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By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

By Thomas Brownfield

Development and production activity in Oklahoma during the year 1940 was of routine nature. Production, according to the Corporation Commission's figures, averaged 409,100 bbl. daily as compared with 421,000 bbl. for the year 1939. Discoveries were of minor importance except for the Cumberland pool in Marshall and Bryan Counties, in the southern part of the state. Maintenance of a relatively stable producing rate is attributable to the drilling of new wells and the recompletion of many old wells in the previously established producing areas. During the year 1785 new wells were drilled, a decline of approximately 10 per cent as compared with the previous year. Of the wells drilled, 962 were oil wells with a combined initial production of 241,000 bbl. daily, 172 were gas wells having aggregate capacities of 1205 million cu. ft., and 651 were dry holes. Wildcat activity increased 20 per cent over 1939 and 227 such wells were completed during the year; that isl 43 oil wells, 16 gas wells, and 168 dry holes. In addition to the new work completed, 603 wells were recorded as having been drilled deeper or plugged back to test new horizons; included were 334 producing wells with total initial production of 65,000 bbl. daily, 37 gas wells with initial aggregating 305 million cu. ft., and 232 abandonments. Footage drilled amounted to 4,730,000 ft., an average of 2650 ft. per well as com-pared with an average depth of 2600 ft. recorded the previous year. The principal new pools discovered as a result of the exploratory drilling were Cumberland; East Cromwell, in Okfuskee County, and Prague, in Lincoln County. At the end of the year Cumberland had 13 completed wells, which averaged 700 bbl. initial through tubing from the Simpson Bromide formation (Ordovician) at 4750 ft. East Cromwell had 10 wells with average initial of 435 bbl. in the Cromwell sand (Pennsylvanian) at 3460 ft. Prague had II wells with an initial average of 220 bbl. from the Senora sand (Pennsylvanian) at 3260 ft. There were notable extensions to the Dill pool, Okfuskee County, and to the Hewitt pool, Carter County. At the end of the year, 19 producing wells had been drilled in the former, with initials averaging 1000 bbl., and 63 wells averaging 150 bbl. daily in the latter. There were no notable changes in the policy of State conservation authorities with respect to proration. The Bureau of Mines recommendations for the year averaged 413,000 bbl. daily; the State author-ities fixed allowables at an average of 406,000 bbl. daily, while, as noted above, production averaged 409,100 barrels. The most important development in the older areas occurred in the following pools: Billings.—Seven oil wells with an average initial production of 2500 bbl. and two dry holes were completed during the year. Production from the Simpson horizon averaged 6025 bbl. daily as compared with 5950 the previous year. Production from this field has been almost steady since reaching its peak early in 1937. The major portion of the pool is efficiently operated as

