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By P. A. Beck, M. N. Parthasarathi

In high purity aluminum single crystals grown by the strain-anneal method (primary re crystallization after a small deformation) Lacombel observed sub-boundaries with disorientations of 1 to 3 deg. In commercial and high purity aluminum crystals grown by the same method Tiedema observed sub-boundaries with disorientations of about 20 min of arc, radiating from a =nuclear spot," centrally lo-

Jan 1, 1959

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls. SOURCES The principal sources of the gas at present are coke ovens, lime kilns, breweries and other fermentation plants, all of which are within easy reach of markets. Natural sources, however, have not received the consideration they merit, mainly because of their isolation. It is asserted by some manufacturers that the carbon dioxide gas produced from wells is unsatisfactory because it often contains impurities that are difficult to remove, while that produced as a byproduct is much purer or contains impurities that are easier to remove.

Jan 1, 1936

By George B. Langford

The McIntyre mine is in the Pearl Lake section of the Porcupine gold area. The rocks are Keewatin lavas intruded by quartz porphyries and albitite dies of Algoman age. Gold-bearing quartz veins are found in the Keewatin rocks near the porphyry stocks. The whole area has been highly compressed by forces acting along a N. 20°W. line. These forces folded the Keewatin rocks before the intrusion of the Algoman rocks, and later schisted both the Keewatin and Algoman rocks. Vein fractures were developed after the folding but before the development of the schist by the compres-sive forces being locally broken up into couples. These couples were set up by the differential resistance to deformation of porphyries and basalts, and also by the competency of the dacites and incompetency of the tuffs and fragmental rocks. During the important period of vein formation, two zones were developed—an inner productive zone in which the quartz veins are ankerite-bearing and an outer barren zone in which the quartz veins are calcite-bearing. The vein solutions originated in the same magrna that supplied the albitite dikes. Introduction The McIntyre mine, in the Porcupine gold area of northern Ontario, has passed its twenty-sixth birthday and has been producing gold since early in 1912. During this time approximately ten million tons of ore has been mined and over three and a half million ounces of gold recovered. This amount of ore would be sufficient to fill 2300 standard railway freight trains, each of 100 cars, and the gold produced, although only equivalent to a cube 51/2 ft. to the side, would weigh approximately 100 tons, a load for three freight cars. Silver has been produced in the ratio of 1 oz. of silver to every 4.4 oz. of gold, so that the total silver recovery is in the neighborhood of 700,000 ounces. The early history of the mine, like that of many others, shows that for several years it fought an uphill struggle for existence. One of the important features in winning this fight was the early recognition of some of the geological conditions responsible for the ore deposits, and the application of this knowledge in the search for ore and in the acquiring of adjoining properties. As early as 1913—only two years after the mine was opened—a geological department was organiaed. It has functioned almost continuously since that date and has demonstrated the importance

Jan 1, 1941

By George B. Langford

The McIntyre mine is in the Pearl Lake section of the Porcupine gold area. The rocks are Keewatin lavas intruded by quartz porphyries and albitite dies of Algoman age. Gold-bearing quartz veins are found in the Keewatin rocks near the porphyry stocks. The whole area has been highly compressed by forces acting along a N. 20°W. line. These forces folded the Keewatin rocks before the intrusion of the Algoman rocks, and later schisted both the Keewatin and Algoman rocks. Vein fractures were developed after the folding but before the development of the schist by the compres-sive forces being locally broken up into couples. These couples were set up by the differential resistance to deformation of porphyries and basalts, and also by the competency of the dacites and incompetency of the tuffs and fragmental rocks. During the important period of vein formation, two zones were developed—an inner productive zone in which the quartz veins are ankerite-bearing and an outer barren zone in which the quartz veins are calcite-bearing. The vein solutions originated in the same magrna that supplied the albitite dikes. Introduction The McIntyre mine, in the Porcupine gold area of northern Ontario, has passed its twenty-sixth birthday and has been producing gold since early in 1912. During this time approximately ten million tons of ore has been mined and over three and a half million ounces of gold recovered. This amount of ore would be sufficient to fill 2300 standard railway freight trains, each of 100 cars, and the gold produced, although only equivalent to a cube 51/2 ft. to the side, would weigh approximately 100 tons, a load for three freight cars. Silver has been produced in the ratio of 1 oz. of silver to every 4.4 oz. of gold, so that the total silver recovery is in the neighborhood of 700,000 ounces. The early history of the mine, like that of many others, shows that for several years it fought an uphill struggle for existence. One of the important features in winning this fight was the early recognition of some of the geological conditions responsible for the ore deposits, and the application of this knowledge in the search for ore and in the acquiring of adjoining properties. As early as 1913—only two years after the mine was opened—a geological department was organiaed. It has functioned almost continuously since that date and has demonstrated the importance

