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By Frederick L. Knouse

THE south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19° to 21° and 30" south latitude; and from 40° to 41° and 30" west longitude. This includes the central part of Espirito Santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Martines, Espirito Santo (Fig. 1). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through Vitoria; and by the E. F. Minas-Vitoria and E. F. Central do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatites, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. EARLY OPERATIONS Mining of quartz crystal in this region began in 1928, and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crystal as small as 10 grams. Since 1941 only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of loo grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, or Domingos Martines, Espirito Santo. Marketable quartz crystal was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large cores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. PRODUCTION The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1946

By Thomas E. Wayland

AN isopachous map is one on which lines connect points of equal thickness of a given unit. This type of map is used by the Florida Phosphate Project of the U. S. Geological Survey to represent the economic phosphate deposits known as matrix and the waste material, or overburden, that overlies the matrix. The top of the bed on which the phosphate was deposited is known as the basement and a subsurface contour map of this old buried erosion surface is known as a basement map. Recent experiments have been made in preparing maps that show tonnages and grades of the phosphate content of the matrix.

Jan 11, 1951

By F. B. Plummer

THE physical properties of oil-producing sands, such as grain size, porosity, and permeability, are becoming more and more important in petroleum production engineering as oil fields are being repressured and rejuvenated. A number of excellent papers have been published recently on all three of these properties. Faucher, Lewis and Barnes1 give a com-plete survey of the work done through 1932 and contribute also much information on sands that they themselves have examined. Muskat and Botset,2 Wykoff, Botset, Muskat and Reed,3 Hurst,4 and Muskat5 have contributed a great deal to the theory and actual measurement of flow of liquids and gases through porous media. Muskat and Botset have measured the permeabilities of different sands with gases and liquids. They find that the radial is always slightly under the linear permeability. However, in most of the previous experiments small samples of the sand were used, and the method of production of fluid or gas through the sands has not been very close to actual oil-field conditions. In addition, so far as the authors are aware, no measurements of linear and radial permeabilities have been made simultaneously under exactly the same conditions. The multiple permeability apparatus described here is a part of the equipment being acquired by this laboratory for thorough investigation of the physical properties of producing sands. It possesses certain advantages for comparative studies of liquid flow. Additional data and descriptions of other instruments will follow in papers to be written later on. The essential features of the permeability apparatus are as follows:

Jan 1, 1934

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By Joseph Kaye Wood

A metal is said to be overstrained when it is deformed beyond the elastic limit at a temperature well below the critical range, as in cold working. Quantitatively, overstrain might be considered as that part of the total elastic deformation of the piece of metal, left over after the external load is removed, that added to the permanent deformation due to plastic action will give the total permanent deformation. Ordinarily the effects of this phenomenon, which vary with the internal residual stress probably in accordance with Hooke's law, are more noticeable when the yield point of the metal is exceeded, but they probably also exist to a smaller degree when the load is just large enough to cause the least amount of permanent set. These effects, which we recognize as the result of overstrain, are as follows: 1. An apparent increase of the elastic limit in tension and a decrease of the elastic limit in compression, provided the external load is tensile. The reverse is true when the load is compressive. 2. An elastic after-effeet in which time and temperature are important factors. 3. A state of imperfect elasticity in which Hooke's straight line becomes slightly curved, giving rise to an hysteresis loop. 4. In addition to the apparent increase in the elastic limit, such properties as the hardness, ultimate strength, and resistance to fatigue failure are increased, provided the overstraining has not been carried far enough to make the metal brittle. 5. Correspondingly the ultimate elongation, reduction in area, magnetic quality, ratio of endurance limit (fatigue breaking stress) to elastic limit, and resistance to season cracking (in certain copper alloys) are decreased. The question naturally arises: how do these changes in the properties of a metal resulting from overstrain influence our method of design? The fact that most of the desirable qualities are increased makes overstraining a favorable process, from an engineering standpoint; but on the other hand, the loss of such qualities as perfect elasticity and complete

Jan 1, 1924

By Walter Bradley

MINING by hydraulic process of the important gold-bearing gravels of the Sacramento Valley in the basins of the Yuba, Bear and American rivers began in 1853, and continued at an ever-increasing rate for 30 years. In its most active days it reached an annual production of $15,000,000, and averaged $10,000,000 per year over the 30 years. During that period no provisions were made to prevent the debris from being dis-charged into the water courses, and ultimately large quantities of silt, sand and gravel were washed down to the lower valleys; filling channels, causing overflow of agricultural lands and difficulty in maintaining navigable depths in the Sacramento River. Agitation and suits filed because of these damages finally resulted in the injunction decision of Judge L. B. Sawyer,1 in the U.S. Circuit Court, Jan. 23, 1884, which closed down practically all hydraulic mining operations not having means to restrain their debris. In 1893 (approved March 1, 1893), Congress passed the act introduced by Representative Anthony Caminetti, of California, creating the California Debris Com-mission, composed of three officers assigned from the Engineer Corps of the U.S. Army, and since that time it has been legal and possible within the drainage systems of Sacramento and San Joaquin rivers to conduct hydraulic mining of gold-bearing gravels behind dams built under this commission's permit and supervision. In the watersheds of the Trinity and Klamath rivers, which flow directly to the Pacific Ocean and do not affect navigation or agriculture, operating permits from the California Debris Commission are not required. There is a measure of restriction there, however,. through what is known as the Trinity and Klamath River Fish and Game Dis-trict. Chap. 215, Stat. 1931, in order to secure relatively clear water for the fishing season, provides that between July 15 and October 15 each year there must not be discharged into these rivers debris that will cause a turbidity greater than a content of 50 parts per million in the

