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By A. L. Labbe

SOON after the Cottrell treater was placed in operation in the Murray plant in 1918 to treat combined lead sinter and Wedge roaster smoke, it was noticed that the power flowing through the treater did not remain constant. This was indicated by the varying milliamperes and also by the total amount of power consumed by the rectifiers. At times, for then unknown reasons, the treater current fluctuated through a wide range of from 40 to 300 milliamperes. Fortunately, these variations in power did not affect the treater's overall recovery, as this installation consisted of three independent units in series, a feature which made the Murray Cottrell an outstanding installation over many years of operation. Water conditioning of the smoke as a means of improving recovery was already known, but was not adaptable to this installation for reasons of excessive corrosion, which had been the case with other treaters using water as a conditioner exclusively. Tests conducted on the smoke had proved conclusively that water vapor played no part in the fluctuation of power, and the same was true of the SO2 contents and dust burden of the smoke. Neither did temperature variations of from 150 to 400°F have any effect on the power. Finally it was noticed that the variation in power taken by the treater, and the efficiency of recovery, had some definite relation to the number of Wedge roasters operating, and particularly to the sulphur contents of the charge. This observation soon led to the discovery that free sulphuric acid was the conditioner for Murray smoke and that variations in acid contents of smoke accounted for fluctuations of treater power. Analysis of recovered dust revealed that only a few hundredths of a per cent free acid was necessary to maintain a very efficient recovery. Once this knowledge was available, the roaster charge was adjusted as to sulphur contents to produce the necessary acid conditioner. For a number of years this practice was followed, but with improvements in the field of flotation, excess pyrites were eliminated from the smelting picture, so with a change in metallurgical practice we were confronted with the problem of providing the deficiency in acid by some other means. The situation was aggravated and our problem of acid conditioning made more difficult by the increase in the lead contents of concentrates roasted resulting from better flotation methods. The first step towards introducing acid vapors into the smoke stream by accessory means was accomplished by boiling sulphuric acid in cast iron pots placed in an open fire box. Acid fumes evaporated from the pots together with the combustion gases from the fire box were discharged into the flue through a cast iron pipe. Capacity of the iron pots was quite limited because of the comparatively slow rate of evaporation and the use of lump coal as a fuel, which did not lend itself to practical temperature control. This method of firing resulted in frequent pot failures due to overheating. In spite of these incidental difficulties, encountered in any new venture, the pot evaporator demonstrated the practicability of fuming sufficient acid to make up the deficiency in that naturally evolved in the Wedge furnace operation. As time progressed, less and less high sulphur material was available for Wedge roasting, and the necessity for accessory acid conditioning reached a climax when the supply of this material was entirely eliminated. Since the cast iron pots could only evaporate a few hundred pounds of acid per day, and were costly to replace, the logical thought presented itself of spraying the acid in a heated chamber. This new type of acid evaporator was simpler and more economical to operate and had sufficient capacity to fume several thousand pounds per day. The attached fig. 1 presents the outstanding features of the new furnace. A is the vaporizing drum, which is heated by the combustion gases of coal stoker fire box, B. Acid is sprayed into the hot gas stream within the drum through a number of air-acid atomizers, C, and the acid vapor, together with combustion gases, is introduced into the smoke stream through two cast iron pipes extending to different points in the flue. The operation of this type of furnace requires control of temperature inside the drum to prevent overheating, which dissociates the acid vapor to SO, and eventually to SO2, with resulting loss of acid. The dissociation to SO, at elevated temperatures is comparatively high, and in some cases accounts for as much as 60 pct of the acid sprayed into the drum. To reduce the loss of acid, through dissociation, some Cottrell plants, where the rate of acid sprayed reaches at times 9 ppm, use two evaporating units. Fuming the acid into the smoke stream is only

Jan 1, 1951

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By O. E. Kiessling

THIS announcement of the topics relating to production control, which the Committee hopes to have discussed at the February meeting, supplements the preliminary announcement published in the November number of MINING AND METALLURGY. In the previous article, the writer indicated the kaleide-scopic nature of the questions involved in obtaining better coordination in industry, and that, as a matter of practical expediency, the discussion in February would be limited to the more obvious difficulties in industry which need attention and to those questions which the Committee thinks would be of greatest interest to members of the Institute. But while practical considerations necessitate limiting the program, free discussion of all phases of the subject is urged by 'the Committee. In a preliminary consideration of the production control problem, there loom up two questions which have to be faced: (1) First, there is the question of the extra industrial capacity necessary to meet demand during the ordinary fluctuations of business, commonly characterized as `the "business cycle." Anyone who tries to formulate a program pertaining to productive capacity must decide whether he wishes to discuss the control of business cycles. While this question may eventually lend itself to treatment, the Committee does not feel that it can be considered at present with much profit. (2) The second question arises from the existence of over-stimulated capacity above and beyond peak demands in boom times. Discussion of this topic, it is felt, would be most fruitful. How to prevent capacity from being over-stimulated to an extent beyond any hope of possible demand is a

