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By R. E. Reed, C. J. McHargue

Single crystals of aluminurn were reduced 90 pct in diameter by extrusion at 296" and 77°K. The resultant double fiber texture had a strong (111) component with a weak (001) component. The relative anzounts of these components varied with starting orientation. Decreasing the Lemperatuve of defovtnation increased the amount of (001) texture component in crystals with inilia1 orientations near (111). The starting orientation and temperature of deformation strongly affected the morphology of the (001) component. The effects of orientation and Lemperatuve upon the distribution of the (001 ) texture component in extruded aluminum single crystals were rationalized on the basis of deformation band formation and interaction. MANY papers since the early 1920s have discussed the occurrence of the double fiber texture (111) + (001) in wires and rods of deformed fcc metals. Aside from the reporting of experimental results for the various metals under a variety of fabrication conditions, emphasis has been placed on two related problems. One problem deals with the prediction of ideal end orientations based on the glide systems and flow directions. The other problem seeks the reason why different amounts of each component may be produced by the same fabrication schedule for metals apparently having the same deformation systems. Some of the difficulties in developing a satisfactory explanation have their origin in the experiments themselves. One mistake has often been the assumption of an initially randomly oriented specimen or complete ignorance of effects of starting orientation. Recent studies by Grewen and Wassermann,1 Cullity and co-workers,2' and McHargue4 have shown that the initial orientation may be the most important factor in determining the final orientation. Hence only limited comparisons of data from different studies can be made unless all conditions of the initial material are specified. Another question has been the nature of the (001) component. Hibbards suggested that any (001) present was the result of re crystallization during fabrication. Although Fleischer6 found no (001) texture in aluminum swaged at room temperature, and Dayal 7 found that component to disappear at very high reductions, a double fiber texture has usually been reported for aluminum. Vandermeer and McHargue showed that, while some (001) in aluminum may be the result of recrystallization, much of this component has its origin in the deformation process. Ahlborn and Wassermanng found the (001) component in silver deformed at low temperature not to be the product of recrystallization.

Jan 1, 1968

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1-4 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio,' in the 1920's to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably those from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu's in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920's were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1952

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By Jerome Strauss, Carl L. Shapiro

THIS is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years,, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I INFLUENCE OF BODY-CENTERED CUBIC ELEMENTS The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tantalum) are reviewed individually. Iron-carbon-chromium System.-In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts' concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.-Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. a; these results have received general approval. Iron-carbon-molybdenum System.-In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and Reed,8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-

Jan 1, 1943

By O. G. Bell

While all of the Southwest Texas fields lie within the Gulf Coastal Plain this area may be divided into three subdivisions—the Coastal Plain zone proper, the Reynosa Escarpment zone, and the interior zone. The Coastal zone includes that strip adjacent to the Gulf of Mexico and . extending inland for a distance of about 60 miles and includes the Palo Blanco, Palangana, Piedras Pintas, Kingsville, Agua Dulce, Saxet, White Point and Refugio fields. The Reynosa Escarpment zone includes a Pliocene overlap over older Tertiary sediments lying west of the Coastal zone. The western margin of the Reynosa formation forms a more or less well-defined westward facing escarpment with which the so-called Reynosa Escarpment fields are indirectly related. These fields include those in eastern Zapata, eastern Webb, western Jim Hogg, western Duval, McMullen, Live Oak, Bee, Goliad and Victoria counties. The interior zone includes these fields west of the Reynosa Escarpment which are not in any way related to it and are on separate types of structure. Production data by fields and wells are shown in Table 1. Roma.—During 1928 the Texas Co. completed two small gas wells at 198 ft. on the Roma Structure near the town of Roma on the Rio Grande in Starr County. This gas is of no commercial importance but was used for fuel in drilling other deep tests on this structure. Three dry holes ranging from 3600 to 4200 ft. were drilled; then their No. 4 Guerra, the fourth deep test, was completed during December as a small producer of 37" Bé. oil from a sand at 3560 to 3590 ft. No production was marketed during December but arrangements were being made to handle the output from this well during 1930. This is the first commercial producer in Starr County. Driscoll.—In 1929, Robert Driscoll discovered gas on his Santa Rosalia Ranch in Duval County while drilling water wells. Two sands were developed, one at 2400 ft. and another at 2936 ft. and several gas wells were completed in each, ranging in volume from 15,000,000 to 40,000,000 cu. ft. and in reservoir pressure from 500 to 1,000 Ib. Early in January of 1929, Mr. Driscoll's No. 14 Fee was completed as a 50-bbl. oil producer at 2894 ft. Two other oil producers were completed early in 1929. Mr. Driscoll's death early in the year curtailed develop-