Jan 1, 1941

By Thomas Brownfield

Development and production activity in Oklahoma during the year 1940 was of routine nature. Production, according to the Corporation Commission's figures, averaged 409,100 bbl. daily as compared with 421,000 bbl. for the year 1939. Discoveries were of minor importance except for the Cumberland pool in Marshall and Bryan Counties, in the southern part of the state. Maintenance of a relatively stable producing rate is attributable to the drilling of new wells and the recompletion of many old wells in the previously established producing areas. During the year 1785 new wells were drilled, a decline of approximately 10 per cent as compared with the previous year. Of the wells drilled, 962 were oil wells with a combined initial production of 241,000 bbl. daily, 172 were gas wells having aggregate capacities of 1205 million cu. ft., and 651 were dry holes. Wildcat activity increased 20 per cent over 1939 and 227 such wells were completed during the year; that isl 43 oil wells, 16 gas wells, and 168 dry holes. In addition to the new work completed, 603 wells were recorded as having been drilled deeper or plugged back to test new horizons; included were 334 producing wells with total initial production of 65,000 bbl. daily, 37 gas wells with initial aggregating 305 million cu. ft., and 232 abandonments. Footage drilled amounted to 4,730,000 ft., an average of 2650 ft. per well as com-pared with an average depth of 2600 ft. recorded the previous year. The principal new pools discovered as a result of the exploratory drilling were Cumberland; East Cromwell, in Okfuskee County, and Prague, in Lincoln County. At the end of the year Cumberland had 13 completed wells, which averaged 700 bbl. initial through tubing from the Simpson Bromide formation (Ordovician) at 4750 ft. East Cromwell had 10 wells with average initial of 435 bbl. in the Cromwell sand (Pennsylvanian) at 3460 ft. Prague had II wells with an initial average of 220 bbl. from the Senora sand (Pennsylvanian) at 3260 ft. There were notable extensions to the Dill pool, Okfuskee County, and to the Hewitt pool, Carter County. At the end of the year, 19 producing wells had been drilled in the former, with initials averaging 1000 bbl., and 63 wells averaging 150 bbl. daily in the latter. There were no notable changes in the policy of State conservation authorities with respect to proration. The Bureau of Mines recommendations for the year averaged 413,000 bbl. daily; the State author-ities fixed allowables at an average of 406,000 bbl. daily, while, as noted above, production averaged 409,100 barrels. The most important development in the older areas occurred in the following pools: Billings.—Seven oil wells with an average initial production of 2500 bbl. and two dry holes were completed during the year. Production from the Simpson horizon averaged 6025 bbl. daily as compared with 5950 the previous year. Production from this field has been almost steady since reaching its peak early in 1937. The major portion of the pool is efficiently operated as

Jan 1, 1941

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By William P. Blake

Postscript to the paper read by Prof. William P. Blake at the Lake Superior meeting, September, 1904. POSTSCRIPT.*-Since the publication of my paper upon the blackening of the surface of rocks in desert regions, I have noted that similar views of the origin of superficial discoloration in the case of certain rocks from the Salt Lake basin of Utah have been expressed by Prof. George P. Merrill. In the pamphlet, he described the brown-coated weathered boulders from Tooele county, reaching the conclusion that the discoloration was due to the solution of the manganese and iron compounds 'in the interior of the boulder, while they were in the water, and the gradual bringing of this material to the surface through capillarity and its oxidation when exposed.

Mar 1, 1905

By Pei-Yung Huang, Carle R. Hayward

IN order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. CHOICE OF SLAG COMPOSITION The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, average:2.3 45 to 47 pct FeO; 38 to 42 pct Si02; 5 to 6 pct CaO; 5 to 6 pct A1203. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-Si02-A1203, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the com¬position near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093° ± 3°C) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the resulting slag is decidedly too basic. Composition K has a slightly higher melting point (1105° ± 3°C) and a higher silica content, but this is preferred because the slag is saturated with respect to tridymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The final slag composition, therefore, was chosen to

Jan 1, 1947

By Leonard Grimshaw

THE idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a com-posite steel.

Jan 1, 1936

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By Luke L. Y. Chang, Bert Phillips

ThE tendency toward further oxidation of the intermediate oxides and the high volatilization rates of the higher oxides have prevented direct attainment of equilibrium data for the system tungsten-oxygen. As a result, St. Pierre et al.1 have proposed a phase diagram (to 800°C) based on thermody-namic data to 1200°C for the known tungsten oxides (WO2z, W18O49, W20O58, and WO3) and a report on a tungsten suboxide W3O.2 Recent modification of a technique previously described3 5 now permits adequate preservation of compositions of mixtures of metallic tungsten and metal oxides (e.g., of tungsten, cobalt, calcium, samarium, titanium) in order that condensed phase relations may be established to 1700 This method has been applied to study the high-temperature stability of tungsten oxides. In the method used, the desired compositions were sealed in nonreactive containers such that only a small gas volume remained. Each sample then established its own equilibrium atmosphere at temperature. This method has advantages in the study of systems of the W-0 type where knowledge of the condensed phases is desirable but for which composition and pressure of the gas phase are not readily attainable because of oxide volatility. Mixtures of 99.99 pct tungsten metal powder and purified tungsten anhydride (WO3) or in some cases W18O49* were equilibrated in pellet form in sealed

