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By G. A. Vissac

O. R. LYONS *—I wish to thank Mr. Vissac for his compliment. I hope that his paper is not only well received, but that it will serve to bring forth more papers on the subject of thermal drying. One of the primary purposes of the work performed by Battelle for Bituminous Coal Research in investigating the thermal drying of coal was to stimulate other investigators and to get them to contribute their knowledge in the form of papers such as this one. We at Battelle and the personnel of Bituminous Coal Research are very gratified that Mr. Vissac and other persons have responded in this matter of the thermal drying of coal. I wish to state that I think that Mr. Vissac's paper is a very clear and easily understood description of a method of calculating the design requirements for a screen type drier, and I think that it would be exceedingly valuable to operators and to those who intend to purchase any type of thermal drier and use it in the future, if the manufacturers or operators who have such information for other types of driers would provide the same type of information for the other makes of driers now on the market. 1 also wish to point out—an idea that is new to me, and I know is new to most of the operators of driers in the United States-—the idea of recovering the heat that is normally lost in the coal and in the exhaust gases. This heat is not being recovered at most (of the thermal drying operations in the United States, and the possibility of recovering it should be called to the attention of every single one of those operators. I know many of them have never given any thought to the matter, but they will be interested once they realize the ease with which it could be done and the savings that could be realized. I also wish to compliment Mr. Vissac for presenting the method of analysis that he uses to determine the difficulty of drying any particular coal. It is a very simple method, and yet it seems to me that it should be a very effective, very efficient method for determining the difficulty of drying for his particular problems. C. Y. HEINER*—I do not know that I can add anything very illuminating to what Mr. Vissac has said. I think anything that Mr. Vissac said in regard to coal drying is a contribution because, to my personal knowledge, he has studied the matter carefully for many years and made many valuable contributions. I am not too familiar with coal drying problems in the east, but I know in the west we have not made enough coal drying studies. I think coal operators too often just take the coal as it is and make more or less the best of it. There are relatively few washing plants in the west now, and so the problem has not come to the front as much as it probably will in the future. In this connection, it seems to me that this matter of drying the raw coal, as Mr. Vissac brings up, is an extremely important one. We have not a continuous miner ourselves, yet, but we expect to get some this year, and we think the percentage of fine coal-—that is, minus 3/16 in.—will double. We have about 20 pct minus 3/16 in. in the 8 in. by 0 size now, and we think we will likely have 40 pct, which will have a surface moisture of the order of 8 pct. To wash it satisfactorily, we will have to dry the raw coal first in order to screen it, and after that, I suppose, there will have to be dry cleaning of some sort. We have not really used dry cleaning on fines in the west yet to my knowledge, but it is a matter that has to be faced by the industry, and I am very hopeful that Mr. Vissac's study will assist us in that connection. W. L. McMORRIS*-In my company we are preparing largely metallurgical coal for a great number of byproduct coke plants. The most outstanding thing to me about the requirements of moisture in the finished product is that there is a different requirement for almost every coke plant. Each operator has a different set of factors on which he establishes his coking costs where they involve moisture. For our corporation operations in Birmingham, my company does not produce the coal, but in Birmingham they are getting away with moistures very much higher than our plant at Clairton, Pa., would tolerate. The moisture that we have to produce for the plants along the lakefront where they are subject to much more severe weather is something else again. We have not tackled heat drying, primarily because our customers do not know what heat drying will do to the coking characteristics of the coal. If the temperature of drying can be held down