Jan 1, 1941

By George Kunz

(Butte Meeting, August, 1913.) THE manifold inconveniences resulting from the absence of a uniform standard of mass for determining the weight of precious stones have long been obvious. This lack has been keenly felt in commercial transactions, and those who have devoted time and research to the study of historic diamonds and precious stones have had frequent occasion to deplore the absence of such a standard in the past. In a paper read in Chicago in 1893, before the International Congress of Weights and Measures, held in connection with the World's Columbian Exposition, the writer suggested dividing the carat into 100 parts, and constituting a standard international carat of 200 mg. ; that is, 5 diamond carats or 20 pearl grains to a French gram, making 5,000 carats or 20,000 pearl grains to a kilogram. He also called attention to the fact that while this would depreciate the present diamond carat or pearl grain only about 2.5 per cent., it would abolish the troublesome discrepancies between the various carat-weights now in use, and could be easily explained and understood everywhere.1 The subject of the various diamond carats, their incongruity, and the resulting confusion as to the correct weights of historic gems when definite records of them are searched for, has been fully treated by me in an extensive study of this subject in The Book of the Pearl.2 To the earnest and unremitting efforts of C. E. Guillaume, Director of the Bureau Internationale des Poids et Mesures at Sèvres, is largely clue the eventual success of this eminently desirable reform, which lie has constantly urged both by articles on the subject and by addresses delivered in Paris before the International Committee for Weights and Measures.3

Jan 7, 1913

By Charles Austin

IT has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A, critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publications1,2 have shown that the factors controlling graphitization below the A, are different from those operating above the A, inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemi-cal analyses. Many years ago it was recorded' that the rate of graphitization at subeutectoid tem-perature is not a maximum just below the A, critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is im-possible to spheroidize certain steels in the temperature range of 650° to 710°C. with-out the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A, (720°°C,) these same steels may be completely sphe-roidized at constant temperature. In previous studies1,2,4 on 1 per cent plain carbon steels graphitization was en-countered during prolonged tempering. The limited number of steels studied did not provide sufficient data to permit adequate study of the factors controlling this graphi-tization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, fur-nished by four steel companies, who also supplied information regarding the history of manufacture.

Jan 1, 1940

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

THE effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions The large number of alloys investigated made it impossible to study every one in the detail it may have merited Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold-working tends to disorder the structure, resulting in very marked lowering of conductivity The random state of atomic arrangement produces lower conductivity than the ordered state for the same composition 1 PREVIOUS WORK previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys The increase of resistivity due to severe working was less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21 7 per cent increase of resistance for an alloy containing 67 9 per cent Cu as severely worked Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens The resistance decreased again when the cold-worked crystals were subsequently annealed Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working The conductivity of 72-28

Jan 1, 1941

By M. F. Smith

BELOW the nose of the bainitic C curves in isothermal transformation diagrams, the rate of the austenite-to-bainite transformation usually decreases with decreasing temperature. However, in some steels and iron-carbon alloys, there is a noticeable acceleration in the initial reaction rate at temperatures just above Ms. Such speeding-up of the bainitic transformation would be understandable at temperatures just below Ms because of the catalytic effect of the martensite formed,' but the reversal in isothermal kinetics just above Ms seems quite anomalous. This behavior was observed by Howard and Cohen' in a 1.35 pct C steel and, on the basis of metallo-graphic examination, it was attributed to the formation of a thin plate-like product not belonging in the bainitic sequence. More recently, schaaber2 found two-stage reactions occurring in the vicinity of Ms in a number of steels, and suggested that the first stage might be the isothermal formation of marten-site, preceding the isothermal formation of bainite in the second stage. A decrease in the bainitic incu-