Jan 1, 1964

By J. F. Tavernelli, L. F. Coffin

The deformation and fracture characteristics of eight metals subjected to fully reversed cyclic strain ranging from 0.2 to 50 pct were investigated at room temperature. Strain-hardening characteristics unique to the interna1 structure of a particular metal were found. Complete removal of the strain-hardening effects resulting from prior deformation was brought about by subsequent cyclic strain. Further support for the validity of the inverse relationship between the plastic strain range and the square root of the number of cycles for failure is given. THE resistance of materials to cyclic plastic strain is of interest both from a fundamental and practical point of view. It is now a well-accepted fact that fatigue failure in metals is a consequence of the localized slip deformation which occurs within the individual crystals of metal.'-' Hence the failure process should be strongly dependent upon the magnitude of the gross cyclic plastic deformation of the metal under conditions where this is a measurable quantity. Therefore, an experimental investigation of metals in which the cyclic plastic strain is the independent variable should shed new light on some of the basic aspects of the problem. From the practical point of view, there are many uses for information relating to the cyclic strain resistance of metals. One is the case of thermal stress fatigue where fatigue failure can occur as a consequence of a com- paratively few cycles of thermally induced mechanical deformation. Another is the mechanical working of metals where large cyclic strains are employed. In recent years several publications have appeared relating to the cyclic-strain resistance of metals,8-11 dealing mostly with the fracture aspects where the temperature is cycled simultaneously with the mechanical strain. Some work has been reported on the cyclic-strain resistance of metals at constant temperature, again oriented more toward the fracture aspects of the problem than the deformation aspects. 12-16 The present research investigation was undertaken to obtain information regarding the deformation characteristics of several metals whose structure-property relationships were simple and straightforward under conditions of both cyclic and monotonic strain. It has been shown for example that under cyclic-strain conditions some materials will strain harden, while other materials, particularly cold-worked structures, strain soften and these effects required further clarification.8,17-19 It was also de-

Jan 1, 1960

By James E. Lawver, James L. Wright

This paper discusses the design and calibration of a Faraday pail for measuring electric charge. The paper also shows that at least for two minerals, quartz and calcite, the phenomenon that Johnson termed "reversibility" can be explained in terms of the contact electrification between the minerals and the metal rotor of an electrostatic machine. Each year the free world produces about 13 million tons of mineral concentrates by electrical separation. However, despite the rather general acceptance of electrical concentration as an industrial process, research in this area has lagged far behind the efforts devoted to competitive processes such as froth flotation. The purpose of this paper is to describe the design and calibration of a Faraday ice pail for measuring charge density on mineral grains and to show some of its applications in the area of electrostatic and electrodynamic research. THE DESIGN AND CALIBRATION OF FARADAY PAILS FOR ABSOLUTE CHARGE MEASUREMENT The electric charge on mineral grains at a given time during an electrical concentration process is de- pendent on many factors and cannot, in general, be accurately calculated a priori. It is thus important to devise a method of measuring absolute charge. One method of measuring electric charge is to note the potential rise of an electrometer when charged particles drop into a Faraday pail. Two types of Faraday pail have been constructed and calibrated. The first type, Faraday Pail I (Fig. 1), is a vertical pail originally designed to measure the charge due to contact electrification between mineral grains and a metal rotor or due to conductive induction when mineral grains are passed over a rotating cylinder in the presence of an electric field. The second type, labeled Faraday Pail II (Fig. 2), is a horizontal pail designed to determine the charge distribution of mineral grains after they pass through the separating zone of the electrical concentrator shown in Fig. 4. The main advantage of the horizontal pail is its low head-room requirement and the long opening which enables the experimenter to sample the entire width of the stream of minerals being separated. The Faraday pails were calibrated in the following manner: A calibration head was constructed in the form of a hollow brass sphere that could be held in an insulated metal cylinder by vacuum (Fig. 1). The capacitance of the sphere was calculated by measuring the capacitance of the sphere and cylinder combined and that of the cylinder alone and subtracting the latter measurement from the former. The sphere was then charged to a known potential (V) and allowed to drop into the Faraday pail which was attached to a Keithley Model 610A electrometer. This instrument has an accuracy of 2% full scale and has