Jan 1, 1936

By Zay Jeffries

TUNGSTEN has the highest melting point of all the known metals, namely 3350° C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely. brittle and fragile at room temperature, and when possessing a fibrous structure it maybe ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and. ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given.

Jan 6, 1918

By J. G. Richardson, K. H. Coats

During the initial growth of a gas bubble in an aquifer storage reservoir the injected gas tends to override the water. The resulting low displacement efficiency and high rate of gas travel down-structure make it difficult to maintain water-free production. This paper illustrates the use of two-dimensional, two-phase calculations to simulate this gas-water displacement. Calculations were performed for a stratified aquifer and for several homogeneous sands differing in permeability, porosity and thickness. Results are discussed and compared with performance predictions obtained from the simpler Buckley-Leuerett and Dietz formulas. This comparison indicates the necessity for the two-dimensional calculations in realistically simulating the gravity override of the water by injected gas. INTRODUCTION In recent years natural gas has been stored near markets in aquifers where insufficient storage capacity is available in depleted fields. Operators of these aquifer storage reservoirs have encountered technical problems relating to the gas-water displacement accompanying initial growth of the gas bubble. Injected gas tends to override the water, with a resultant low displacement efficiency and high rate of gas travel down-structure toward spill points. Low displacement efficiency makes if difficult to sustain water-free gas production. Sometimes the fingering of gas down-structure may be so pronounced that the injection rate must be severely curtailed, which excessively lengthens the time required for bubble growth. This paper is concerned with estimating — for given aquifer characteristics and fluid properties — the displacement efficiency, rate of gas movement down-structure and rate of gravity drainage of water behind the gas front. Several published articles relate to simulative capability necessary to handle this problem. The Dietz formula1 and Buckley-Leverett2 method have some applicability to the problem; Woods and comer3 reported one-dimensional, radial calculations which accounted for the two-phase flow of gas and water. Most recent research directed toward understanding aquifer behavior in relation to gas storage has concentrated on single-phase flow in aquifer.4 Douglas, Peaceman and Rachford5 presented a method for calculating multidimensional two-phase flow in reservoirs; their method has been applied in work reported by Nielsen and Tek,6 Blair and peaceman7 and Goddin.8 Refs. 5 and 7 show comparisons between experimental data and calculations similar to those employed here. One purpose of this paper is to illustrate the use of two-dimensional, two-phase flow calculations in simulating the difficult problem of water displacement by gas in a vertical cross-section. The pronounced fluid density and viscosity differences combine with the disparity in horizontal and vertical dimensions of the cross-section to pose one of the more difficult problems in reservoir simulation. The calculations described account for capillary and gravity forces, relative permeability and reservoir heterogeneity. An example reservoir is described and calculated results are presented for a variety of injection rates and values of permeability, reservoir thickness and dip angle. A second purpose is to compare the two-dimensional calculations with results obtained from the Buckley-Leverett and Dietz formulas. For this reason most calculations were performed for a simplified example reservoir to which the latter techniques might reasonably be applied. However, the computer program employed applies equally well to cases involving arbitrary spatial variations of permeability, porosity, reservoir thickness and dip angle.

