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By Arne F. Westgren

X-ray analysis and single-crystal study have been utilized in recent years as a new means of following constitutional changes in alloys. If such transformations can be suppressed by rapid cooling, they can be followed at room temperature in a particularly convenient manner. In the following we shall consider changes in solubility and polymorphic transformations with particular reference to phenomena of the age-hardening type. Finally a thermodynamic viewpoint is developed for examining such transformations. Changes in Solubility 1. Determinations of solubility limits in the solid state which show decreasing solubility with falling temperature are made as follows: A series of alloys extending into the heterogeneous region is prepared and quenched fromas high a temperature as possible, whereupon their lattice parameters are determined. Then one or more alloys are quenched from temperatures at which they are heterogeneous and their lattice parameters likwwise determined. For the purpose of determining the parameter the apparatus shown in Fig. 1 has been very useful for it produces sharp films in a short time which can be accurately read. High-order reflections (interferences) from the object are recorded on a film which is placed exactly perpendicular to the X-ray beam. The specimen usually has the shape of a small round bar.l Fig. 2 shows a selection of such exposures of silver-rich Cu-Ag alloys, and Fig. 3 gives the measurements made from these films. Fig. 4 gives the solubility curve which results.2 This curve is shifted to lower concentrations than the curve that is obtained from metallographic or physical methods. The X-ray method unquestionably gives more reliable data

Jan 1, 1931

By Edwin R. Phelps, Charles W. Porterfield

BACKGROUND OF SURFACE MINING Surface mining refers to the process of removing the material (over- burden) overlying a coal seam and exposing the coal so that it can be loaded out and conveyed by trucks or other methods to the preparation plant or other facility. Surface mining has not always been important in the coal industry. In the early 1900s, almost all of the coal mined in the United States was mined by underground methods. In 1900, about 192 Mt (212 million st) of bituminous coal mere mined and less than 1% was mined by surface methods. The development and use of larger equipment has allowed surface mining to gain prominence throughout the years. Table 1 shows the total production of coal by mining method in the United States for ten-pear periods since 1920 and indicates the growth of surface-mined coal production. Surface mining will undoubtedly continue to account for a large percentage of the coal production in the US for many years because: 1) The capacity of surface mining excavators has continued to increase. Today, mining companies are using shovels (see Fig. 1) which are able to move up to 137.6 m3 (180 cu pd) in each bite and draglines (see Fig. 2) which move up to 168.2 m3 (220 cu pd) in each bucketful. 2) Increasing tonnage from the thick western coal seams is being produced by surface mining methods. 3) Surface mining has normally had lower costs and a better safety record than underground mining. 4) Surface mining normally recovers a much higher percentage of the coal reserve than can recovered by underground mining. 5) Some coal measures call best be extracted by surface mining

Jan 1, 1981

By H. K. Shearer

North Louisiana (including all townships north of the Louisiana base line) had a year of normal development in 1940, marked by the discovery of two shallow oil fields producing from the Wilcox formation in La Salle Parish and a large increase in drilling in the old Caddo shallow field. This renewal of shallow drilling activity led to a somewhat unexpected increase in the number of wells drilled, although the total footage and average depth continued to decline, as in several preceding years. Well completions and depth statistics for 1940, with previous years for coinparison, are as follows: Wildcat producers in 1940 include the discovery oil wells in the Olla and Nebo fields; also three gas wells in the vicinity oi the Olla field and a shallow gas well, which opened a new field or extension in the Greenwood area of Caddo Parish. This table illustrates the lack of important deep discoveries since 1937, in which year the Rodessa, Lisbon and Cotton Valley fields were being actively developed. Operators have been forced to return to the old type of shallow drilling, which necessarily means smaller producing wells. Oil production in 1940 was 24,381,760 bbl., a decrease of 867,880 bbl. from 1939, or 3.44 per cent. The newly discovered fields of La Salle Parish produced over a million barrels, and other increases worthy of note were at Cotton Valley, Caddo, Sligo and Sugar Creek. The greatest decrease was again at Rodessa, although this remains the principal producing field. Geological Names Revised Deep drilling during 1940 did not provide a great deal of new geological information. However, by agreement of a majority of the members of the Shreveport Geolog- ical Society, the names of some of the Lower Cretaceous formations have been revised in the interest of greater clarity and in order to make the descriptions agree better with the facts discovered in recent years. The geological section is discussed in detail and reasons for changes in nomenclature are stated in a recent publication by Ralph W. Imlay. Although not yet in universal use among field men, the new names are employed in this report and accompanying tables, as