Jan 1, 1950

By Theron Wasson

The oil and gas fields of Michigan that have been under development since 1925 are in an area that extends across the middle of the lower peninsula from northeast to southwest, a distance of about 200 miles, and with a width of about 80 miles. In 19 years 70 fields have been discovered. Most of these are relatively small when compared with other oil-producing areas. This is borne out by the fact that since the first wells were drilled these fields have produced a total of only 204,000,000 bbl. However, Michigan is still maintaining its production, for during the past five years the annual production has remained fairly constant at approximately 20,000,000 bbl. Production for 1943, as reported by the Bureau of Mines, was 20,682,000 barrels. Roughly, one third oi Michigan's production in 1943 came from the Reed City field, which was discovered in 1941. During the year, 237 oil wells were completed in Michigan in 1943. The decrease of 56 from the 1942 total is probably due to the continuance of Government regulations requiring a 40-acre spacing pattern over most of the state. Fig. I shows the principal oil and gas fields of Michigan, and the columnar section, Fig. 2, shows the principal producing horizons in relation to the section drilled. The data of Table I and Table 2 have been carefully checked with previous reports to eliminate errors. Six new producing areas were discovered during 1943 and five areas discovered in 1942 were developed during the year. Both the new discoveries and the 1942 discoveries that were developed appear to be small and relatively unimportant. Goodwell Field.—The best discovery of the year is the Goodwell field, T. 14 N., R. 11 W., Goodwell township, Newaygo County. This small structure was located by core testing done by The Pure Oil Co. in 1942 and early 1943. The first producing well, C. R. Harris No. I, was completed on July 5, 1943, ill the Traverse limestone at a total depth of 2742 ft., with ail estimated potential of 1100 bbl. per day. By the end of the year, 18 wells had been completed in this field and approximately 281,000 bbl. of oil produced. The field operated under proration of 262 bbl. per day per well from Oct. I to Dec. I; 150 bbl. per day per well after that date. Woodville Field.—The small Woodville pool, T. 15 N., R. 11 W., 3 miles north of the Goodwell field, was discovered by core testing by the Ohio Oil Co. The discovery well was completed on May 5, 1943, flowing 650 bbl. of fluid, including 18 per cent salt water the first 18 hr., from the Traverse limestone at a depth of 2810 to 2815 ft. Seven wells had been completed by the end of the year and 67,000 bbl. of oil had been produced. Development is now practically at a standstill because further drilling does not aDDear economically iustified.

Jan 1, 1944

By Theron Wasson

The oil and gas fields of Michigan that have been under development since 1925 are in an area that extends across the middle of the lower peninsula from northeast to southwest, a distance of about 200 miles, and with a width of about 80 miles. In 19 years 70 fields have been discovered. Most of these are relatively small when compared with other oil-producing areas. This is borne out by the fact that since the first wells were drilled these fields have produced a total of only 204,000,000 bbl. However, Michigan is still maintaining its production, for during the past five years the annual production has remained fairly constant at approximately 20,000,000 bbl. Production for 1943, as reported by the Bureau of Mines, was 20,682,000 barrels. Roughly, one third oi Michigan's production in 1943 came from the Reed City field, which was discovered in 1941. During the year, 237 oil wells were completed in Michigan in 1943. The decrease of 56 from the 1942 total is probably due to the continuance of Government regulations requiring a 40-acre spacing pattern over most of the state. Fig. I shows the principal oil and gas fields of Michigan, and the columnar section, Fig. 2, shows the principal producing horizons in relation to the section drilled. The data of Table I and Table 2 have been carefully checked with previous reports to eliminate errors. Six new producing areas were discovered during 1943 and five areas discovered in 1942 were developed during the year. Both the new discoveries and the 1942 discoveries that were developed appear to be small and relatively unimportant. Goodwell Field.—The best discovery of the year is the Goodwell field, T. 14 N., R. 11 W., Goodwell township, Newaygo County. This small structure was located by core testing done by The Pure Oil Co. in 1942 and early 1943. The first producing well, C. R. Harris No. I, was completed on July 5, 1943, ill the Traverse limestone at a total depth of 2742 ft., with ail estimated potential of 1100 bbl. per day. By the end of the year, 18 wells had been completed in this field and approximately 281,000 bbl. of oil produced. The field operated under proration of 262 bbl. per day per well from Oct. I to Dec. I; 150 bbl. per day per well after that date. Woodville Field.—The small Woodville pool, T. 15 N., R. 11 W., 3 miles north of the Goodwell field, was discovered by core testing by the Ohio Oil Co. The discovery well was completed on May 5, 1943, flowing 650 bbl. of fluid, including 18 per cent salt water the first 18 hr., from the Traverse limestone at a depth of 2810 to 2815 ft. Seven wells had been completed by the end of the year and 67,000 bbl. of oil had been produced. Development is now practically at a standstill because further drilling does not aDDear economically iustified.

