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By Jerome Alexander

The object of this paper is to show that many of the important phenomena of metals and alloys are due to the facts that, at some stage, metals and alloys, or some of their constituents, are in a colloidal state and that a portion of the metal or alloy tends to remain in this state. The so-called amorphous phase in pure metals is an isocolloid, consisting of colloidal groups of metal molecules that may be dispersed in still more finely subdivided metal; these colloidal particles are not truly amorphous, but may consist, in part, if not entirely, of ultramicroscopic crystals; as a result the expressions amorphous phase and amorphous theory might he replaced by the expressions colloidal phase and colloidal theory. Any substance is in the colloidal state when the constituent particles consist of molecular or atomic groups, whose size varies approximately from about 100 down to about 5pp, that is from just below the limit of microscopic resolvability to the dimensions commonly ascribed to the larger molecules. Colloidality involves no assumption as to the shape, internal structure, or orientation of the colloidal particles; size alone is the critical factor. A colloidal system may therefore contain crystalline groups, or amorphous groups (non-crystalline, random or haphazard clusters), or a mixture of the two. All colloids consist of at least two phases, the subdivided substance, or dispersed phase, and the substance into which this is subdivided, the dispersion medium. It is not necessary that there be any chemical difference between the dispersed phase and the dispersion medium. As molecular forces are extremely powerful, their application may produce marked changes in the physical properties of metals. It is doubtful whether metal in the interior, especially of large masses, possesses the same properties as that on or near the surface, which alone is open to inspection.

Jan 1, 1921

Jan 1, 1920

By Henry Morris

AS STATED last year, in a similar review by David White and the author, any review of the petroleum industry purporting to cover such a wide field can only mention the principal facts. This incompleteness is necessitated not only by the limitations of space, but by the delay in receiving detailed information. The principal feature of the year, in Europe, was a material increase in the consumption of petroleum products, and a notable decline in prices. Although there we relative increases in production in Roumania and Poland, the total did not by any means keep pace with the increase in consumption, which, as usual, was supplied "from America and both the Near and Far East. The interest in Asiatic production, as usual, centers around the Persian fields, which, according to the annual report of the Anglo-Persian Oil Co. published at the close of last year, it was estimated would amount to 3,775,000 tons by the close of the fiscal year, March 1, 1924. Russia also showed an increase in production. In Africa there was nothing of outstanding interest in production, although Egypt showed a decrease and the goverment refinery at Port Said was closed.

Jan 3, 1924

By E. S. Fisher

GRAIN coarsening implies a discontinuous type of grain growth during which a few grains in a fine grained recrystallized matrix grow to large grain sizes at the expense of the matrix. Studies of this phenomenon in various metals1,2 indicate that grain coarsening may result when continuous grain growth in a fine grained matrix is inhibited by either a dispersion of very fine inclusions or by a strong texture. In the former case a period of annealing time exists prior to grain coarsening during which grain growth inhibition is gradually de- creased by dissolution or coalescence of the dispersed inclusions. This mechanism can be made to occur in uranium during anneals at high a phase temperatures. ' A study of some of the factors influencing the kinetics of grain coarsening and the coarse grain sizes in a uranium has led to a method for preparing a uranium single crystals. Previously such single crystals containing considerable substructure were prepared at this laboratory by a phase change method, similar to that described by Cahn.3 Attempts to prepare more perfect single crystals by strain-anneal techniques were unsuccessful. Cahn3- as reported his attempts to apply such techniques to uranium. He proposed that the failure of strain-anneal techniques is basically due to the many twins which

Jan 1, 1958

By Peter Haasen

INDIUM antimonide has the zincblende structure. A possible defect that does not disturb the indium tetrahedron surrounding any antimony atom in this lattice (or vice versa) is obtained when neighboring