Jan 1, 1941

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

By F. Cadena

Hiwassee Darn, now under construction by the Tennessee Valley Authority on the Hiwassee River, a tributary of the Tennessee River, will require aggregate for approximately 800,000 cu. yd. of concrete. Near the damsite deposits of natural sand or gravel are not available and graywacke, a rock that is found in abundance, suggested itself as a likely source of manufactured aggregate. Graywacke is a metamorphosed sandstone composed principally of a mixture of quartz (65 per cent), mica (25 per cent), and feldspar (10 per cent). Other minerals are present in negligible amounts. The rock varies in different parts of the quarry from very fine to a coarse grain containing particles of about ¼ in. maximum size, although the bulk of the deposit is medium grain. Extensive tests showed that graywacke would be suitable as a source of both coarse and fine aggregates. The aggregate plant available for use at Hiwassee Dam consisted of the coarse-aggregate and sand plant used on the Norris project. The coarse-aggregate plant had also been used at Chickamauga Dam. Although most of this plant equipment is now in use at Hiwassee, the present flowsheet is not only different from that at Norris and Chickamauga but is also unique as compared to the flowsheet of the average crushed-stone aggregate plant. It is hoped that this paper will show the importance of proper arrangement of equipment if the optimum in flexibility and capacity is to be attained. Flowsheet Rock is ioaded by 3-yd. electric shovels into 12-yd. dump trucks, which carry the rock to the primary crusher, a 42-in. Superior McCully gyratory unit set at 4¾ in. (Fig. 1). The primary crusher discharges directly onto a 42-in. inclined belt conveyor, which carries the product to a surge storage pile with a maximum live storage capacity of approximately 3000 tons. A concrete tunnel under this storage pile houses the feed end of a 36-in. belt conveyor (conveyor B) fed by a 36 by 66-in.

Jan 1, 1942

By Allen D. Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITON OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939

By H. J. French

WITHIN the past few years, particularly because of the rapid growth of the airplane industry during the war, considerable attention has been paid to the manufacture of light-wall cold-drawn seamless and welded steel tubing for structural purposes. While the manufacture of such tubing is not, in itself, a difficult matter, some difficulties have. been encountered in producing the same under specifications requiring definite physical properties. It is the purpose of this paper to describe the methods of manufacture and the properties that may be obtained by such methods for tubing coming within about ½ to 2 in. (12.7 to 50.8 mm.) outside diameter and 10 to 22 Birmingham wire gage (0.134 to 0.028 in. wall thickness). Such tubing is largely used as structural material in the aircraft industry, and it is of the utmost importance that the physical and chemical properties should be known, and also that the various factors entering into the manufacture should be under such control as to allow these properties to be varied and held within definite limits. In general, tubing may be divided into four classes: namely, specialty tubing, such as riveted-sheet or plate, lock jointed, etc.; brazed tubing; welded tubing; and seamless tubing. Welded tubing may be divided into hot product, such as lap welded and butt, welded, and cold product, such as acetylene and electric welded. Seamless tubing may be hot rolled or cold drawn.

Jan 9, 1919

By E. S. Hutchinson

The subject of the influence of coal-dust in mine-explosions has received considerable attention both in England and on the continent of Europe, but until the recent disaster at Pocahontas, Va., it seems not to have been of special interest to engineers in this country. The reason, perhaps, is that most of our bituminous mines are worked by short shafts, slopes and drifts; few have been specially dry; and the explosions that have occurred could readily be traced to fire-damp with 110 complicated circumstances. The object of the present paper is to bring together, for the convenience of members of the Institute, the principal English opinions upon this important subject. Messrs. Lyell and Faraday, in their report to the Home Secretary," in England, on the Haswell Colliery explosion in 1844, seem to have been the first to point out that dust fed the flame originating in a