Jan 1, 1969

By S. C. Dhara

A process of solvent extraction and separation of platinum group metals (PGM) and gold using primary, secondary, tertiary, and quarternary organic amines has been briefly described. The effects of amine structures; the use of diluents; the principle of synergism and antisynergism in the mixed extractants; the oxidation states of metal ions are explained in the amine extraction process of precious metals.

Jan 1, 1984

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman&apos; provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry&apos;s law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of &apos;composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert&apos;s-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.&apos; The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

P. Herasymenko (New York University, New York) —The authors&apos; experiments on equilibria between water vapor and liquid synthetic slags represent a valuable contribution to our knowledge of the nature of liquid slags. They can be regarded as a proof of ionic splitting of water molecules dissolved in slags. The assumption that water dissolved in slag was com- pletely ionized was made in my report on hydrogen equilibria in steelmaking as early as 194010. In that paper, the first systematic data were given on the content of ionized hydrogen in acid and basic open-hearth slags. The paper probably escaped the notice of the authors, although they mention the articles published later by other investigators who reported erratic and

Jan 1, 1958

By I. R. Kramer

The apparent activation energy, U, JOY plastic deformation of aluminium, copper, and gold single crystals and polycrystalline aluminum was found to he dependent upon surface condition. At low strains, the value for U for aluminum single crystals was 4200 cal per mole ; however, this value decreased to 920 cal per mole when the specimens were polished during the test at a rate of 50 X 10-5 win-1 The activated volume also was found to increase with the rate of metal removal. That the surface plays an important role in plastic-deformation processes has been adequately demonstrated.1-4 Of particular interest at this time are the observations4 that the creep rate of single crystals of fee metals is increased markedly when specimens are polished during the deformation process. These observations were interpreted in terms of a dislocation debris layer at the surface regions of the crystal. This layer, which appears to be a region containing a high concentration of dislocations or segments of dislocations, not only will impede the egress of dislocations on the primary slip system, but will also provide a barrier against which dislocations may pile up. By this means, a stress which opposes the motion of dislocations will be generated. It is considered that this stress must be taken into account in any theory which describes the plastic-deformation process. Although a detailed dislocation model cannot be given at this time, it may be stated that the stresses opposing the motion of dislocations arise from the dislocations in the debris layer, Ts, and ti due to the resistance to motion imposed by internal obstacles such as Lomer-Cottrell barriers, subgrain and grain boundaries, forest dislocations, and so forth, as well as the resistance due to the presence of jogs on dislocations and the interaction of the stress fields of dislocations, and so forth. In essence, we have added an additional term, ts, to the usual form of the equation T = Ta- Tb, where Tb is the back stress due to the various types of obstacles which impede the motion of dislocation. Accordingly, the net stress, t, acting on a dislocation may be written as where Ta is the applied shear stress. For deformation which occurs by a thermally activated process5,8 ?=Ae-u/kT = A e(u,-VT)/kT [2] and U = Uo- Vt PI where U = activation energy for plastic flow, y = shear strain rate, Uo = activated energy for plastic deformation in the absence of stress and depends upon the particular deformation process, V = activated volume, k = Boltzmann constant, T = temperature, OK, and A = frequency factor. From Eqs. [I] and [3], U = Uo- V(Ta - Ti - TS) [4] and it is seen that if Ts decreases, the activation energy, U, must decrease if V remains constant. However, as will be shown, V is a function of the surface conditions. In their work on aluminum, Lytton and coworkers7 reported that at low strains the activation energy was 3400 cal per mole and at high strains it was 28,000 cal per mole. The lower value was interpreted in terms of the energy necessary to overcome the Peierls force, while the higher value was associated with the energy necessary for dislocations to move by a cross-slip process. It will be shown that the lower activation energy is associated with the surface debris layer rather than with the Peierls force. EXPERIMENTAL PROCEDURE Single crystals having a nominal cross section of 1/8 in. and a 3-in. gage length were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The initial purity of the metals was 99.997, 99.999, and 99.999 pet for aluminum, copper, and gold, respectively. The orientation of the specimens is given in Fig. 1. The measurement of the activation energy as a

