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By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By S. Grinsfelder

Although wildcatting was hampered by the general overproduction and low price of crude, several developments, worthy of note in the history of the petroleum industry in the Rocky Mountain region, were made in 1927. This district records production from six new fields, two of these having been heretofore productive of gas. Deeper pay horizons were found in two other oil fields. In order to facilitate transportation from fields, six new oil pipe lines were completed or in the course of construction at the end of the year, and one line is proposed for 1928. Four gas lines were completed, one was under construction, and one was proposed for 1928. The total production in 1927 in the Rocky Mountain district was 29,591,379 bbl.,' a decrease of 7,771,991 bbl., or 21 per cent., fro111 the previous year. This was occasioned by natural decline and the general curtailment of production and drilling. A review of the development by states follows. Colorado Production from horizons in the Morrison and Sundance at Craig and at Ilrs Dome, and the bringing in of the deepest producing well in the Rocky Mountain district on North McCalluin anticline (Waltlrn) in Jackson County are the outstanding developments for the year in Colorado. In March the Midwest Refining Co.'s Parkinson 21 SD, SW SE, Sec. 22 T p. 4 N R 92 W, Iles Domr, Moffat County Colorado, found gas in sands in the Morrison estimated at 15,000,000 cu. ft., and at 3242 ft. an oil sand was encountered in the Sundance. Initial production from this horizon was 2575 bbl. in this well. This structure previously was only productive of water in the sands of the Dakota group but has been producing shale oil from horizons in the Benton. The second well completed by the Midwest Refining Co., No. 18 SD in Sec. 23 was also productive of gas in the Morrison and made an initial of 300 bbl. from sands in the Sundance. By the end of the year three other wells wrrc nearing the completion stage but none of them indicate that they will be as big producers as the discovery. To date the productive area has

Jan 1, 1928

By H. F. Yancey, M. R. Geer, Franklin T. Davis

Coke with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning, An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. Previous Work Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,' and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.'

Jan 1, 1944

By M. R. Geer, Franklin T. Davis, H. F. Yancey

Coke with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning, An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. Previous Work Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,' and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.'

Jan 1, 1944

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals'-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

By E. F. Miller

The subject " Safe Timbering of Working Places in Mobile Loading" is one that requires an analytical study of the strata both above and below the coal seam as well as the characteristics of the coal seam itself. The projection or mining plan must be based on economic roof control in which the application of timber can be minimized without incurring cost increases in other phases of production. The several types of loading machines in common use today are not adaptable to the same projections or timbering systems. Consequently the type of equipment to be used must also be considered. For these reasons the writer does not believe that the problems of timbering in working places can be discussed without simultaneously considering economic production as well as the safety of men and the conservation of equipment. Prior to the introduction of loading machines as a substitute for the pick and shovel system of loading coal, the care and maintenance of the individual working places were generally the responsibility of the coal loaders who worked in them. Up to that time very few coal companies had developed and applied fixed and definite standards for timbering the working places in the mines they operated. It is common knowledge that mechanical loading of coal has had several false starts in the last twenty-five years and it is only in the last decade that it has developed to the stage at which we now find it. During this twenty-five year period the management of the more responsible companies have come to realize the tremendous importance of roof control in coal mining. From a safety viewpoint, the lack of roof control has been and still is responsible for more than a third of the industry's annual fatality experience. In recent years workmen's compensation and insurance rates have steadily increased while the profit margin has decreased almost to the point of elimination. From an economic operating viewpoint, the failure to properly control roof is quite often the most costly single phase of coal mining. Since the manufacturers of loading machine equipment have so improved their machines that normal care and maintenance can reduce to a minimum the time lost because of mechanical failure the production delays from other causes have assumed a far greater importance. Roof control in the broad sense and in the light of concentrated mining plans or projections that are adapted to mobile loading should be regarded as one of the major problems in the inseparable phases of production and safety of the workman and equipment at the working face. The subject of this paper cannot be treated properly unless what is said here is based upon the broad and fundamental problem of genera' roof control. The suc-cessful solution of a problem arising in any industry must have its origin in a complete analysis of the known facts or factors that pertain to it. The several illustrations