Jan 1, 1930

By Herbert Haas

ChEap power is essential to large-scale mining and metallurgical operations, particularly where fine grinding of large tonnages has to be resorted to, as is the case with an increasing number of mines treating disseminated copper ores, or low-grade gold ores, in the grinding of which considerable power is consumed. A comparison of the cost of generating power with Diesel engines and steam turbines and a brief discussion of the different factors governing the profitable use of either type of prime mover may be timely in view of the importance of a cheap supply of power to the mining industry, and the prominence that has lately been given to Diesel engines in America. As many of our most important mines and largest producers of metals are located in sections where neither cheap coal nor water power is available, and the price of oil fuel is increased by long hauls, the Diesel engine will become a prime mover of increasing importance. This applies particularly to the Southwestern States, where an ample supply of cold water for condensing purposes is unusual and local climatological conditions interfere in securing the high vacua essential to high turbine efficiency. About 12 times as much water will be required for condensing purposes with steam turbines under general conditions as is needed for jacket-cooling of two-stroke cycle Diesel engines; four-stroke cycle Diesel engines require only one-twentieth of the cooling water. Another condition favoring the use of Diesel engines is the high load factor at which most mine power plants operate. The influence of load factor on the cost of generating power is shown in Tables 1. and 2 and in Fig. 1. The higher the cost of fuel and the load factor, the greater will be the proportion of the fuel to the other costs making up the total cost of generating power. Capital charges (interest and redemption), maintenance, operating labor, and lubrication are practically constant amounts regardless of the load-output of the station; the fuel consumption and its cost are practically the only variables with the load. The costs here given are based on conditions as generally found in the Southwestern States, and on Diesel engine operating experience in European countries, where this type of prime mover has reached a high state of perfection, units upward of 4,000 hp. having proved entirely successful in operation.

Jan 1, 1917

By Robert H. Richards

(Read at the Wilkes-Barre Meeting, May. 1877.) THE Institute of Mining Engineers has shown so much interest in the educational problem of profitably combining theory and practice, that it seems especially appropriate to lay before its members the methods and aims of the mining laboratory of which I have charge, and in which one form of combination of hand with head work is now being tried. If anything may be contributed toward the solution of this problem by the discussion which follows, my purpose will be attained. Whether it was wise or not to establish a mining school so far from the principal mining centres, does not now enter into the question. Given, a mining school already begun, how shall it be made most efficient in developing engineers who are trained to think for themselves as well as versed in the works of others? This is the ques¬tion with which we have had to deal. In considering the bearing of this laboratory work upon the students' preparation, it will be convenient to take it up under five different heads 1. The methods and aims of the laboratory. 2. The advantage to students of having a part, at least, of their practical work in the curriculum of their school. 3. The advantage to be derived by mines and works. 4. Degree of accuracy which may be attained in working ores on a small scale. 5. Results of work in the laboratory. 1. The Methods and Aims of the Laboratory.-During the May meeting of 1873, held in Boston, I had the privilege of reading before you a paper stating the plans and aims of this laboratory. Since that time we have been constantly following out those plans, and are more than ever convinced that we are working in the right direction. We do not feel that the time we have spent has been in any sense thrown away. Perhaps the aims of the laboratory can be most clearly shown by illustration. Many young engineers leave school thinking that they know everything. They go to the works, and expect to teach the superintendent something and the men a good deal, regardless of the fact that it is this spirit that has prejudiced workmen against schoolmen. They are often more trouble than they

Jan 1, 1878

By Rossiter W. Raymond

It is scarcely necessary to augment or amend the "Appreciation" of Dr. Douglas, from the pen of Dr. Albert A. Ledoux, which appeared in January, 1916, in Bulletin No. 109 of the Institute. The author of that admirable summary enjoyed the great privilege of expressing while Dr. Douglas was yet among us (though already marked for death) the love and esteem with which we all regarded him. But now that his earthly life has ended, the historian must still be the eulogist. No line need be added or deleted in the portrait of him already drawn; it has only to be accepted now as a true likeness, and hung in the gallery of the immortals, illuminated by the crowning glory of another world. James Douglas was born at Quebec, Canada, November 4, 1837. His father, James Douglas, was a distinguished physician and surgeon, known in many lands, especially in the Orient, and famous in his own country for his philanthropy as well as his skill, having established and directed for many years the first retreat for the insane in the Dominion. of Canada. One of the latest literary labors of the son was the editing and publishing of his father's journal and reminiscences—a fascinating volume, the review of which, though a tempting task, I must here forego. Nearly fifty years ago, I had the great pleasure of spending an hour with the elder Douglas, who guided me through his collection of Egyptian and Asiatic treasures. I might almost say souvenirs; so many of them were connected with personal experiences and exalted personages. The veteran's memory had already begun to fail with age, but his vivacity and imagination glowed all the more brightly; and his reminiscences of travel and adventure were embroidered with Oriental magnificence. I felt, after that hour, as if I had visited a stately, half-ruined edifice, overgrown with vines and flowers. The father's genius, adventurous spirit and generous philanthropy descended to his versatile, yet practical son. Like other men of such temperament, James Douglas tried many things before circumstances beyond his own control forced him into the line of his principal lifework. At the age of 18, he was sent to the University of Edinburgh, where he studied for two years. Returning to Canada, he entered Queen's University, at Kingston, Ontario, where he was graduated as Bachelor of Arts in 1858. Subsequently he studied medicine at Lava1 University, Quebec;