Jan 1, 1944

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies', the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,' vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell' published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson' has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By Gust Bitsianes, Joseph H. M. Beaty

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By Joseph H. M. Beaty, Gust Bitsianes

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By R. J. Cowan

In the art of cementation a controversy has been going on for years as to whether solid or gaseous carbon is the active agent in carburizing steel. More recently opinion has crystallized into a compromise to the effect that carburizing is a gaseous cementation of steel in the presence of solid carbon. The importance of this theory has a particular bearing upon the work to be described. In the art of carburizing, use is commonly made of such words as '' Catalytic" "atomic," "nascent" and "activated," in an attempt to describe the process. These words are used indiscriminately. For instance, the gas is said to be "catalytic" and carbon to be "nascent," or vice versa. In using these expressions, investigators are confirming the acceptance in their minds of the active conditions of both gas and carbon in the cementation process. Reactions at Metal Surfaces For many years attention has been directed to the consideration of reactions that occur on metal surfaces. When heated under the influence of certain metals a complex gas will be broken down and one of the constituents thereof usually found to be very active chemically in combining with the metal. The process of nitriding is an example of this type of reaction. In this case ammonia (NH3) breaks down at the metal surface and the nitrogen which is thus liberated reacts with the surface to form a nitride whereas molecular nitrogen not so liberated is inert and will not react chemically with the metal. Whatever term or terms may be used to describe such reactions, the fact remains that they are highly important and valuable in their commercial applications. Since the metal surface plays so important a part in these reactions, it is evident that any accumulation of reaction products thereon interferes seriously with the progress of the reactions. For this reason it is desirable to remove all such products as rapidly as they are formed in order to bring active gas into contact with the surface and thus facilitate the desired reactions. This is accomplished best by conducting the operation in a continuous manner, thereby causing the reacting gases to pass over the

Jan 1, 1931

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis' and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations' that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By John V. Beall, John Cameron Fox

Organization In 1948, the Committee on Divisionalization and Publication Program of AIME, known as the Johnson Committee, recommended the reorganization of the Institute into three branches, Mining, Metals and Petroleum. This recommendation was accepted and the new organizational structure was implemented in Jan., 1949. The Mining Branch, at the time of the formation, had three divisions: the Coal Division formed in 1929, the Industrial Minerals Division (IndMD) dating from 1935, and the Minerals Beneficiation Division (MBD) formed in 1948 from the Milling Methods Committee, which had existed for many years. There did not exist, however, a division for the geologists and mining engineers. From the time of the founding of the Institute, this group was the main stem of AIME and never felt the need to segregate. The disciplines of mining and geology were served by a number of technical standing committees of AIME. With the birth of the new Branch, a new Division, the Mining, Geology and Geophysics Division (MGGD) was formed, completing the divisional structure of the Mining Branch and providing a home for all members. The governing body was the Mining Branch Council, with two members from each Division of the Mining Branch and one each from the Mineral Industry Education Division and the Mineral Economics Division. These last two divisions served all three Branches of AIME. The Division is such an important unit in the organization structure that it is of value to explain that it appoints committees to handle pro- grams, publications, and awards - representing the main functions of the Institute - as well as many others. There is enough flexibility in the organization so that each Division may have its own special committee structure as long as primary functions are provided. The past is indeed prologue to the future, for in 1957 the Johnson "Branches" gave way to the Fletcher "Societies." The Fletcher Committee, in 1958, recommended a new reorganization into Societies, each with the authority to administer its own finances and to designate certain officers and directors to the AIME Board. The date on which the Society of Mining Engineers was formed in Feb., 1957, has become known as "R" Day. A smooth transition from the loose Branch structure to Society organiza-

