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By William L. Fink, Kent R. Van Horn

Zinc is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd1 first established the existence of a solid solution region at the aluminum end of the diagram (-v phase) by specific volume and microscopic determinations. Bauer and Voge12 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined. The solubility was placed between 15 to 20 per cent at 60" C., 20 to 22 per cent at 140" C. and 36 to 38 per cent at 270" C. Sander and Meissner decidedly modified the limits of the -y phase field of Hanson and Gayler's diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,s utilizing dynamic hard-ness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler's at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400" to 500" C., that the solubility of zinc in aluminum at room temperature is less than 5 * Metallurgical Division, Aluminum Research Laboratories. 1 E. S. Shepherd: Aluminum-Zinc Alloys, Jnl, phys. Chem. (1905) 9, 504. 2 0. Bauer and 0. Vogel: Aluminum-Zinc Alloys, Int. Jn1. Melallog. (1916) 8, 101. 3 D. Hanson and M. V. L. Gayler: A Further Study of the Alloys of Aluminum and Zinc. Jnl. Inst. Met. (1922) 27, 267. 4 W. Sander and K. L. Meissner: ZII~ Kenntnis der Konstitution der Aluminium-Zinklegierungen. Ztsch. f. Metallkunde (1922) 14, 385. 4 T. Tanabe: Studies in the Aluminum-Zinc System, Jnl. Inst. Met. (1924) 32, 415 6 H. Nishimura: On the Age-Hardening of Aluminum-Rich Al-Zn Alloys. Mem. Kyoto Imp. Univ. (1924) 3, 133.

Jan 1, 1932

By Cyril Stanley Smith, W. Earl Lindlief

A study of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published' giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. Preparation of Allots The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 per cent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2 in. dia. cast-ing, the turnings being separated into three parts according to the position

Jan 1, 1932

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C. C. Wright, T. S. Spicer

A characteristic property of bituminous coal is that upon being heated the coal becomes plastic, evolves volatile gases, and finally solidifies into coke. This fundamental characteristic is of utmost importance and is utilized in the production of the high-temperature coke upon which the steel industry is so dependent; but from the standpoint of operation in the domestic underfeed stoker this coking tendency seriously interferes with efficient combustion. When the coke formed has too strong a structure, certain difficulties result, such as low rate of burning, slow response to heat demand, and, in extreme cases, extinction of fire. The plastic mass prevents uniform distribution of air through the fuel bed and, with strongly coking coals, large dense pieces of coke are produced which have much less reacting surface than was possessed by the original coal. In both ignition and combustion of solid fuels, the extent of the reacting surface is an accelerating factor. Poor combustion permits a surplus of fuel to accumulate in the furnace because the rate of feed and the rate of combustion are not in equilibrium, and this produces an unbalanced condition detrimental to continued automatic service. In order to bum strongly coking coals satisfactorily in a conventional stoker during the three requisite types of operation—continuous, intermittent and hold-fire, frequent attention is necessary. Domestic stokers are defined by the industry as residential stoker heaters that burn 60 lb. of coal or less per hour. With a few exceptions, these units employ the underfeed principle of combustion in which both air and coal move in the same direction up and through the fuel bed. Domestic combustion equipment has difficulty in meeting the problems presented by the several variations in ash and volatile matter, in ash-clinkering tendencies, in coking properties, and in the particle size of bituminous coals. The work of Bituminous Coal Research Inc. at Battelle Memorial Institute has shown that, of these, coking characteristics and the clinkering tendencies have the greatest effect upon the operation of the conventional clinkering type of stoker. Typical coke formations in a clinkering type of underfeed domestic stoker are illustratcd in Fig. I, which shows (A) the ideal fuel bed obtained with a noncoking or free-burning coal; (B) the type of fuel bed formed with a coal that produces a weak coke; and (C) the type of fuel bed obtained with a strongly coking coal. C is characteristic of the fuel bed developed when the average Pennsylvania bituminous coal is burned in an underfeed stoker of conventional type. It is apparent from these pictures that the formation of coke trees will seriously interfere with the efficient automatic combustion of Pennsylvania bituminous coals.