Jan 1, 1964

By Howard Martens, Pol Duwez

XPERIMENTS were performed on a Cr-Fc alloy Econtaining 44.7 pet Cr in order to determine the heat evolved during the transformation of the a solid solution into the s phase, and the change in volume accompanying the transformation. Since previous measurements on the rate of formation of a from s indicated that the reaction was quite fast as soon as the equilibrium temperature of 820°C was exceeded by some 50°, standard thermal analysis experiments were performed on heating specimens of s at the rate of approximately 40°C per sec. A definite thermal arrest was observed at 870"C, Fig. 1. This result indicates that the reverse seaction of into a is exothermic. From the heating curve of Fig. 1, taking 15°C per sec as the heating rate in the neighborhood of the transformation, 2.4 sec as the time for transformation, and assuming that the specific heat of the alloy at 850°C is an average between iron and chromium, namely 9.5 cal per mol per "C, the latent heat of transformation is approximately 342 cal per mol. The order of magnitude of this latent heat was also obtained by comparing the heating curve of Fig. 1 with a similar curve obtained with pure iron under identical experimental conditions. It was found that the length of the thermal arrest for s was about 1.8 times as long as that for iron. Since the latent heat of the a to 7 iron transformation is 203 cal per mol1, 2 the latent heat of it to a would be 365 cal per mol, which is in relatively good agreement with the value determined from the heating curve. For the determination of volume change, thermal expansion curves were recorded using a specimen containing 44.7 pet Cr and completely transformed to cr by previous treatment. The curves were recorded at a rate of heating of about 4°C per min and at approximately 840°C a sharr, increase in length of about 0.08 pet took place. Fig. 2. It is therefore established that the specific volume of a near the transformation temperature is about 0.24 pet smaller than that of a, and consequently, when the s phase forms in an a matrix, it would tend to shrink away from the matrix. Since the s phase is known to be extremely brittle, these results offer an explanation for the microscopic cracks often observed in the a phase under the microscope. The results of this study are in qualitative agreement with previously published data on stainless steel 19-9DLa and on a Cr-Fe alloy containing 45 pet Cr.&apos; The increase in density due to the transformation from n to s given in ref. 4 is 0.90 pet. These measurements, however, were made at room temperature. whereas the presently reported 0.24 pet is the change at the temperature at which the transformation takes place during heating. In the graph of Fig. 2, the percentage change in length that would be observed at room temperature is given by the length X, which is about 0.27 pet. This would correspond to 0.81 pet in volume change. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-ORD-18 with the Army Ordnance Corps, Washington, D. C. The authors wish to thank this agency for permission to publish the results of this investigation. References I H. Klinkhardt: Measurements of True Specific Heats at High Temperatures. Annalen der Physik (1927) 84, pp. 167-200. - H. Esser and W. Runghardt: Influence of the Method, of Dctcrmination on the Measured Heat Content of Iron. Archtvo ffur Dct Eisenhiittenwesen 11934) 8, pp. 37-38. J. J. Gilman, P. K. Koh, and 0. Zmeskal. Delta Ferrite Formation and its influence on the Formation of Sigma in a Wrought Heat Resisting Steel. Trans. ASM 1 1949) 11, pp. 1371-1388. 1 J. M. Thomas: Discussion of ref. 3. Trans. ASM (1949) 41, pp. 3 390-1392.

Jan 1, 1957