Jan 1, 1929

By J. B. Urnfileb

THE function of gas in the development and production of oil has far reaching consequences that should be emphasized. The technical aspects of the subject have recently had a great deal of attention but less thought has been given to fundamental concepts underlying oil and gas law and the many customs and practices that have grown up in the industry. I shall re- view briefly the advance in knowledge of the subject and attempt to relate these concepts to legislative, judicial and operating problems. Early writers on oil and gas in Pennsylvania noted their close association in oil pools and their contemporaneous decline in output; also, that as gas pressure decreases so does production, that new offset wells reduce the output of existing wells, and even that tubing a well lengthens its flowing life. Expanding gas was deduced as the principal expulsive force. These fundamental observations had been made at least as early as 1880.l They were treated, however, as academic considerations and did not greatly influence law or practice for many years except to instil into all operators an urgent desire to hasten offset drilling to obtain as much of the flush as possible.

Jan 1, 1932

By F. Weinberg

INTEREST is currently being directed toward grain boundary morphologies in zinc in terms of grain boundary facetingl and grain boundary energies.' Some years ago the present author attempted to measure grain boundary energies in 99.999 pct purity Zn as a function of boundary angle, using the standard procedure of measuring equilibrium angles of the boundary traces at triple points. This followed an investigation he carried out on preferential melting of |H (112) Fig. 1—Electron transmission micrograph of a stacking fault, grain boundary intersection in copper. GRAIN BOUNDARY STACKING FAULT Fig. 2—Schematic representation of the intersection of Fig. 1, indicating inclination angles 0 and trace angles $. specimens were prepared by the Bollman technique in an electrolyte of 70 pct methanol, 30 pct HNO3 main-tained at -30°C. The interfacial free energy of the high angle grain boundary and of the stacking fault is assumed to be thermodynamically equivalent to the corresponding in-terfacial tensions. In terms of the true dihedral angles & between the intersecting interfaces, the equilibrium of interfacial tensions in the direction parallel to the stacking fault yields: ysF = -ygb(cos F1+ cos ±cosF2) Here, ysF is the stacking fault free energy and ygb is the grain boundary free energy, assumed equal on both sides of the intersection. Forces acting normal to the grain boundary, of the form ??gb/?F,l are assumed negligible as the grain boundary remains straight for a considerable distance on either side of the intersection. The micrograph of Fig. 1 may actually consist of several closely spaced stacking faults on the same slip plane. The actual point of intersection between the grain boundary and the first stacking fault, and the equilibrium configuration of the intersection, should not be affected by the presence of the other faults, as

Jan 1, 1970

By C.P. Proctor, J. T. Crawford, J.A. Younkins

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By C. P. Proctor, J. A. Younkins, J. T. Crawford

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By William F. Boericke

THERE was a time when the selection of fire brick was .left to the judgment of the head bricklayer of the plant, whose choice was not unaffected by a box of Christmas cigars from a friendly salesman. But the days are past when it was generally believed, with complacent philosophy, that bricks were bricks without much distinction, and should be bought on a price basis alone. Gone, too, is the belief that in certain types of industrial work the eventual failure of refractories was assured. Modern metallurgical practice, with its trend toward handling larger tonnages at higher temperatures, demands the use of refractories that cannot be supplied by random guess. The logical development is to inquire into the properties of the brick to be purchased, and this resolves itself into the use of specifications. In 1925, the General Refractories Co., with the active support and hearty cooperation of some of its larger customers, established a laboratory, at its Baltimore plant, for testing and research in refractories. This was the outgrowth of a growing appreciation of the value of research in the refractory field. Since then the work has become more involved' and the aims more ambitious, so that the present laboratory now employs a staff of 11 men working, under the direction of trained refractory technologists, on problems of research as well as the routine control of manufacture. It is believed s that `this type of laboratory is a comparative novelty among refractory manufacturing plants. It handles the testing and research work for all the 15 plants of the organization. Being at one of the works has the advantage of making it possible to carry on large scale plant tests on new products after the preliminary laboratory tests have been successfully completed.