Jan 1, 1919

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"' could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.' The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite' as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,' but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion' in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ'. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By C. M. Wayman, R. Bullough

The rediffraction of Bragg diffracted beams by differently oriented regions (such as twins) of a crystal may give rise to "extra" reflections or reciprocal lattice points. These two papers are concerned with predicting these additional reflections which result from twin related regions of a lattice. Analysis is made for {111}fcc twins, (112)bcc twins, and {hkil}hcp twins. It is first required, knowing the specific variant of the twinning plane in each case, to predict the positions of the twin reflections relative to the matrix reciprocal lattice. Once this is done, the positions of the "extra" multiply diffracted reflections may be deduced. Part I is devoted to establishing "selection ru1es" for twinning, i.e., the necessary and sufficient conditions for the existence of twinned reciprocal lattice points. 1. INTRODUCTION. Transmission electron diffraction patterns are frequently complicated by multiply diffracted beams. Pashley and stowell1 have recently demonstrated that certain extra reflections in evapo- rated films of gold result from the rediffraction of matrix Bragg diffracted beams by (111) microtwins in the gold. It was previously (and erroneously) suggested 2,3 that observed "irrational" reflections in fine-grained gold were due to the presence of some hcp gold. A similar situation exists, apparently, for some bcc materials; fine (112) twins in bcc martensite in Fe-Ni alloys4 give rise to extra reflections. There are many other examples. The number of transmission electron microscopic investigations is continually increasing, and because of the importance of double (and multiple) diffraction in the interpretation of diffraction patterns, it was judged that a detailed elaboration of the principles involved is desirable, as well as the extension of these principles in reasonably closed form to other crystal structures, particularly bcc and hcp. The present analysis considers double diffraction caused by (111) twins in fcc metals, (112) twins in bcc metals, and {hkil} = {hkl) twins in hcp metals. For each case of twinning, the various possible (variants of) twins give rise to a set of interpenetrating reciprocal lattices. The relative spatial arrangements of these reciprocal lattices can be deduced (Part I) and are expressed in terms of simple "selection rules". The resulting sets of interpenetrating reciprocal lattices are then analyzed for possible doubly diffracted reflections (Part II). The notation used, and some important formulas are given in Appendices I and 11.

Jan 1, 1967

By W. J. Skewes, C. T. Holland

Properly constructed stopes are necessary underground for proper ventilation and safe, healthful working conditions. Mining companies are concerned with providing the best possible stoppings at an economic cost. It is important to consider 1) proper materials, 2) construction that ensures maximum performance from the material used, and 3) keeping costs within reasonable limits for the unit operation—stopping—involved. The authors investigated all aspects of the problem and have attempted to layout a study program to provide information on all phases. Mining companies every year purchase huge amounts of material for the construction of ventilation stoppings. This material by the time it is in place in the stoppings will cost the company many thousands of dollars. In addition and more importantly these stoppings are supposed to confine air travel along certain well defined paths into areas where it is needed to provide safe and healthful atmospheres for workmen. The cost of forcing this air through the mine is large and in general increases as the total quantity increases. Consequently, if the stoppings leak, increased cost results and in addition unsatisfactory ventilation may prevail in the mine. Therefore, it is essentia1 to provide the best possible stoppings at an economic cost. When attempting to provide the best stoppings possible at an economic cost, three aspects of the problem must be considered. These are 1) getting the most suitable material for stopping constructions, 2) constructing the stopping so as to get the best performance from the material used, and 3) keeping the cost of stopping construction to a minimum for a suitable stopping. This investigation is concerned with all phases of the problem and has attempted to lay out a study to provide information on all of them. In order to develop information on the best stopping material available it seemed wise, after con- sidering the job a stopping must do, to investigate the following aspects of material used for stoppings: 1) strength in compression, 2) compressibility or yield under load, 3) porosity, and 4) permeability. To provide information on the best manner of construction the following aspects of air leakage through the stopping were investigated: 1) when the stopping is built of dry stacked materials—i.e., the joints are not mortar-laid (See Fig. 1); 2) when the stopping is built of dry stacked material and then plastered on one side (see Fig. 2); 3) when the

