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By A. E. Wraith, J. Protheroe Jones, P. J. Mackey

The world’s first copper electrorefinery started production in 1869 at Burry Port in South Wales. Built within the Pembrey Copper Works which had commenced smelting operations in 1849, the new refinery was based on principles described in the British patents issued to J.B. Elkington in 1865 and 1869. Refining principles and practices pioneered there were key to the foundation of modern electro-refining practice in what is now a dominant international industry producing over 16 Mt of electrical grade copper annually. This paper explores the background to this pioneering application of the new, early 19th century, science of “electro-metallurgy” and examines its links to the contemporary decorative electro-plating industry and to the shortcomings of 19th century fire refining. The beginnings and early years of the Pembrey electrorefinery are briefly discussed in relation to the quality, applications and pyrometallurgy of copper at the time. More than a decade would elapse before the birth of the electrical age: the Pembrey refinery may be seen as one of its vital precursors. Note: This paper was originally published as part of the Copper 2013 proceedings (A.E. Wraith, P.J. Mackey and J. (formerly R.) Protheroe Jones, “Origins of Electrorefining: Birth of the Technology and the World’s First Commercial Electro-Refinery”, paper in Electrorefining, Vol. V, Book 2, (Eds. R. Abel and C. Delgado), Cu 2013 International Conference, pp. 19-33, IIMCh, Santiago, Chile, 2013). It is reproduced here together with a new Appendix and supporting references that lists the year of commencement of the first electrolytic copper refinery by country, 1869 to 1956. It all, the year of the first electrolytic copper refinery established for 15 countries is included. These 15 countries now produce more that 70% of world refined copper (for 2018). INTRODUCTION In the 1840s, the new science of ‘electro-metallurgy’, a term coined by Smee in 1841 (Smee, 1841), was being adapted to the decorative electro-deposition of silver in a thin, bright adherent coating that was evidently equal in appearance to traditional silverware (Williams, 1976). Chief among innovative manufacturers of decorative objects who took up the new art of silver electro-plating was the acclaimed firm of G.R. Elkington and Co. of Birmingham, England. The company, which vigorously developed all aspects of electro-metallurgy for the decorative trade, entered the field of ‘electrotyping’, a technique in which the surface features of a mould are copied on an electro-deposited copper layer which, when stripped off, can be used to reproduce an imprint of the mould. In essence, it is a form of casting by electrodeposition, invented in 1837 independently by Jacobi in Russia (Pavlova, 1968) and Spencer in England (Wyatt, 1851).

Jan 1, 2019

On the preceding pages, operations of the four major producers of nickel today have been described. There are, however, other operations in the world that, while not as large, are still of importance to the over-all picture of the industry. Among these are the Finnish producer, Outokumpu Oy, a state-controlled company that operates the Kotlahti mine 200 miles northeast of Helsinki. The ore from this operation, which began production in 1959, is pentlandite, chalcopyrite and pyrrhotite, occurring as disseminations in the host rock and in breccias. The flowsheet of the 1500-tpd mill at Kotlahti follows standard practices of crushing, grinding, and flotation to produce a pentlandite-pyrrhotite concentrate and a copper concentrate, both of which are shipped to the smelter at Harjavalta.

Jan 10, 1968

By William H. Bassett

RECENTLY it has become the custom of retiring presidents to talk of the relations of the Institute to its membership and its constituency- and it seems a good precedent to follow. Past-president Smith reviewed our relations to materials and to society in general. Mr. Bradley spoke of the value and use of our publications and of our educational duties. My message will be in regard to the coordination of our various groups of member interests and of service to industry. This Institute has, within its organization, four divisions and fourteen technical committees--each interested in a separate put very definite subject, and each covering a phase of mining engineering interest. These vary from geology and the geophysical methods of prospecting, to the physics of the structure of metals, truly "from the mine to the consumer"-from the preparation for mining to the final use of that which has been mined.

Jan 1, 1931

By R. E. Murray

"It is a gloomy moment in the history of our country. Not in the lifetime of most men has there been so much grave and deep apprehension; never has the future seemed so incalculable as at this time. The domestic economic situation is in chaos. Our dollar is weak throughout the world. Prices are so high as to be utterly impossible. The political cauldron seethes and bubbles with uncertainty. Russia hangs, as usual, like a cloud, dark and silent, upon the horizon. It is a solemn moment. Of our troubles, no man can see the end." By now you, no doubt, are asking, 'Where did Murray get this bit of philosophy?' Well, I obtained it from an editorial entitled. "The Worst of Times", which was published in the Harper's Magazine in 1847. That's right, 1847! The parallelism between the situation in our country at this time and in 1847 is un- canny. But wait, there is one major exception the size of government. To my knowledge, the citizens of 1847 were not stifled by the extreme governmental excesses that we are experiencing today.

