a micrograph or the screen of a projection microscope. d)A Lineal Analysis—A measurement of the fractional line length intercepted. It is usually performed by traversing the specimen under the cross hairs of a microscope and recording the distance travelled in each constituent. e) 4 One-Dimensional Random-Point Count— This could be performed by traversing the specimen with stops at random intervals to identify the constituent then present under the cross hairs. f) A One-Dimensionul Systematic Point Count— Similar to e) except that the traverse is stopped at prescribed (usually equal) intervals. It will be noted that the point-counting procedures b) and c) can be regarded as methods of estimating the areal fraction. Similarly, e) and f) are indirect methods of making a lineal analysis. All of the six procedures described above involve at least one stage of sampling. Thus, quite apart from any experimental errors, there will always be a statistical uncertainty associated with the final results. It is with the calculation of this uncertainty that we will be concerned. To avoid unnecessary repetition, the statistical relationships that will be used in the calculations are collected together in the appendix. For a fuller discussion reference should be made to one of the many textbooks5,6 on statistics. For symbols relating to the specimen structure we will follow as far as possible the terminology used by Smith and Guttman.7

Jan 1, 1962