Jan 1, 1958

By C. O. Swanson

In the iron ranges of northern Michigan, magnetic data have been used as an aid in geologic field work since the time of the earliest surveys. The presence of complex structures containing magnetic formations, and the general scarcity of exposures, guided the early work into this line of attack, and later field studies tended to place more and more emphasis upon this geophysical relationship, until, at present, the collection of magnetic data is a matter of routine in any areal survey. At first, horizontal deflections of the compass needle were the only data collected. In subsequent surveys, greater dependence was placed on dip-needle readings, which record variations in the intensity and inclination of the earth's magnetic field. Recently the trend has been toward adjusting the instrument so as to reduce the influence of changes in inclination, and using a more sensitive modification, called the Superdip,' in weakly magnetic areas. To a minor extent, the magnetometer has also been employed. The object of this paper is to present the writer's experience with magnetic data in this region. The conclusions are based on work covering a period of 10 years, and spread over nearly all of the iron ranges and a large part of the intervening areas. The viewpoints expressed are purely geological ones. In other words, any opinion as to the usefulness of a certain relationship is based upon the writer's experience with it as a guide in interpreting the structures of this region, and not upon its soundness theoretically, nor its usefulness under other conditions. A very brief summary of the conclusions is as follows. The most important step is that of collecting the magnetic data. This requires a suitable adjustment of the dip needle, and sufficient readings to accurately portray the variations in the magnetic field, which are apt to be irregular. Once the readings are taken and plotted in some clear fashion, the interpretation of them is usually merely a matter of observing their relation-

Jan 1, 1934

By A. A. Burr, D. G. Ebeling

The effects of casting texture, grain orientation and grain size upon the performance of Alnico permanent magnets is described. Single-crystal specimens were produced by special sintering and grain coarsening techniques to study the effect of crystal orientation. In addition to texture and orientation effects, an analysis of the results indicates that the permanent magnet performance is impaired by a refinement of the grain size. AN excellent historical review of the development of Alnico permanent magnets has been prepared by Bozorth.1 The desirable permanent magnet characteristics of Fe-Ni-A1 alloys were discovered in 1932 by Mishima.2,3 The work of Ruder' showed that the alloys were age-hardenable, and Betteridge5 defined the best composition and heat treatment for the magnetically isotropic alloy known as "Alnico 3." Horsburgh and Tetley0 increased the energy product by the addition of cobalt and copper, "Alnico 2," and Oliver and Sheddon7 demonstrated that cooling in a magnetic field improved the residual induction of this alloy. Jonas8,9 then disclosed the great practical benefits of heat treating an alloy of higher cobalt content in a magnetic field and the resulting alloy, "Alnico 5," has become the standard of the industry. This paper describes the fundamental aspects of a procedure which can be used to further improve the properties of these anisotropic permanent magnet alloys. A study of the casting techniques used in the production of anisotropic Alnico permanent magnets indicated that the magnetic quality was affected by the as-cast macrostructure. Improved performance was observed in magnets containing a high percentage of columnar grains whose long axes were parallel to the magnetic axis of the casting. McCaig10 studied the effect of such columnar grain structures upon the magnetostriction characteristics of similar alloys, however no data was presented showing the effects on other magnetic properties. The following paragraphs describe two experiments which were conducted to determine the effect of various grain orientations upon the energy product. Special composite molds were prepared of highly conductive and highly refractive components to remove the heat of solidification from the casting in a controlled manner. Representative macrostructures produced by these techniques are shown in Fig. 1, along with the relative volumes of favorably oriented columnar grains. The alloy, Alnico 5, has the highest permanent magnet performance of any commercial magnet material. It has the nominal weight composition of 8 pct Al, 14 pct Ni, 24 pct Co, 3 pct Cu, and 51 pct Fe. A heat of this material was cast into molds producing the type A and B grain structures shown in Fig. 1 and pairs of the resulting magnets were placed in heat-treating boats so as to eliminate any biasing effects of boat position. After a standard heat treatment the type A magnets, with 16 pct of the volume composed of favorably aligned grains, had a maximum energy value of 3,940,000 gauss-oersteds, while the type B magnets with 73 pct aligned grains averaged 5,090,000. This large im-