Jan 1, 1949

By Walter Herd

FoR the past eight years No. 2 mine of the Cumberland Railway & Coal CO., Springhill, Nova Scotia—a subsidiary of the Dominion Coal Co., Ltd.—has had an unenviable reputation for bumps. As the workings extended in certain directions under a greater cover, these bumps increased in severity and it became apparent that some change in the system of extraction was necessary if the mine was to continue to operate. In September, 1924, following several fatalities resulting from bumps, the Mines Department of Nova Scotia requested from the U. S. Bureau of Mines the services of George S. Rice, Chief Mining Engineer of the Bureau, to report on the conditions then prevalent in No. 2 mine, Springhill. This request was promptly and courteously granted. Mr. Rice made a full investigation and a comprehensive and helpful report, which is embodied in the 1924 Annual Report of the Department of Public Works and Mines, Nova Scotia. Prior to 1925, the room and pillar method was employed and in January of that year (there being a cessation of work from March to August due to labor troubles) longwall retreating on the west side, on a limited scale, and in a small section on the east side of the mine was started. The major portion of the east side was not operated on this system till August, 1926, as there was developed a considerable area ready for pillar extraction between an arbitrary boundary and a point up to which bumps of any consequence had not been experienced. In the interval development work for longwall retreating below the 5900-ft. level was vigorously pushed. This longwall retreating system was suggested by Mr. Rice as a possible remedy and was heartily endorsed by the company officials. This paper describes the conditions and happenings subsequent to Mr. Rice's report and more especially the results with the longwall retreating system of mining under the peculiar circumstances pertaining to mining No. 2 Seam, Springhill, at depth, and records the conclusions which experience with several severe bumps under this mode of extraction would suggest. Except where necessary to make the paper intelligible as an entity any duplication of Mr. Rice's report will be avoided.

Jan 1, 1930

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter's tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.' The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"', an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967

Editors of engineering periodicals usually read the advertising pages. It may be hard' for some men, let alone engineers, to understand what value there is in reading "dry advertisements." Yet it is a fact that valuable suggestions have been obtained from these so-called "dry advertisements" which have been the means of securing greater efficiency in the performance of some undertaking and consequent saving of time and money. It seems to be an editorial practice to look to the advertisements for suggestions for the reading pages. It is a fact that some of the most appreciated descriptive articles were suggested by advertisements. Every undertaking is limited to that point where tools and machinery for its successful performance and completion may be purchased or manufactured. No work can he planned without having in mind such limitation, and the technical journals may be relied upon to furnish descriptions, both editorially and through the advertising pages, of methods and plant used in successfully performing various tasks. This being so, why should not the reader or subscriber to a magazine or periodical avail himself of such a fountain of knowledge? Such perusal proves of value to the up-to-date engineer or man occupying a -position. of responsibility where initiative is essential. Authorities agree that advertisements are on a par with technical articles for their educational value, and this Is as it should be. Also, most subscribers to a publication realize that a, successful advertising medium means a continuance of advertising patronage, which in turn enables the publisher to turn out a better and larger volume of reading matter.

Jan 6, 1915

By K. L. Temple, A. R. Colmer

ACID coal mine drainage presents a peculiarly difficult problem for two principal reasons. First is the fact that the amount of acid water discharged from active and abandoned mines constantly increases as coal fields are developed and thereby creates a steadily worsening nuisance of rapidly growing importance to the general public as well as to the coal industry. Second is the even more significant fact that there is no method yet known that will appreciably alleviate the acid water problem except at totally prohibitive cost to the coal operators. The problem is thus seen to be an urgent one. With a growing need for good quality water and a growing public demand for abatemknt of stream pollution, a large portion of the soft coal industry finds itself in the position of year by year dumping more and more acid into the streams and waterways and having no way in sight of improving the situation or even of keeping it from getting worse. While some studies have been made, it is only in the last few years that the problem has been seriously considered, chiefly by the group of workers under the direction of S. A. Braley at Mellon Institute and by the Bituminous Coal Research, Inc. fellowship at West Virginia University. Hinkle and Koehlerl reported the results of the earlier West Virginia work. This work pointed to certain biological aspects which had not been noticed previously. These may be summarized as two separate findings. One was that sulphur oxidizing bacteria were present in acid mine water and that their possible role in contributing to the acidity should be investigated. The other was