Jan 1, 1980

By L. BENEDICT

COMMENTING on the report of the latest Royal Commission for India, the September, 1926, issue of the National City Bank's monthly letter states, among other things, that "The decision of the Royal Commission is against the proposal for a gold coinage, but in favor of placing the silver coins and paper currency now redeemable in silver on a gold basis." Also, it quotes the following from the Royal Commission's report: The essence of the proposal * * * * * is that the ordinary medium of circulation in India should remain as at present the currency note and the silver rupee, and that the stability of the currency in terms of gold should be secured by making the currency directly convertible into gold for all purposes, but the gold should not circulate as money. It must not circulate at first, and it need not circulate ever. In this connection it may be stated that during the last one hundred and fifty years or so unsuccessful attempts have been made by the governments of different nations of the world to devise a plan or plans by which gold and silver could be used concurrently for money purposes and, particularly, as standard money; such, for example, as bimetallism, which, of course, is impracticable. But, since none of such plans has been adopted generally it is logical to conclude that their proponents did not shape them so as to conform to the basic principle of standard money, or else political issues were deemed to be dominant, or, perhaps, it was partly due to each.

Jan 1, 1926

By C. W. Handy

ONE LAW cannot he evaded, the economic law of supply and demand. Silver, like any other commodity, is subject to this law; and its price in the long run is determined by existing conditions. I say "in the lone run because at times silver has appeared to mope contra to basic coalitions. Such movements, however, are, occasioned by the market's attempt to anticipate changes in these governing conditions. If the expected changes materialize then the new market level is justified, but if they do not then the market will revert to its previous status, A striking example of such a move occurred in November when the price advanced over 70, in ten days and then in the next two weeks lost more than it had gained. The reasons for this advance were that the speculative element interpreted certain events as favorable to silver namely, England suspension of the gold standard, higher shat prices, and the Chinese-Japanese crisis. When these expectations proved unjustified the inevitably, elapse followed became the governing conditions had not channel.

Jan 1, 1932

By Joey Hoang, Robert Johansson, Tapani Keronen, Mikael Jåfs, Jani Jansson, Mikko Korpi

At the Copper 2016 conference in Kobe, Japan, Outotec introduced a vision for the year 2020, wherein smelting would make use of four digital cornerstones: intelligent instruments, advanced process control, improved information management and transparency of and access to data. Since then, this vision coined the phrase “Fully Automated Smelter” with the mission promising a concept where no manual actions from human operators would be needed during normal smelter operations. Replacing repetitive physical work, collection and analysis of everyday production data has a great potential for further automation and will provide productive ways to improve efficiency and safety of smelters in the future. Therefore, a lot of emphasis has been put into developing solutions to automate these tasks and to move people out of harm’s way. A lot of new equipment, systems and optimization tools are under development. In addition, a lot of effort is going into developing dynamic process models and advanced control systems to interface with the plant automation systems. The goal is to integrate all these concepts to meet Outotec’s Fully Automated Smelter vision. This paper will cover these latest achievements toward this vision and introduce the near-future of digital smelting. INTRODUCTION As is well known already, the humankind is currently experiencing a change, extent of which is broadly studied by the governmental, educational and industrial institutions and parties. The wellbeing and quality of life have traditionally been improved alongside the developments in industrial production, which is now about to enter its fourth revolution. Therefore, the current change is often described as fourth industrial revolution, or industry 4.0 (or industrie 4.0, as named by Acatech, 2013) and can be considered anything from small incremental development to a ground-breaking global reset that will affect everyone’s lives. Many seem to agree, that the scale of change will indeed be big, even significantly bigger than the three industrial revolutions before it (Pellini, Weyrauch, Malho & Carden, 2019; Geissbauer, Vedso & Schrauf, 2016; Jansson, Bjorklund, Lahtinen, Heinonen, Jafs & Fagerlund, 2016).

Jan 1, 2019

The use of coal as a fuel causes air, pollution in; a number of different forms, and in nearly all stages of its, handling, preparation, storage, use and-disposal of its residue. First let us consider the handling of coal. As shipped, particularly to large utilities, it is run-of-mine bituminous made up of large chunks as well as pulverized particles. Because it 'is in an open car or barge, it is subject to the action o winds and the small particles may be blown around adding to the-particulate load in the atmosphere. Mien un¬loaded from the barge or car, there is again an opportunity for the wind to blow the fine particles around. All of us I am sure have seen a barge at the dock of a utility plant being unloaded by a clamshell bucket. This, after grabbing its load from the barge, lifts it some 60 or 70 feet and, then drops it on a conveyor, which carries the coal to a storage area.