Jan 1, 1971

By James K. Stanley

When a plastically deformed mctal is heated to a certain temperature, it undergoes a complete change in microstructure, the consequence of which is a marked alteration of mechanical properties such as hardness, strength and ductility. This change in microstructure occurs by re-crystallization and is a process involving the formation and growth of strain-free nuclei in the deformed matrix. These nuclei continue to form with time and grow until a new grain structure replaces the cold-worked structure. The formation of the nuclei in the deformed sheet of I per cent silicon ferrite is illustrated in Fig. I. If a recrystallization is conducted iso-thermally, a nleasurement of the fraction of the matrix recrystallized plotted against time leads to an isothermal recrystallization curve, first established in 1942.1 Such recrystallization curves are shown in Fig. 4. These curves show that the recrystallization of a cold-worked metal is best considered as a rate process rather than a time independent process such as is suggcsted by the improperly named and misleading recrystallization diagrams involving deformation, temperature, and grain size.2-5 Any study of the rate of recrystallization resolves itself into a study of the component rates of nucleation and growth. The previous paper1 provided an account of the determination of the rates of nucleation; N, the number of nuclei formed per unit time per unit of unre-crystallized area, and growth, G, the radial growth in unit time, in the recrystallization of silicon ferrite (I per cent Si). A method was developed to furnish experimental data for evaluating the effect of the recrystallization variables on N and G. The mathematical analysis for the derivation of the isothermal recrystallization curve was developed for a two-dimensional case (in thin sheets where the diameter of the recrystallized grain is greater than the sheet thickness). The present paper is a continuation of the study of recrystallization of I per cent silicon ferrite begun in 1942.1 In this work the effect of the factors deformation, temperature, grain size, composition, and recovery is studied with respect to the rates of liucleation and grouth. At the same time it is shown how the cooperation of N and G affects the isothermal recrystallization curve. The study of these variables on N and G has a definite bearing on the mechanism of recrystallization and should lay a foundation for a rational theory on the subject. Procedure The procedure used in these experiments was essentially the same as that described previously but in certain details some changes were made in the interests of speed. With few exceptions, the procedure is the same for the study of all the variables. Where the procedure is different from standard manipulations attention is called to this fact.

Jan 1, 1945

T.B.King (Depaytment of Metallurgy, Massachusetts Institute of Technology)— A valuable contribution of the authors is in the factual information which they have been able to gather; this type of information is quite difficult to obtain. In many respects, however, it would have been better if they had not subsequently embarked on a discussion of the chemistry of the converter process. It seems inconceivable that the authors do not refer to the papers of Schuhmann and his associates14 which have set the thermodynamic foundation for the whole copper smelting operation. In addition, a very useful review on the physical chemistry of copper smelting by Ruddle 5 appeared as long ago as 1953. An examination of this literature would have convinced the authors that there is no cause to be surprised at a correlation between the magnetic content and the silica content of converter slags, though they rightly point out that one should distinguish between the total magnetite content of the slag and the amount of magnetite which may be considered to be in solution. It is not true that the lowest melting converter slag is that corresponding to the eutectic between ferrous oxide and silica. The simplest slag system which can be considered is a three-component system, since both ferric and ferrous iron are present. As Schuhmann, Powell, and Michal have shown, there are lower melting compositions than this eutectic in the ternary system. The most unfortunate impression given by this paper is that the driving force for chemical reaction is determined by the heat of reaction: of course the entropy change must be taken into account. It would have been more correct to list, in Table VI, values for free energies of formation. Nor can it be said that the data in Table VI represent the "best available data." They do not corregtond with any of the recent, acknowledged sources. F. E. Lathe and L. Hodnett(author's reply)— We are pleased that Dr. King finds the factual information in our uawer of some interest. Dr. King suggests that it would have been better if our analysis and discussion of the data had been omitted, largely because our list of references is so. incomplete. If he will carefully read our introduction, he will see that the questionnaire was sent out in the hope of obtaining data which would throw light on certain questions relating to the use of converter refractories. We did not attempt (nor would the AIME have published!) a complete review of the literature on copper converting, as Dr. King has apparently assumed, nor indeed a complete analysis of the data submitted, but tried only to find a sound basis for the choice of refractories, taking into consideration common variations in converter practice. We hope our paper indicates that, by raising the silica content of the converter slag and operating at a higher temperature, the normal circulating load of magnetite can be greatly reduced, and the whole reverberatory-converter operation improved to a major degree, with resultant important savings. Under such operating conditions, chrome-magnesite brick may be expected to stand up better than those of straight magnesite. Regardless of the choice as between these brick types, however, we find the cost of converter refractories to be so low in comparison with other converter costs as to justify operation under the more severe conditions suggested. Valuable as are the papers by Schuhmann and associates and the book by Ruddle, we make no apology for omitting reference to them, nor for using heats of reaction without mention of entropy changes or free energies of formation. Our primary object was to interest the practicing copper metallurgist, with whose language we may claim to be fairly familiar; we think it would have been unwise to include the highly theoretical phases of the subject which Dr. King suggests. The interest shown in our preliminary paper presented at the New York meeting in 1956, and the trends in practice whtat we have observed since that time, suggest that we did not wholly miss the target. In conclusion, we sincerely hope that Professors King and Schuhmann will independently review the data obtained in our questionnaire and submit a paper giving their own recommendations as to the choice of refractories and the particular converter operating conditions which will result in the lowest overall cost of copper smelting and converting.