Jan 1, 1952

By C. D. Woodward

THE subject of electric signals for the despatching off mining cages through shafts has received cousiderable attention recently from various mining companies. The Anaconda Copper Mining Co. has found it necessary to develop a system that is reliable, safe and simple in operation, and easy to repair. The movement of all mine cages or skips is under the direction of a station tender, who rides on the cages when men or supplies are being lowered or raised. When ore is hoisted, he is stationed at a skip pocket for loading and despatching the skips. For the station tender's use, two signal systems are installed in each hoisting compartment, and he is the only employee authorized to use them. One system is known as the "AC" or Station bells, as it is operated from the 110-volt, 60-cycle, power service; the other system, called the "DC" or shafts bells, takes its energy from closed-circuit primary batteries. As a supplement to the two main signals, a buzzer system is installed. The general arrangement is similar to "the main signal, except that there is a mine buzzer at each station. When a signal switch connected into the buzzer system is pulled down, all buzzers are operated, thus notifying the station tender that he is wanted at some particular level. Placed on the station posts, and within easy reach of the men on the cages, are the signal pull switches for the main signals. The station, or "AC," pull switches are furnished with a short rope as shown in Fig. 1, while the shaft, or "DC," pull switches are equipped with ropes that extend down the shaft past the next station. To avoid all confusion in the use of the three signal systems, a standard arrangement has been adopted in all mines for the location of the pull switches. Fig. 2 illustrates the position of the pull switch at the various mine stations for the main signal systems, but it does not show the buzzer pull switch; this is fixed to the roof timbers about 25 ft. back from the shaft. If the skip pockets are a considerable distance below the station, a pull switch for each main shaft compartment is connected to the "AC" system and placed at this point. However, if the distance is short, a light cord is attached to the station pull switches and dropped down to the skip pocket.

Jan 2, 1922

By John T. Norton

In recent years, the damping capacity of metals has come to be recognized as an important index of certain types of structural change. In a number of instances, this property has proved to be particularly sensitive, but insufficient work has been done to permit a general interpretation. There is considerable question at the present time as to just what factors are responsible for the internal dissipation of energy when a metal is carried through a cycle of stress, and these factors must be ascertained if the value of the damping method as a metallurgical tool is to be determined. Since internal stresses are among the chief causes of dissipation of internal energy, or damping capacity, it was thought that a study of the changes in damping during the recovery and recrystalliza-tion of a cold-worked metal might throw some light upon the subject, particularly if the damping changes were correlated with other properties that are better understood. Probably more work has been done on the recrystallization phenomena of alpha brass than on any other metal, so this was chosen as the material for the present investigation. Damping measurements on brass have been made by Förster and Köster.1 They showed that the annealing of a brass that had been cold-drawn to 50 per cent reduction produced a rapid fall in the damping, a flat minimum occurring at approximately the temperature of recrystallization. The damping remained at a low value until grain growth was well under way and then it increased rapidly with increasing grain size. Köster and Rosenthal2 continued the work in greater detail. They pointed out that the damping decrease does not correspond to the hardness drop but occurs at a lower temperature, suggesting that the relief or redistribution of internal stresses has a large effect while the actual recrystallization effect is small. They also show the increase in damping at the higher annealing temperatures. Their curves are reproduced in Fig. 1.

Jan 1, 1940

By John T. Norton

In recent years, the damping capacity of metals has come to be recognized as an important index of certain types of structural change. In a number of instances, this property has proved to be particularly sensitive, but insufficient work has been done to permit a general interpretation. There is considerable question at the present time as to just what factors are responsible for the internal dissipation of energy when a metal is carried through a cycle of stress, and these factors must be ascertained if the value of the damping method as a metallurgical tool is to be determined. Since internal stresses are among the chief causes of dissipation of internal energy, or damping capacity, it was thought that a study of the changes in damping during the recovery and recrystalliza-tion of a cold-worked metal might throw some light upon the subject, particularly if the damping changes were correlated with other properties that are better understood. Probably more work has been done on the recrystallization phenomena of alpha brass than on any other metal, so this was chosen as the material for the present investigation. Damping measurements on brass have been made by Förster and Köster.1 They showed that the annealing of a brass that had been cold-drawn to 50 per cent reduction produced a rapid fall in the damping, a flat minimum occurring at approximately the temperature of recrystallization. The damping remained at a low value until grain growth was well under way and then it increased rapidly with increasing grain size. Köster and Rosenthal2 continued the work in greater detail. They pointed out that the damping decrease does not correspond to the hardness drop but occurs at a lower temperature, suggesting that the relief or redistribution of internal stresses has a large effect while the actual recrystallization effect is small. They also show the increase in damping at the higher annealing temperatures. Their curves are reproduced in Fig. 1.