Jan 1, 1960

By Fred C. Bond

DISCUSSION Milton C. Shaw and Donald R. Walker (Massachusetts Institute of Technology)—For many years the two empirical rules of comminution bearing the names of Rittinger and Kick have been applied to grinding processes to account for the energy required to crush brittle materials. The basis for Rittinger's rule was the thought that the energy to grind a substance went largely into supplying the additional energy associated with the new free surface, while Kick's law was prompted by the concept of dimensional similarity and is a special statement of the concept of constancy of strain energy to cause rupture. According to Rittinger the energy to grind a given volume varies as the change in the square of the mean particle size, v - A (D2), while according to Kick this energy varies

Jan 1, 1953

By Fred C. Bond

DISCUSSION Milton C. Shaw and Donald R. Walker (Massachusetts Institute of Technology)—For many years the two empirical rules of comminution bearing the names of Rittinger and Kick have been applied to grinding processes to account for the energy required to crush brittle materials. The basis for Rittinger's rule was the thought that the energy to grind a substance went largely into supplying the additional energy associated with the new free surface, while Kick's law was prompted by the concept of dimensional similarity and is a special statement of the concept of constancy of strain energy to cause rupture. According to Rittinger the energy to grind a given volume varies as the change in the square of the mean particle size, v - A (D2), while according to Kick this energy varies

Jan 1, 1953

By John D. Wiebmer

Lignite Development in North Dakota is a "shotgun wedding" according to former state senator Robert L. Stroup-the unwilling groom (North Dakota) is being led to the altar by the nation's demand for increased coal production. The state's attorney general, Allen I. Olson, reacts to the situation this way: "We have no specific coal policy. We plan to keep the whole matter down to a dull roar and drag our feet until we see how we fit into the national energy picture." But despite a state administration labeled as "cautiously negative" toward resource development, North Dakota has experienced a twofold increase in annual lignite production within the last two years. And within the next four years, three more mine additions will double the state's output again.

Jan 8, 1977

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

SEVERAL constructive and fundamental studies have been made in the analysis of data obtained from experiments carried on with batch ball and rod mills. The operating characteristics of ball milling in small continuous circuits have also been appraised. It is from these analyses that some of the theories of comminution have been developed. Relatively few studies of continuous rod milling have added significantly to the fundamental concepts, because seldom have they yielded sufficiently consistent results. Perhaps they have been too limited in their scope. Careful control of the variables in batch grinding is simple compared with that encountered in a continuous operation. This factor alone has discouraged many investigators. Occasionally results of systematic changes made in industrial rod mill circuits have been published, but usually the data are sketchy and are restricted because -of the unwieldiness of the equipment used. The work, in general, has not been comprehensive; nevertheless it has provided empirical relationships that have bridged the gap between postulate and practice so that by proper manipulation of formulae, a mill designer can anticipate mill size and power requirements.1-3 Although operating variables of a small continuous mill are not so easy to control as with the batch mill, with present day devices, and with careful experimental work, consistent results can be obtained.

Jan 10, 1954

By J. Burbank

A TECHNIQUE has been developed for the microscopic study of the three-dimensional structure of the Pb-Sb alloys by the formation of a chemical replica in which the internal structure of the metal may be seen directly. In the replica process one of the phases present in the structure as-cast is converted into a translucent material, and the second phase remains virtually unaffected, permitting microscopic examination by transmitted light. Alloys of lead and antimony were made from the chemically pure metals, cast in a sooted and pre-

Jan 1, 1954

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Jan 1, 1938

By W. B. Hall, Joy D. Lewis

Mine-run ore is received at Vitro in gondola cars and fed directly to a Cedar Rapids impact crusher. Following screening, the undersize travels through a recently installed three-stage sampling plant where successive cuts are executed by conventional Geary-Jennings type cutters to produce a final sample of 1 lb per ton of raw ore fed. Crushed ore is transported to one of three storage silos or to stockpile, depending upon grade and type of amen- ability. This permits the blending of a mill feed with some degree of consistency. Final grinding is accomplished in one of two closed circuit ball mill-classifier systems allowing simultaneous processing of two basic types of ores. High acid consumers may be leached separately in the required environment. Part of the free acid remaining can then be utilized by an ore stream entering later whose component ores require much less free acid for leaching.

Jan 11, 1958

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By Thomas H. Leggett

The conditions surrounding this mine are, perhaps, not sufficiently rare or significant to warrant special attention. A certain interest, however, attaches to the locality through the recent discovery of fossil cycads made there by Mr. Charles M. Rolker, of New York, who has repeatedly visited this district, fixing the geological horizon

Jan 1, 1889

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,' who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968