Jan 1, 1885

By H. K. Shearer

North Louisiana (including all townships north of the Louisiana base line) had a year of normal development in 1940, marked by the discovery of two shallow oil fields producing from the Wilcox formation in La Salle Parish and a large increase in drilling in the old Caddo shallow field. This renewal of shallow drilling activity led to a somewhat unexpected increase in the number of wells drilled, although the total footage and average depth continued to decline, as in several preceding years. Well completions and depth statistics for 1940, with previous years for coinparison, are as follows: Wildcat producers in 1940 include the discovery oil wells in the Olla and Nebo fields; also three gas wells in the vicinity oi the Olla field and a shallow gas well, which opened a new field or extension in the Greenwood area of Caddo Parish. This table illustrates the lack of important deep discoveries since 1937, in which year the Rodessa, Lisbon and Cotton Valley fields were being actively developed. Operators have been forced to return to the old type of shallow drilling, which necessarily means smaller producing wells. Oil production in 1940 was 24,381,760 bbl., a decrease of 867,880 bbl. from 1939, or 3.44 per cent. The newly discovered fields of La Salle Parish produced over a million barrels, and other increases worthy of note were at Cotton Valley, Caddo, Sligo and Sugar Creek. The greatest decrease was again at Rodessa, although this remains the principal producing field. Geological Names Revised Deep drilling during 1940 did not provide a great deal of new geological information. However, by agreement of a majority of the members of the Shreveport Geolog- ical Society, the names of some of the Lower Cretaceous formations have been revised in the interest of greater clarity and in order to make the descriptions agree better with the facts discovered in recent years. The geological section is discussed in detail and reasons for changes in nomenclature are stated in a recent publication by Ralph W. Imlay. Although not yet in universal use among field men, the new names are employed in this report and accompanying tables, as

Jan 1, 1941

By Robert A. Cook

In the increasing struggle to cheapen the cost of our iron and steel products a great deal of attention lias been given to economies in the manufacture of coke; and while but little lias been accomplished in this direction in the United States, the narrow margin between cost and market-price, which has obtained here for the past few years of continuing manufactur ing depression, has brought the coke-maker face to face with the problem, how to save, and benefit by it, the hitherto waste products of distillation. I These may be summed up under three heads, generally rank ing, in value, in the following order: 1. Ammonia salts.. 2. Oil- or tar-products. 3. Gas. There are cases in which the last may assume the position of greatest importance. The greatest obstacle encountered by the American coke maker, on investigating the subject, has been the apparent necessity of discarding his existing plant of bee-hive ovens, and erecting an entirely new and very expensive system of retort ovens, against the product of which Be has probably been prejudiced from his earliest knowledge of the subject. The object of this paper is to bring prominently before our coke-experts a brief history of the development at Sheffield, England, of a most successful system of the utilization of by products in connection with all already existing plant of bee hive ovens. This system has now been in satisfactory operation for about five years, and is applied to a series of blocks of ovens, comprising-about 140- in all At this plant, belonging to the well-known firm of Newton,

Jan 1, 1897

By H. Hansen, A. U. Seybolt, P. Yurcisin, B. W. Roberts

The Bi-Mn phase diagram in the region near BiMn was investigated, using principally thermal analysis and changes in magnetization with temperature. Of chief interest are the findings related to the magnetic transformation in Bi-Mn. THE Bi-Mn system is of both theoretical and practical interest because of the occurrence of the compound BiMn which exhibits unusual ferromagnetic properties. Because the Bi-Mn phase diagram reviewed by Hansen' (see Fig. 1) in 1936 is based on work done by BekierY in 1914 and by Siebe" in 1919, which left considerable doubt about the nature of the diagram. it appeared desirable as an aid in understanding the alloying characteristics and magnetic behavior to examine the pertinent regions of the phase diagram. The most interesting reaction is the peritectic at 445°C which forms BiMn by the reaction: Liquid + Mn(sulfield) ? BiMn(sol field) There is also a eutectic at 262° C between pure bismuth and BiMn. Hansen draws in BiMn dotted, since in 1936 evidence for its existence was uncertain. Experimental Materials—Preparation of Alloys Electrolytic manganese of about 99.97 pet purity and bismuth of 99.99 + pet purity were used as starting materials.