Jan 1, 1964

As the chief field of the gold dredging industry in Otago is the district traversed by the Molyneux River (called above Cromwell the Clutha) and its tributaries, a brief reference to the geology of that region and the origin of its alluvial gold will not be out of place. The prevailing rocks are metamorphic schists, chiefly mica and quartz schists, pr.obably of Silurian age. Though these rocks do not contain many payable quartz reefs, gold appears to be distributed in small quantities all through them,chiefly associated with the quartz lamime and lenses. The river drift, however, contains numerous pebbles of quartzite, quartzoze conglomerate, and fme-grained slate. Seeing that these rocks are hardly known to occur in situ within the watershedof the Molyneux River, though Devonian and carboniferous rocks of similar character occur to the north-east and south-west, it seems probable that the schists were at one time overlaid by carboniferous and Devonian rocks, and that these have been removed by denuding agencies. Be this as it may, it is certain that the schists themselves have been greatly eroded by the action both of water and of ice, and that the resulting drifts have themselves, in many cases, been sorted and re-assorted by the same agents.Consequently the drifts are very varied in character and often developed on a grand scale. In geological age they vary from Early Tertiary (though some may be older) to Recent.

Jan 1, 1903

By G. P. Halliwell, C. R. Austin

The investigation described in this paper deals with the development of high-temperature alloys of the Konel series over a considerable period of time at t,he Research Laboratories of the Westinghouse Electric and Manufacturing Co. The word ''Konel" has been coined to designate a class of alloys which are essentially nickel-cobalt-iron with other elements added, usually in small quantities. Most of these alloys contain titanium, usually about 2.5 per cent. The main consideration related to strength at high temperatures but the thermionic characteristics of the alloys was also of considerable importance. It is, however, with the mechanical properties at elevated temperatures that we are herein concerned. Much attention has also been devoted to their age-hardening characteristics. There is little need to stress the utilitarian aspect of this subject, as it has been discussed frequently. Alloys exhibiting superior properties at normal or elevated temperatures rapidly find many suitable applications. There may be some question, however, as to what constitutes a "superior alloy," or an alloy that may have good service possibilities at high temperatures. The problem is complex and various means have been employed to predict the useful life that may be expected of a material. In recent years the "creep limitJ' has been used as the best means of evaluation. Such tests necessarily are prolonged and hence collection of data is very slow. In a general survey of many alloys therefore the creep test is not desirable and recourse must be had to much shorter time tests in order more rapidly to select alloys which appear to show promise. For this reason the present survey has been made using the high-temperature tensile test and a bend test developed by Howard Scott.' In the tensile test the conditions have been standardized for all tests, so that values obtained are at least comparable, one alloy with another, although the absolute values recorded merely indicate the mechanical properties at the given temperature under a definite rate of loading.

Jan 1, 1932

By J. R. Campbell

The need for standardizing methods of arriving at definite conclusions regarding the cleanability of a given coal, and for measuring the performance of coal-cleaning equipment, is constantly increasing. Earlier notes by the author on this subject are amplified in this paper, because he believes that better preparation of bituminous coal is a partial solution of the coal operators' troubles. Washability Studies The term "washability" of coal was coined when washing was the universal method of separating coal from its impurities by utilizing their difference in specific gravity. This and analogous terms are still used in their broad sense although pneumatic or air separation is now used to clean coal. These terms are so used in this paper. Too much time or money can hardly be spent on "feed surveys') to get a "picture" of the coal that is to be cleaned. There have been too many "rule of thumb" methods used. Screen analyses and "sink-and-float" tests on the raw coal enable the coal operator and washery man to predict within reasonable limits the results that may be expected from any efficient cleaning apparatus. The sizes to be examined to get the picture are optional to the investigator. In modern wet washing, the range is from 4 to 0 in. Hand-picking on properly constructed belts is perhaps the standard for cleaning above these sizes. A good picture of the coal may be obtained by the following screen analysis: 3½ to 1¼ in. 1¼ to 3½ in. ½ to 5/16 in. 5/16 in. to 14 mesh 14 to 28 mesh 28 to 48 mesh and for very complete data on the fines: 48 to 100 mesh 100 to 200 mesh and through 200 mesh