Jan 1, 1929

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By J. J. Van Nouhuys

THE economics of aerial survey and the technical processes by the aid of which vertical and oblique aerial photographs are turned into line maps showing the most profuse topographical detail such as contours, rivers, roads, plantations, habitations and cultivated lands do not concern us here. They have been ably and exhaustively described in the publi-cations of the British War Office, handbooks on surveying methods and on photogrammetry and in the South African mining, engineering and geological press. Suffice it to mention that for geological interpretation vertical photo-graphs are used on such scales as soon to 1/5,000 to 1/10,000, overlapping each other by 55 to 60 per cent in the direction of flight and some 10 to 20 per cent sideways on to the next sequence or strip. Through this duplication in the overlap the stereoscopic examination becomes possible. The standards by which monochrome aerial photographs are inter-preted can be grouped under the following headings: 1. Continuity.-The continuity of topographic relief not obtainable on the ground owing to the smallness of man relative to that relief. Here lies the greatest value of aerial survey with relation to geology. An immediate alignment can often be made of drainages running in different directions on each side of a hill; saddles and gorges in the mountainsides; abrupt termination of outcrop or indubitable signs of faulting. Most conclusive evidence is thus often obtained about faults which may be perfectly visible at one place on the ground but cannot elsewhere be identified because of decreased throw. Similarly, dikes can often be followed notwithstanding frequent interruption and disappearance under the soil. Scattered outcrop in scrub-covered or bush-covered country can be conveniently located and often correlated, with a large saving of time compared with field work. The same applies to geological contacts. Once these have been established at a few points on the ground, the intervening stretches can be drawn in.

Jan 1, 1937

By E. Peters

As in other fields of Extractive Metallurgy, Hydrometallurgy is preoccupied with separation processes and with oxidation-reduction processes. The physical chemistry of each type of process can be described in terms of thermodynamic equilibria and in terms of reaction kinetics. Reaction kinetics are much more important at the low temperatures limiting hydrometallurgical processes than in com- parable pyrometallurgical operations and the number of cases in which the kinetics can be described by simple liquid-phase mass-transfer models are sharply limited. It is convenient to subdivide the applicable rate phenomena into processes in which (a) interface reactions control the rate,(b) mass transfer processes control the rate, (c) solid state process affect the rate, (d) thermodynamically predicted phase changes or molecular reactions fail to take place, (d) metastable substances or supersaturated phases persist, and (elchomogeneous reactions in solution affect the chemistry and the kinetics. Examples are drawn from the unit steps of leaching, cementation, hydrogen reduction, and electrowinning.

Jan 1, 1973

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By Ernest Darby

WHEN bronze is melted in open-flame furnaces a considerable amount of slag is formed during the melting operation. This slag may be incidental to the melting practice or it may be formed intentionally by slag-forming constituents added to the furnace charge to provide a covering for the melted metal. When this slag is removed from the furnace, it contains, in addition to the free metal carried with it by the skimming operation, a considerable amount of metal as oxide either combined or mechanically mixed with it. By the usual crushing and washing methods this metallic oxide generally goes to the tailings pile, so diluted by other foundry waste that its recovery is economically impossible. If this furnace slag is not mixed with other foundry waste, practically all of the metal oxide as well as the free metal may be recovered by some form of smelting operation. The first side of the problem to be considered is the amount of slag produced. It may not be true that the majority of foundries have no record of the amount of slag made, but it is certainly true that a very great many either have no record or pay little attention to it. Usually the collection of furnace slag for one normal week's run will be sufficient to determine the advisability of its being handled in a different manner from the crushing and concentrating generally employed. If a large representative sample of the accumulation is crushed and concentrated and the recovery compared with the results of a careful assay, it will be found that a large percentage of the total metal content was lost in the washing process. The percentage of loss will be greater than the metallic oxide content, as some free metal in extremely fine particles always is carried away in grains of slag. From such a comparison, it may be determined whether or not the slag should be melted, sold or treated as before. An example of an actual test of this kind is given below.