Jan 1, 1940

By C.H. Davis, W.H. Bassett

The ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst. Impurities in raw material are often a source of annoyance, especially when their detection involves delay and costly analytical work. Whethcr low conductivity in copper is due to arsenic, nickel, or something else may be cluickly found out. Residual traces of boron, magnesium, manganese, silicon, vanadium, and other deoxidizing agents are easily identified where wet analysis may fail to reveal their presence, even after days of effort. Complex alloys of any kind are dissociated by the spectro-

Jan 1, 1923

By W. H. Bassett, C. H. Davis

The ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst. Impurities in raw material are often a source of annoyance, especially when their detection involves delay and costly analytical work. Whethcr low conductivity in copper is due to arsenic, nickel, or something else may be cluickly found out. Residual traces of boron, magnesium, manganese, silicon, vanadium, and other deoxidizing agents are easily identified where wet analysis may fail to reveal their presence, even after days of effort. Complex alloys of any kind are dissociated by the spectro-

Jan 1, 1923

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By T. T. Read

A short time ago, one of the large steel companies courteously furnished the author with detailed records of the operations of a considerable number of iron blast furnaces over a period of two months. These will be made the basis of a subsequent study, but in beginning this study one of the first points requiring consideration was the probable error of the records, for what otherwise might be regarded as significant differences of performance under different conditions were perhaps really due to errors of observation, or failure to observe and record variations. If it is assumed, in blast-furnace records and calculations, that known quantities or factors are constant, .when as a matter of fact they are variable, the effects of these variations may erroneously be ascribed to some other cause. This is quite clearly expressed in the following quotation from E. Buckingham:l Theory always operates on an ideally simplified picture of reality because real phenomena are unmanageably complicated. The results obtained are not exactly true for any real phenomenon, though they may be for an ideal one; and the approxi-mation with which a theoretical equation, however obtained, represents the actual facts, always depends on the approximation in essentials between the ideal picture and its real prototype. The purpose of dimensional reasoning is to find out how some quantity which is involved in the phenomenon under consideration is related to certain others; or to find the relation connecting two or more quantities which vary, or may vary, simultaneously during the course of the phenomenon. Since we know that we must have a complete equation to start with, we begin by thinking the matter over, to see whether the quantities we have in mind are the only ones involved. Usually it is evident that they are not; so we next make a list of all the quantities we can think of which might under any circumstances be important. Upon considering this list, which is often a long one, it is usually evident that under the actual circumstances a number of these quantities may safely be ignored; so we cross them off the list and thus pass from our most general conception of the phenomenon to an ideal simpler one, in which these quantities are not involved at all.

Jan 1, 1926

By AIME AIME

METALLIC corrosion, which results from the chemical affinity of different metals for non- metallic elements, should be considered from both the kinetic and static viewpoints. From the stand- point of statics the metals may be arranged in the order of their affinity for oxygen, chlorine or any other acid- forming element. They may also be arranged in the order of the magnitude of the heat of combination of their corresponding compounds. It is misleading to talk about some metals as "noble," because these relations are all relative; and the order varies for oxygen, chlorine or whatever the element may be. A third way to arrange the metals is by their solution pressures. These three methods indicate that one metal is better under one set of conditions, but not so good under other conditions. Considering the problem from the standpoint of kinetics, the thing which saves most metals is what may be called the sluggishness of reactions. Using organic substances as an example, we know they will all oxidize, but fortunately they do so rather slowly. An increase in temperature always means an increase in the reaction rate, and preventing corrosion at high temperatures is a greater problem than at low temperatures. A second consideration is to avoid all sub- stances which might provoke catalytic action, and as it is generally impossible to foresee what substances might do this, the thing is to avoid all substances other than the main constituents of the alloys. A third consideration is to avoid local electrolytic action, which again indicates the advisability of avoiding the contact of differing substances.

Jan 1, 1926