Jan 1, 1961

By Joseph A. Holmes

Although Venezuelan production attained a new peak in 1938, passing the 190 million barrel mark for the first time, there was a distinct flattening of the steep upward trend that marked 1937 and preceding years. The annual total of 190,231,780 bbl. was only 31/3 million barrels above the 1937 figure, an increase of slightly less than 2 per cent, which contrasts sharply with the 20 per cent increase of 1937 over 1936. As in the previous year, the Lake Maracaibo fields supplied approximately 73 per cent of the oil produced, Lagunillas remaining the largest single contributor in spite of a 17 million barrel decrease in its annual output. Tia Juana increased its percentage of the Venezuelan total from 14.1 per cent in 1937 to 23.4 per cent in 1938; La Rosa showed little change with 13.7 per cent; Quiriquire in eastern Venezuela was also little changed with 13.2 per cent; Mene Grande, the only other field of real importance, declined from 7.7 per cent of the total in 1937 to 6.6 per cent for 1938. Two new fields, Temblador and Bachaquero, began actively to ship oil during the year, and by November were averaging 7600 and 10,000 bbl. per day, respectively. The former is in eastern Venezuela, and the latter is the most southern of the proven Lake Maracaibo fields. (A map of Venezuela was published in Volume 127 of the Transactions.) Table 1 gives a complete résumé of Venezuelan production by fields for 1937 and 1938, and shows that 1,685,575,663 bbl. had been produced to Dec. 31, 1938. The percentage contributed by each of the principal fields to this total is shown in Table 3, as well as their trends over the past several years. From these data it is apparent that the Maracaibo Basin is the principal source of Venezuelan production, and will probably continue to hold this position for some years. At the year's end 2657 oil wells were producing, of which 2425 were in western and 232 in eastern Venezuela; 36 per cent were on natural flow, 57 ppr cent were pumping, and 7 per cent were on air or gas lift. Out of 523 wells drilled, 507 producers were completed in 1938, five less than in the previous year and nearly 100 less than in 1929. These

Jan 1, 1939

By Joseph A. Holmes

Although Venezuelan production attained a new peak in 1938, passing the 190 million barrel mark for the first time, there was a distinct flattening of the steep upward trend that marked 1937 and preceding years. The annual total of 190,231,780 bbl. was only 31/3 million barrels above the 1937 figure, an increase of slightly less than 2 per cent, which contrasts sharply with the 20 per cent increase of 1937 over 1936. As in the previous year, the Lake Maracaibo fields supplied approximately 73 per cent of the oil produced, Lagunillas remaining the largest single contributor in spite of a 17 million barrel decrease in its annual output. Tia Juana increased its percentage of the Venezuelan total from 14.1 per cent in 1937 to 23.4 per cent in 1938; La Rosa showed little change with 13.7 per cent; Quiriquire in eastern Venezuela was also little changed with 13.2 per cent; Mene Grande, the only other field of real importance, declined from 7.7 per cent of the total in 1937 to 6.6 per cent for 1938. Two new fields, Temblador and Bachaquero, began actively to ship oil during the year, and by November were averaging 7600 and 10,000 bbl. per day, respectively. The former is in eastern Venezuela, and the latter is the most southern of the proven Lake Maracaibo fields. (A map of Venezuela was published in Volume 127 of the Transactions.) Table 1 gives a complete résumé of Venezuelan production by fields for 1937 and 1938, and shows that 1,685,575,663 bbl. had been produced to Dec. 31, 1938. The percentage contributed by each of the principal fields to this total is shown in Table 3, as well as their trends over the past several years. From these data it is apparent that the Maracaibo Basin is the principal source of Venezuelan production, and will probably continue to hold this position for some years. At the year's end 2657 oil wells were producing, of which 2425 were in western and 232 in eastern Venezuela; 36 per cent were on natural flow, 57 ppr cent were pumping, and 7 per cent were on air or gas lift. Out of 523 wells drilled, 507 producers were completed in 1938, five less than in the previous year and nearly 100 less than in 1929. These