Jan 1, 1954

By M. R. J. Wyllie, Michael A. Torcaso

With the continued deep drilling of today, increasing numbers of high pressure and high temperature gas-condensate reservoirs are being discovered. Correspondingly, the ranges of properties of gas-condensate reservoir fluids are also being increased. The literature1*'." contains several excellent reviews of the property ranges in presently known condensate reservoirs. When one examines these property ranges, it becomes apparent that the need for reliable data is great if the engineer is to evaluate properly or appraise a gas-condensate reservoir. It is the purpose of this paper to present phase-behavior data that will point out some of the important variables that influence recovery from gas-condensate reservoirs produced by pressure depletion. All these variables may be resolved into two major categories: the hydroc:arbon composition of the reservoir fluid and the physical properties of the reservoir. But the variables which we will consider are those which are usually determined from well tests shortly after discovery and are, consequently, readily available to the engineer. They are as follows: (1) the producing separator gas-stock-tank liquid ratio, (2) stock-tank liquid gravity, and (3) reservoir temperature. Laboratory depletion studies have been performed on several reservoir fluids to illustrate the effect of changes in the cronsidered variables upon ultimate recoveries. The deviation factors, Z, of a series of reservoir fluids were determined experimentally to illustrate their order of magnitude and their effect upon the calculation of in-place reserves existing at high pressurcs and temperatures. The procedures followed in conjunction with the performance of these studies and their associated calculations are illustrated in Fig. 1. For the purpose of this paper, the depletion recoveries are expressed only in terms of pcr cent of initial stock-tank liquid, with the abandonment pressure assumed to be 500 psig. VARIATION OF RECOVERY WITH INITIAL PRODUCING SEPARATOR GAS-STOCK-TANK LIQUID RATIO The producing separator gas-stock-tank liquid ratio has long been one of the principal criteria in assumptions and generalized correlations' used for the estimation of ultimate recovery from gas-condensate reservoirs. Fig. 2 presents a plot of the cumulative recovery of stock-tank liquid at abandonment as a function of the initial producing separator gas-stock-tank liquid ratio. The graphical illustration represents the results of 44 laboratory depletion studies performed on actual gas-condensate fluids. These data are presented not only to illustrate the general trend of ultimate recovery increase with initial producing ratio increase but to emphasize the considerable variation in possible recovery at any given producing ratio. Table 1 presents the properties of two actual reservoir fluids chosen to illustrate the approximate extremities of producing ratios for gas-condensate systems. The fluids designated as A and B exhibited initial producing ratios of 3,400 and 114,000 scf/bbl, respectively. Fig. 3 presents a graphical comparison of the cumulative stock-tank liquid recoveries, calculated from the well-stream compositions and produced volumes for each fluid during depletion. It is to be noted that Fluid A exhibited a recovery of only 16.5 per cent when produced to an assumed abandonment pressure of 500 psig while the corresponding recovery for Fluid B was calculated to be 62.2 per cent. This difference in recovery, which exemplifies the general trend of recovery increase with initial producing ratio increase, is readily explained by consid-

By H. C. Chang, N. J. Grant

REEP studies and measurements in most in-V> stances are based on a relatively gross gage length. Even in some recent theoretical studies on the mechanism of creep, changes were followed by means of X-rays and metallography without regard for the behavior of the individual grains and grain boundaries.'" Analytical studies of creep have frequently indicated that more than one competing process is operative and that the ultimate creep performance depends on the effects of temperature, time, and strain rate as well as grain size.'-" he grains and grain boundaries are known to respond differently to these variables but the extent of the response is still little known, especially in poly-crystalline materials where the relative orientations of grains and grain boundaries are important. This paper reports some experimental observations of the behavior of the grain boundaries and their effect on the deformation in the grains. High purity aluminum was used to avoid complications of aging reactions, second phase, inclusions, etc. Experimental Procedure A small vertical nichrome wound furnace was built to permit direct loading on the test specimen. This furnace is capable of operating up to about 1300°F with reasonable temperature distribution. A ground rectangular quartz window, 1.25x0.5 in., is imbedded in the external stainless steel tube to permit observations of the creep process with a microscope. An argon atmosphere ,was provided to prevent oxidation. The quartz window caused a temperature gradient between the back and front surfaces of the specimen of 15" at 700°F. The temperature gradient could be cut down to 3°F along the length of the specimen by adjusting shunts across the furnace windings. An ordinary metallurgical microscope with a working distance of 14 mm was rebuilt so that it could be moved in three mutual perpendicular directions. Visual examination could be made with either a 30X eyepiece or a 15X filar eyepiece. Using an objective of focal length 24.3 mm and a numerical aperture 0.20 a total magnification of 120X or 240X could be obtained. High purity aluminum rated at 99.995 pct was supplied by the Aluminum Co. of America as % in. then the gage portion was further machined to 3/16 in. diam. The ends were Y4 in. diam and threaded to fit available specimen holders. Two opposite flat surfaces of the gage portion were obtained by milling, giving final dimensions of the gage portion of 3/4x3/16x3/32 in. Machined specimens were first electropolished in Jacquet's solution.' Reference marks were produced by pressing a thin sewing needle into the surface of the specimen. The specimen was then annealed at 900°F for 24 hr and at 1150°F for 12 hr. Typical macrostructures of specimens treated in this manner are shown in Fig. 1. The range of the grain size was 1 to 5.5 mm (see Fig. l), but most of the grains were of 2.5 mm and went through the whole thickness of the specimen. The specimen was re-electropolished and etched electrolytically to reveal the grain boundaries. In order to reveal the orientation difference of the grains, etch pits were produced on the surface of the grains by etching in a mixture of hydrochloric and nitric acids (HC1, 45 pct; HNO,, 10 pct; H,O, 45 , by volume). The specimens were very carefully put into the holders and furnace; yet even with this care, fine slip lines were developed on the specimen surface.