Jan 1, 1957

By F. Cadena

Hiwassee Darn, now under construction by the Tennessee Valley Authority on the Hiwassee River, a tributary of the Tennessee River, will require aggregate for approximately 800,000 cu. yd. of concrete. Near the damsite deposits of natural sand or gravel are not available and graywacke, a rock that is found in abundance, suggested itself as a likely source of manufactured aggregate. Graywacke is a metamorphosed sandstone composed principally of a mixture of quartz (65 per cent), mica (25 per cent), and feldspar (10 per cent). Other minerals are present in negligible amounts. The rock varies in different parts of the quarry from very fine to a coarse grain containing particles of about ¼ in. maximum size, although the bulk of the deposit is medium grain. Extensive tests showed that graywacke would be suitable as a source of both coarse and fine aggregates. The aggregate plant available for use at Hiwassee Dam consisted of the coarse-aggregate and sand plant used on the Norris project. The coarse-aggregate plant had also been used at Chickamauga Dam. Although most of this plant equipment is now in use at Hiwassee, the present flowsheet is not only different from that at Norris and Chickamauga but is also unique as compared to the flowsheet of the average crushed-stone aggregate plant. It is hoped that this paper will show the importance of proper arrangement of equipment if the optimum in flexibility and capacity is to be attained. Flowsheet Rock is ioaded by 3-yd. electric shovels into 12-yd. dump trucks, which carry the rock to the primary crusher, a 42-in. Superior McCully gyratory unit set at 4¾ in. (Fig. 1). The primary crusher discharges directly onto a 42-in. inclined belt conveyor, which carries the product to a surge storage pile with a maximum live storage capacity of approximately 3000 tons. A concrete tunnel under this storage pile houses the feed end of a 36-in. belt conveyor (conveyor B) fed by a 36 by 66-in.

Jan 1, 1942

By L. J. Klinkenberg

It is pointed out that the current concept of pore size distribution is not unequivocally defined and that different methods aiming at a determination of such a distribution therefore do not lead to the same results. A pore size distribution should not be based on the idea that a core should, under all circumstances, behave as a bundle of straight non-interconnected capillaries of the same pore size distribution. This is illustrated by calculations and experiments on the displacement of miscible liquids. INTRODUCTION The introduction of the concept of pore size distribution has been an attempt to characterize the intricate geometry of the flow channels in porous media. As pores in a porous medium are interconnected it is impossible to describe exactly what is meant by a "pore" and, therefore, the term pore size distribution requires further amplification. In the visual method for the determination of pore size distribution "the pore" is considered to be the hole between the grains as observed on thin sections or on a polished surface of the rock under a microscope. In all other presently known methods,1,2 a displacement process is studied and it is ascertained what as- semblaae of straight cylindrical capillaries would show the same behavior. The distribution of the capillary diameters of this assemblage is said to represent the size distribution of the pores of the actual porous medium. From the foregoing it is already apparent that it is useless to try to decide which process or which method of investigation leads to a "correct" pore size distribution. To illustrate this further a displacement process in which a fluid is displaced by another miscible with it will be discussed and the results will be interpreted in terms of a pore size distribution. DISPLACEMENT EXPERIMENTS WITH MISCIBLE LIQUIDS OF NEARLY IDENTICAL VISCOSITY AND DENSITY Interpretation in the Form of a Pore Size Distribution If distilled water is displaced from a homogeneous unconsolidated sand pack by, for instance, a dilute solution of NaCI, the breakthrough recovery i.e., the amount of distilled water produced at the moment the first trace of NaCl can be detected in the effluent water, is between 95 and 100 per cent of the pore volume of the pack. This result can be understood by following in imagination the course of one particle of the liquid. Imagine a length, ?l, at the end of which a liquid particle has an independent chance of a renewed choice of pores of different diameters. In other words, the particle has a choice of traveling time, at, for any length ?l; instead

Jan 1, 1958

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

President MRS. HARRISON SOUDER south Paramus Road Ridgewood, N. J. First Vice-president MRS. ROBERT HURSH New York N. Y. Second Vice-president MRS. RICHARD LLEWELLYN LLOYD Great Neck, L. I'. N. Y. Third Vice-president MRS. PERCY E. BARBOUR New York N. Y. Fourth Vice-president MRS. E. P. MATHEWSON Tucson Ariz.

Jan 1, 1937

By J. A. Kitchener, J. P. Anfruns

Measurements have been made of the rate of capture of single particles of strongly hydrophobic, surface-methylated, quartz, of sizes ranging from 12 to 40 µm diam., by single rising bubbles of diam. 0.5 to 1.1mm. The results agree closely with the theoretically calculated hydrodynamic collision rates, indicating that, in this system, every collision results in capture and retention of a particle.

Jan 1, 1976

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By Guillermo Zuloaga

THE iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana High-lands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Profes-sor Lindgren and Professor Newhouse.

Jan 1, 1933

By W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 31..4-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 19:36, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photo-graphed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods.

Jan 1, 1937

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967