Jan 1, 1942

By T. S. Spicer, C. C. Wright

A characteristic property of bituminous coal is that upon being heated the coal becomes plastic, evolves volatile gases, and finally solidifies into coke. This fundamental characteristic is of utmost importance and is utilized in the production of the high-temperature coke upon which the steel industry is so dependent; but from the standpoint of operation in the domestic underfeed stoker this coking tendency seriously interferes with efficient combustion. When the coke formed has too strong a structure, certain difficulties result, such as low rate of burning, slow response to heat demand, and, in extreme cases, extinction of fire. The plastic mass prevents uniform distribution of air through the fuel bed and, with strongly coking coals, large dense pieces of coke are produced which have much less reacting surface than was possessed by the original coal. In both ignition and combustion of solid fuels, the extent of the reacting surface is an accelerating factor. Poor combustion permits a surplus of fuel to accumulate in the furnace because the rate of feed and the rate of combustion are not in equilibrium, and this produces an unbalanced condition detrimental to continued automatic service. In order to bum strongly coking coals satisfactorily in a conventional stoker during the three requisite types of operation—continuous, intermittent and hold-fire, frequent attention is necessary. Domestic stokers are defined by the industry as residential stoker heaters that burn 60 lb. of coal or less per hour. With a few exceptions, these units employ the underfeed principle of combustion in which both air and coal move in the same direction up and through the fuel bed. Domestic combustion equipment has difficulty in meeting the problems presented by the several variations in ash and volatile matter, in ash-clinkering tendencies, in coking properties, and in the particle size of bituminous coals. The work of Bituminous Coal Research Inc. at Battelle Memorial Institute has shown that, of these, coking characteristics and the clinkering tendencies have the greatest effect upon the operation of the conventional clinkering type of stoker. Typical coke formations in a clinkering type of underfeed domestic stoker are illustratcd in Fig. I, which shows (A) the ideal fuel bed obtained with a noncoking or free-burning coal; (B) the type of fuel bed formed with a coal that produces a weak coke; and (C) the type of fuel bed obtained with a strongly coking coal. C is characteristic of the fuel bed developed when the average Pennsylvania bituminous coal is burned in an underfeed stoker of conventional type. It is apparent from these pictures that the formation of coke trees will seriously interfere with the efficient automatic combustion of Pennsylvania bituminous coals.

Jan 1, 1942

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By William Carton, Cyril U. Cooledge

BecauSe the rich La Colorada orebody of the Cananea Consolidated Copper Co. does not outcrop at surface, after its discovery (by churn drill) and before mining was begun, a large amount of development work was done to learn the shape and extent of the ore and to provide for economic and effective mining. As these openings progressed, the actual shape of the orebody became known and with this knowledge came the realization that mining this rich and unusual deposit without loss of ore or danger to workmen presented several difficult problems. This paper will describe one of these problems; namely, the handling of an inverted cone-shaped core of barren rock, on the periphery of and below which the ore occurred. It mas clear that as the ore was mined out from around and under this inverted cone of rock, weighing about 3,000,000 tons, it would hang over the workings, held suspended only by its own tensile strength and threatening to crash into the stapes below with disastrous results to men and mine. The method of mining developed during the years 1928,1929 and 1930 anticipated and provided for the eventual collapse of this core of rock. In November 1936 the core settled down gradually on the edges of the stopes, descending a total of about 50 ft. vertically. The men in the stopes had ample warning and no lives were endangered. There were no air blasts in the mine. The core broke loose from its top support at the 500-ft. level along old fracture planes and evidently is crushed to the ninth level. Movement was of short duration; the following shift went to work in the stopes as usual. No ore was lost. Geological Structure The shape of the orebody is illustrated in Fig. 1. The geology of the Colorada orebody has been described by V. D. Perry1 and by W. G.

Jan 1, 1940

By Cyril U. Cooledge, William Carton

BecauSe the rich La Colorada orebody of the Cananea Consolidated Copper Co. does not outcrop at surface, after its discovery (by churn drill) and before mining was begun, a large amount of development work was done to learn the shape and extent of the ore and to provide for economic and effective mining. As these openings progressed, the actual shape of the orebody became known and with this knowledge came the realization that mining this rich and unusual deposit without loss of ore or danger to workmen presented several difficult problems. This paper will describe one of these problems; namely, the handling of an inverted cone-shaped core of barren rock, on the periphery of and below which the ore occurred. It mas clear that as the ore was mined out from around and under this inverted cone of rock, weighing about 3,000,000 tons, it would hang over the workings, held suspended only by its own tensile strength and threatening to crash into the stapes below with disastrous results to men and mine. The method of mining developed during the years 1928,1929 and 1930 anticipated and provided for the eventual collapse of this core of rock. In November 1936 the core settled down gradually on the edges of the stopes, descending a total of about 50 ft. vertically. The men in the stopes had ample warning and no lives were endangered. There were no air blasts in the mine. The core broke loose from its top support at the 500-ft. level along old fracture planes and evidently is crushed to the ninth level. Movement was of short duration; the following shift went to work in the stopes as usual. No ore was lost. Geological Structure The shape of the orebody is illustrated in Fig. 1. The geology of the Colorada orebody has been described by V. D. Perry1 and by W. G.

Jan 1, 1940

By C. A. Pierce

Studies of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its commercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft, in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft. of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding formations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresse."1

Jan 1, 1942

By C. A. Pierce

Studies of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its commercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft, in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft. of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding formations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresse."1

Jan 1, 1942

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938

By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938