Jan 1, 1930

By S. C. Sun, A. M. Gaudin

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By A. M. Gaudin, S. C. Sun

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By G. C. McLachlan

Two papers dealing with Noranda's milling operations have already been presented. The first1 of these covered the initial metallurgical problems connected with the treatment of the ore, while the second2 described the development of the mill from a 500-ton unit in 1928 to one with a daily capacity of 3000 tons less than six years later. At the time the second paper was written the equipment whirh had been installed to bring the mill capacity up to 3000 tons was being tuned into production and for this reason, though each step had previously been tested by a large-scale pilot operation, it was thought advisable to withhold metallurgical data until any starting-up difficulties had been overcome and anticipated requirements fulfilled. These requirements called for an improvement in gold recovery without any lowering of the previous ratio of concentration, and the pages that follow deal with the methods by which this result was obtained. An idea of the character of Noranda concentrating ore will be gained from an inspection of the following mineralogical analysis of the ore treated by the mill during 1933: MineRal Content Mineral ConteNt Chalcopyrite, per cent..... 6.8 Silica and silicates, per cent............ 18.3 Pyrite, per cent........... 22.1 Gold, native and as telluride, oz. per ton 0.15 Pyrrhotite, per cent....... 51.5 Silver, probably as argentite, oz. per tou 0.35 Magnetite, per cent....... 0.5 Thesr figures, which are typical, show that over 73 per cent of the ore treated consists of pyrite and pyrrhotite. Determirnation of the proportion of unrecovered gold associated with each of these minerals was therefore of primary importance in developing a suitable method for improving gold recovery. As pyrrhotite is magnetic, this information was obtained by making magnetic sorting tests on samples of the mill tailing and screening the material thus segregated. This showed that the magnebtic material finer

Jan 1, 1935

By Walter Fuchs

It is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. Synopsis of Biological and Chemical Facts The biosphere is not sterile; i.e., microorganisms are always present. Microor- ganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life—proteins, fats, carbohydrates, lignins, waxes, resins— may serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1942

By Walter Fuchs

It is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. Synopsis of Biological and Chemical Facts The biosphere is not sterile; i.e., microorganisms are always present. Microor- ganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life—proteins, fats, carbohydrates, lignins, waxes, resins— may serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1942

By C. M. Wright

Siendo la veta principal San Cristóbal, una de las estructuras que atraviesan el Anticlinal Chumpe en la provincia de Yauli, su explotación ha sido limitada a las rocas volcánicas y filitas en el flanco sur-oeste del anticlinal. Por tal motivo, el texto señala que el análisis de la distribución de los metales y minerales dentro de la veta, revela un zoneamiento horizontal bien definido, que es compatible con el origen de las soluciones hidrotermales en el centro del anticlinal. Asimismo, este estudio cuantitativo determina las características de las partes ricas de la veta, trazando líneas de contornos de los cuatro tipos de metal en secciones longitudinales, como los controles de la distribución de metal y relaciona las áreas ricas de la veta con su medio geológico. De otro lado, en San Cristóbal, la distribución del metal presenta una característica zonal donde la paragénesis y el zoneamiento están íntimamente relacionados. Concluyéndose que con la aplicación de los resultados de este estudio, se permitirá una mejor exploración y desarrollo de las áreas ricas de la Veta Principal San Cristóbal y se proporcionará una guía útil para la exploración y desarrollo de vetas paralelas en esta área.

Aug 20, 1963

By John H. Weigand, Stephen V. Crum

"VIBRONICS, INC. instrumented and monitored a residential structure for response to,blasting at aMidwestern surface coal operation. The residence was owned by the mining company and was extremely close to the operation. Blasting was conducted within 120 feet (36.5 meters) of the test structure. Up to seventeen (17), four (4)-channel seismographs were used during the monitoring period. The basement walls and floor were monitored. VIBRONICS, INC. also monitored a brick chimney in the basement and attic. Structural responses were then compared to outside vibration measurements taken in the soil near the foundation."

Jan 1, 1998

By A. U. Seybolt, R. E. Honnemon

THE purpose of this communication is to present activity data of nickel in the Ni-A1 binary system that was obtained for oxidation studies in this system. This data has been calculated from previous aluminum activity data at 1000°C1,2 by two types of Gibbs-Duhem integrations. These results should be of particular current interest to oxidation studies of aluminide coated nickel-base superalloys3 as well as other problems. The aluminum activity of Steiner and Komarek1 is plotted in Fig. 1 as a function of composition in Ni-A1 alloys at 1000°C. The dashed parts of the aluminum curves represent our approximate extrapolations from the directly measured regions. In the terminal solution regions (a and L phases) standard parabolic solution functions of the following form are assumed: where i is the component subscript, Ki is a constant at a fixed temperature, and xi is the atom fraction. The resultant nickel activity curve at 1000° C from the Gibbs-Duhem integration4 of the aluminum data is shown in Fig. 1. The solubility ranges of the phases present in the Ni-A1 binary at 1000°C are also denoted at the bottom of Fig. 1. Corresponding values of the nickel activity, aNi and yNi, are listed in Table I at useful compositional intervals. including phase boundary values. The aNi and yNi data listed in Table I are subject to the uncertainties present in the experimental aluminum activity data1 and to deviations from parabolic solution behavior in the terminal solutions. The errors introduced into aNi and yNi due to the parabolic solution assumption are expected to be relatively small (<20 pct of the values given) in all the phases except the liquid phase. Some deviation from parabolic solution behavior in the liquid phase is indicated

Jan 1, 1970

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.&apos;1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970