Jan 1, 1928

By Ernest Darby

WHEN bronze is melted in open-flame furnaces a considerable amount of slag is formed during the melting operation. This slag may be incidental to the melting practice or it may be formed intentionally by slag-forming constituents added to the furnace charge to provide a covering for the melted metal. When this slag is removed from the furnace, it contains, in addition to the free metal carried with it by the skimming operation, a considerable amount of metal as oxide either combined or mechanically mixed with it. By the usual crushing and washing methods this metallic oxide generally goes to the tailings pile, so diluted by other foundry waste that its recovery is economically impossible. If this furnace slag is not mixed with other foundry waste, practically all of the metal oxide as well as the free metal may be recovered by some form of smelting operation. The first side of the problem to be considered is the amount of slag produced. It may not be true that the majority of foundries have no record of the amount of slag made, but it is certainly true that a very great many either have no record or pay little attention to it. Usually the collection of furnace slag for one normal week's run will be sufficient to determine the advisability of its being handled in a different manner from the crushing and concentrating generally employed. If a large representative sample of the accumulation is crushed and concentrated and the recovery compared with the results of a careful assay, it will be found that a large percentage of the total metal content was lost in the washing process. The percentage of loss will be greater than the metallic oxide content, as some free metal in extremely fine particles always is carried away in grains of slag: From such a comparison, it may be determined whether or not the slag should be melted, sold or treated as before. An example of an actual test of this kind is given below.

Jan 1, 1928

By Anson G. Betts

A solution of lead-fluosilicate, containing an excess of fluosilicic acid, has been found to work very satisfactorily as an electrolyte for refining lead. It conducts the current well, iseasily handled and stored, non-volatile and stable under electrolysis, may be made to contain a considerable amount of dissolved lead, and is easily prepared from inexpensive materials. It possesses, however, in common with other lead electrolytes, the defect of yielding a deposit of lead lacking in solidity, which grows in crystalline branches toward the anodes, causing short circuits. But if a reducing-action (practically accomplished by the addition of gelatine or glue) be given to the solution, a perfectly solid and dense deposit is obtained, having very nearly the same structure as electrolytically-deposited copper, and a specific gravity of about 11.36—that of cast-lead. Lead-fluosilicate may be crystallized in very soluble, brilliant crystals, resembling those of lead-nitrate and containing four molecules of water of crystallization, with the formula PbSiF,,4H20. This salt dissolves at 150 C. in 28 per cent. of its weight of water, making a sirupy solution of 2.38 sp. gr. Heated to 60° C., it melts in its water of crystallization. A neutral solution of lead-fluosilicate is partially decomposed on heating, with the formation of a basic insoluble salt and free fluosilicic acid, which keeps the rest of the salt in solution. This decomposition ends when the solution contains, perhaps, 2 per cent. of free acid; and the solution may then be evaporated without further decomposition. The solutioi~s desired for refining are not liable to this decomposition, since they contain much more than 2 per cent. of free acid. The electrical conductivity depends mainly on the acidity of the solution. My first experiments were carried out without the addition of gelatine to the fluosilicate solution. The lead-deposit con-

Jan 1, 1904

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By Harrison R. Cooper

With problems of diminishing ore grades and increasing cost of facilities, the mineral industry is acutely aware of the needs for improving beneficiation processes. Industry and universities are directing intensive technical effort to develop- ment of techniques with potential for using digital computers in automation and process analysis. The main problem of early attempts at on-line computer process control methods was that of economics. Now, with new advances in analysis and modeling making practical application economically important, it appears that minerals beneficiation is on the threshold of a significant jump in operating technology. In reviewing this work, particular note was taken of research and development applied to fundamental processes and the significant areas of effort where operations research techniques are used for process applications leading to the current state-of-the-art. Development of data automation and on-line control methods for process industries is deferred to the next section of this volume. This section deals with computer-facilitated mathematical-modeling development and reviews this work in conjunction with associated prior fundamental research leading to development of the methods. Flotation The 1960 state-of -the -art in flotation modeling was com- piled by Arbiter and Harris in the volume, 50th Anniversary of Froth Flotation, edited by Fuerstenau1. Many workers in the field of flotation initiated their research through flotation models, and this effort has led to use of simulation and operations re search methods employing computer techniques to facilitate advance of this work. The flotation model of Imaizumi and Inoue, published with supporting data in 1962, was expanded in 1968 with the objective of developing a basis for process automation.2,3 The fundamental work of Woodburn and Loveday in 1965 has led to techniques applicable to flotation circuit design optimization.4 This analysis is described in this volume by Woodburn in conjunction with King, Buchalter, and Piper. Niemi5,6 derived models for dynamics of a flotation circuit which were employed in developing a model describing

Jan 1, 1969