Jan 1, 1953

By William B. Phillips

The concentration of natural magnetites has been carried on in this country for several years, and more or less information has been collected on the subject. Various inventors, availing themselves of the magnetism which is inherent in such ores, have devised machines for separating the impurities from the ore by means of the electric current; and a greater or less degree of success has rewarded their painstaking and persevering efforts. We are now fairly in position to judge of the value of the process as applied to such material. It is not my purpose to speak of this matter further than may be required by the emergencies of the case. I shall assume that most engineers and metallurgical chemists are already acquainted with what has been done at the Chateaugay mines, at Mineville, at the Benson mines, at the Weldon and Ogdensburgh mines, and at Cranberry; although, at this latter place, there has not been so much done as we could wish. I shall not now speak of the various types of separators. From the time of William Fullarton, to whom was granted an English patent, in 1792, for separating iron-ore by the application of magnetic attraction, down to the present time, a great. many devices have been suggested, and a great many patents taken out for this purpose; but it is not necessary now to enter upon a discussion of their merits. Perhaps, at some future meeting of the Institute, after we shall have experimented further with some of the machines on the market, there may be an opportunity to contribute something to the current knowledge of the efficiency and economy of separating-machines. In this paper I propose to give, as briefly as possible, the results already reached in converting a non-magnetic ore into magnetic ore, and then concentrating it over a magnetic separator of the alternate-polarity type. I am aware of the work

Jan 1, 1896

By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau's pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115' C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg's investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,' using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By C. P. Karr

FOR several years, the Bureau of Standards has been working in cooperation with an Advisory Committee on non-ferrous metals on various phases of the production and testing of zinc bronzes. The work has dealt, especially with the type of metal known as "Admiralty bronze" in England and as "Government bronze" in this country and consisting of 88 copper, 10 tin, and 2 zinc. Several reports have been made on this subject and these should be considered in connection with this paper.1 FIRST SERIES OF FIVE FOUNDRY TESTS A very brief summary of the first series of five foundry tests has been made,2 but for the sake of clearness the results are given here in different form. The five foundries cooperating in this investigation were: Ohio Brass Co., Mansfield, Ohio; Titanium Alloy Mfg. Co., Niagara Falls, N. Y.; Packard Motor Car Co., Syracuse, N. Y.; National Cash Register Co., Dayton, Ohio; Bureau of Standards, Washington, D. C. The object of the work was to determine whether uniform results could be obtained with this alloy in different foundries working under definite instructions. One of the participating foundries prepared, from virgin metal, a stock of ingots of the composition 88 copper, 10 tin, 2 zinc, and at the same time poured nine test bars from this melt of virgin metal. The results of the physical tests of these bars are shown in Table 1. Examination of this table shows that the highest and most nearly uniform results were obtained when the virgin metal was cast flat in chill molds and the lowest and most variable results were encountered when it was cast vertical in green-sand molds. In this, as in all other tables, the mean

Jan 9, 1919

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943

By John N. Hobstetter

IT is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spontaneous diffusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow,' Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Becker1 in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r. beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration, The increase in free energy per mole accompanying the formation of a nucleus which is just stable, ?fe, is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. THE NATURE OF THE NUCLEUS It is necessary to have rather detailed knowledge of the nature of a nucleus if ?Fe is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown3

Jan 1, 1948