Jan 1, 1960

By Albert McIntosh

One of the most interesting as well as important factors connected with the petroleum industry is the consumption of motor fuel. A few years ago we always spoke of "gasoline," but when natural gasoline and benzol became more important it seemed desirable to include all of these products in the petroleum statistics and so there was adopted the term "motor fuel," which embraces these three products in their entirety. Gasoline always included all stove and motor gasolines, high-grade naphthas, cleaning naphthas, solvents, varnishmakers' and painters' naphtha and gas-machine gasoline. "Motor fuel" includes all of these products also; therefore, technically the term "motor fuel" is incorrect, but as the total quantity of these non-motor naphthas is small their inclusion does not distort the results to any appreciable extent. When the Federal Oil Conservation Board appointed its first semiannual forecasting committee early in 1930 to project the demand for gasoline and crude oil into the year 1930, it was necessary for that committee to formulate a method of forecasting. It adopted the system in use by some of the oil companies at that time, of using automobiles and per-car consumption. Six months later the American Petroleum Institute also formed a committee for forecasting, which adopted the committee principle of asking each member to produce his own forecast of demand by any method he thought best and to give a full explanation to the committee. The result of the latter method was to get the benefit of as many different methods of forecasting demand as there were members. The writer does not recall any two members ever using exactly the same method. By studying the different forecasts and their methods, there evolved a composite opinion, which was presented to the industry as the committee's estimate. The same method has been followed by the American Petroleum Institute or Planning and Coordination Committee ever since.

Jan 1, 1935

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By H. Papazian, Robert A. Lad

SINCE it can be shown both theoretically&apos;&apos; : and experimentally that disordered Cu3Au has a greater internal energy than the ordered alloy, it might be expected that its chemical reactivity would be greater. Experiments were initiated&apos; to test this hypothesis. This note will describe some recent results obtained in the study of the rates of corrosion of ordered and disordered polycrystalline Cu3Au by aqueous FeCl., The work of Robertson&apos; has indicated that the attack by such solutions is intergran-ular and highly orientation dependent. It was of interest to see whether the order-disorder effect was great enough to overcome the variations from specimen to specimen which would arise from this type of attack. The polycrystalline alloy specimens (0.020 in. wire, 1¾ in. long) were preannealed in ½ atm H, at 700°C for 2 hr. The subsequent heat treatments to produce order and disorder were performed in M atm He. Disordered specimens were obtained by heating at 450°C for 2 hr and quenching in water. Ordered specimens were produced by heating for 2 hr at 450°, furnace cooling to 380°, and soaking at 380°C for 80 to 90 hr. Room temperature was reached by cooling to 150" at a rate never exceeding 7" per hr, and water quenching from 150°C. The specimens so produced exhibited electrical resistivities characteristic of the two states; of the order of 11.27x10 ohm-cm for the disordered, and 4.28x10 ohm-cm for the ordered specimens. The corrosion rates were studied at 30°C in ferric chloride solutions of several concentrations (?,¼, 1.5, and 1 molar). The specimens were attached to a stirrer during the tests. Tests were interrupted at intervals, and the specimen weight change was determined after washing and drying. Analysis of the solutions showed that the attack was limited to the copper. The higher corrosion rate for the disordered alloy, as illustrated in Fig. l, is typical of the results obtained. The effect of variation in ferric chloride concentrations is indicated in Table I for typical specimens. The variations in the ratio of reactivity for disordered and ordered specimens at the different concentrations are within experimental error, and the best value is estimated to be near 1.4. The experimental variation was due in part to the mode of attack, as mentioned, and in part to the fact that films were formed on the specimens under some conditions. Electron diffraction patterns of the films were very complex and indicated the presence of metallic iron, as did chemical analysis. In an attempt to eliminate the difficulties arising from the mechanism of attack, single crystal specimens were used. A greater reaction rate was again measured for the disordered specimens, but the reproduci-bility was no better than that for the polycrystalline metal. This would indicate that film formation was primarily responsible. It was concluded that the reaction with aqueous ferric chloride served to demonstrate that the reactivity of disordered Cu3Au is greater than that of the ordered alloy. However, the difficulties with film formation did not permit determinations of a precision great enough to warrant extension of the study to partially ordered alloy systems.

Jan 1, 1957