Jan 1, 1939

By J. E. Lawver, J. D. Raulerson, Charles C. Cook

The agriculture industry has made great strides during the past decade to increase agriculture yields through increased use of fertilizers. Increased use of fertilizers may prevent, or at least delay, mass starvation due to the alarming increase in world population. Phosphate was added to soil as a plant nutrient in the form of calcined bones at least 2000 years ago (Anon., 1964), and man has used phosphate minerals as a source of fertilization in one form or another for at least 100 years. During 1977 the world produced about 116 Mt of phosphate rock, with about 86% used for fertilizers and another 4% for animal feed supplements. More than three-fourths of the total production comes from the United States, Morocco, and the Soviet Union. From a mineral beneficiation point of view, the major sources of phosphate rock and the methods of beneficiation can be classified as follows: marine deposits not containing appreciable carbonate minerals, marine deposits requiring a francolite carbonate mineral separation, igneous deposits not containing appreciable carbonate minerals, and igneous deposits requiring apatite carbonate mineral separation. [ ] Guano, mostly from Chile and Peru, accounts for 0.1% of the total world production, and the calcium phosphates from Ocean, Nauru, and Christmas Islands and the aluminum and iron phosphates from Brazil and Aruba account for less than 4% of the world production and are thus not considered in this classification (Lawver, et al.). At present, marine phosphorite deposits account for about 75% of the world's production; the igneous deposits account for 20%. The igneous deposits low in carbonate minerals are easily concentrated by crushing, grinding, and apatite flotation. The most important igneous deposits are those of the Kola Peninsula, USSR (Woodrooffe, 1972). The igneous deposits high in carbonate materials are of corn appreciably more difficult to beneficiate, but they have been concentrated by froth flotation for a number of years. An interesting but rather complicated flowsheet of this type is at Phalabonva, in the Republic of South Africa (Lovell, 1976). The Phalaborwa deposit is an igneous complex of pyroxenite with a central core of carbonatite surrounded by a serpentine- magnetite-apatite rock called phoscorite. The phoscorite containing about 10% P2O5, 35% magnetite, and 35% calcium magnesium carbonate is currently being processed. The process involves comminuting the material for fiberation and subjecting it to a copper float using a potassium amyl xanthate as collector and triethoxybutane as a frother followed by a magnetic separation of the tailings to produce a feed for phosphate flotation. This process produces a phosphate concentrate containing greater than 36% P2O5 at a P2O5 recovery ranging from 75 to 80%. Considerable success has been claimed for recovering apatite from carbonate-bearing ores at the Jacupiranga Mine of Serrana S/A (Silva and Andery, 1972). The carbonatite currently being mined contains an average of only 5% P205 and is concentrated using a unique flotation process (Andery, 1968) to yield 96% P205 concentrates. The ore contains about 12% apatite, 5% magnetite, 80% calcite plus dolomite, and minor amounts of phlogopite, olivine, zircon, ilmenite, and pyrochlore. Feed preparation consists of crushing to -31.75 mm (-1 M in.), rod milling in closed circuit with hydrocyclones to about 92% (-50 mesh), and two-stage cyclone desliming of the -50 mesh sands at 20 m. Weight recovery in the deslimed feed is normally 85 to 88% and the corresponding P2O5 recovery is usually about 90%. The deslimed feed is conditioned at 60 to 70% solids for 15 min at pH = 8-10 with 0.6 kg/t of causticized starch for iron oxide and calcite-dolomite depression. The conditioned slurry is diluted to 20 to 30% solids, about 0.2 kg/t of fatty acid or soap collector is added to the conditioner discharge, and the reagentized ore is subjected to rougher-scavenger flotation with additional fatty acid added to the scavenger float. The scavenger concentrate is returned to rougher circuit distributor, and the rougher concentrate froth is subjected to two stages of cleaner flotation to yield a final apatite concentrate analyzing 36 to 38% P205. Flotation recovery of P205 is, in general, above 90% when treating fresh carbonatite. The high-carbonate flotation tails normally analyze 1 % P2O5 or less and are suitable for portland cement production. The marine deposits. Types 1 and 2 of central Florida are representative of enormous reserves of phosphate rock that will undoubtedly account for much of the world's production in the near future. Until very recently the sedimentary deposits high in carbonate minerals (Type 2) have not been considered reserves due to the difficulty in making a francolite-carbonate separation. Although no commercial plant has yet been built to beneficiate Type 2 ore, laboratory and pilot plant data indicate the process is viable. If so, the reserves of Florida and similar deposits throughout the world will be substantially increased. A discussion of the beneficiation of these two types of sedimentary deposits and the relation of the resulting concentrates to the fertilizer industry of the United States is the subject of this paper.

Jan 1, 1981

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970