By R. I. Jaffee, R. M. Evans

IN recent years, the interest in liquid metals as heat-transfer media for power plants has been very great. The possibility of the development of nuclear power plants has increased this interest and served as the impetus behind much research on low melting metals and alloys for such purposes. The principal reasons for consideration of liquid metals as heat-transfer media lie in their high thermal conductivity and consequent high heat-transfer coefficients, stability at high temperatures, and the high ranges of temperature possible. The element gallium possesses some of the requisite properties for a heat-transfer liquid. It is a unique material, having a low melting point and a high boiling point. Pure gallium melts at 29.78oC, and suitable alloying will produce a metal which melts below room temperature. The boiling point is about 2000°C. As it is a liquid metal, the heat-transfer characteristics would be good. Gallium is not now readily available, due in part to a lack of uses for the metal. Nevertheless, it is not a rare element, and a sufficient supply of gallium exists to permit its consideration for this use. Since gallium has some promise as a heat-transfer liquid, owing to its unique properties, research on the subject was carried on at Battelle Memorial Institute at the request of the Bureau of Ships, U.S.N. The research had as its objectives the determination of the effect of alloying on the melting point of gallium, and the study of the corrosion of possible container materials. In this research, alloys were found which had significantly lower melting points than pure gallium, but none which simultaneously fulfilled other additional requirements, chiefly the corrosion problem. Neither was it found possible to reduce the melting point of certain otherwise suitable alloys appreciably by small additions of gallium or gallium alloys. The results gave little hope that gallium alloys can be developed which enhance the good properties and minimize the undesirable characteristics of elemental gallium. Thus, gallium now appears less promising than other metallic heat-transfer media. The experimental thermal-analysis techniques used in this work have been described.' Experimental Results As a first approximation, the development of low melting gallium alloys was based on alloying elements suitable for use in a nuclear power plant, which also lowered the melting point of gallium. Information from the literature, summarized in Table I, indicates that. tin, aluminum, and zinc are the only suitable elements which cause a lowering of the melting point of gallium. Indium and silver also lower the melting point of gallium, but are of little interest for use in nuclear power plants. Of the elements reported not to lower the melting point of gallium, there is some ambiguity on the behavior of copper. Weibke3 obtained solidus arrest temperatures of 29°C for Cu-Ga alloys from 60 to 90 pct Ga, 0.8C lower than the generally accepted melting point. This may be the effect of a eutectic close to gallium, or, more likely, the result of impurities, or experimental error. The seven elements listed in Table I whose effects were not known were of potential interest if they lowered the melting point of gallium. Their effects were determined experimentally for this reason. Binary alloys containing nominally 2 pct of each of these elements were prepared in the form of 2-g melts by placing the components in a graphite crucible and holding them in an argon atmosphere at 370°C for 5 hr. These melts were then subjected to thermal analysis. In all cases. the solidus temperature was the melting point of gallium. Since these elements (As, Ca, Ce, Mg. Sb, Si, and T1) did not lower the melting point of gallium, they were not considered further as components of a eutectic-type alloy. Ga-Sn-Zn Alloys Preliminary considerations of this system for low-melting alloys were encouraging. All three binary systems were of the simple eutectic type. The composition and melting points of the eutectics were as follows: Sn-9 pct Zn (199°C), Ga-8 pct Sn (20°C), and Ga-5 pct Zn (25°C). Therefore, the probability of a ternary eutectic was high. For reasons to be discussed later, aluminum could not be used as an alloying constituent, leaving the Ga-Sn-Zn system as the only one of interest for low-melting gallium-

Jan 1, 1953

By C. Schlumberger, M. Schlumberger

The object of this paper is to clarify the idea, so important when exploring by potential methods, of the depth of investigation attainable by electrical measurements. After defining, with some precision, .the term "depth of investigation'' in geophysics, the authors show how it is possible to regulate this depth in potential methods and to obtain an 'electrical drilling" from surface observations. They consider also the difficulties encountered in deep measurements and indicate how it is possible to reach greater depths than those having an industrial interest. Depth of Investigation The term, depth of investigation, in its general sense, is easily understood. For instance, a driller who can pull cores from a depth of 2000 m. is capable of working, with accuracy, to that depth. By means of a properly placed drill, he may locate an orebody at a depth of 1999 m., however small this orebody may be. On the contrary, the term as used in geophysics requires precise elaboration. As a matter of fact, no geophysical method, irrespective of the physical property studied (density, magnetic permeability, conductivity), can discover a very small body at a great depth because, in practice, the physical parameter upon which such a geophysical method is based is never regular enough, throughout the ground, to distinguish the feeble anomaly caused by the small, deep-lying body from the numerous anomalies due to irregularities of the encasing terrains. Aside from this question of the ratio between the size of the body being hunted for and its depth of burial, a second factor plays its role in the possible depth of investigation; that is the difference, for the parameter under consideration, between the body and its surrounding material. The greater this difference, and the more homogeneous the encasing terrains, the greater is the possible depth of investigation. This being generally established for all geophysical methods, it is possible to distinguish two main classes of these methods, from this same point of view

Jan 1, 1932

By AIME AIME

LIFE will not be difficult for those who attend the fall meeting of the Petroleum Division at the Conoco Club, Ponca City, Okla., Sept. 30-Oct. 1. An attractive program to appeal to oil company executives and lawyers, as well as technologists, has been arranged and the Continental Oil Co. has contributed for the occasion the buildings, grounds and facilities of the club. E. 0. Bennett, Continental Oil Co., Ponca City, is chairman of the arrangements committee, and reservations for rooms and trips, requests for information, etc., should be sent to him.

Jan 1, 1932

By AIME AIME

No democracy such as ours, can ever be prepared for war, because we could never conceivably be the aggressor. The aggressor prepares in secret, designs his new tactics, and invents and makes new equipment and selects the time to strike. If a democracy prepare done year and the war came later, all that it had one would have to bed one over. All that England has today in the way of effective armament has been invented, designed, made, and the crews trained since the war began, because the totalitarian aggressor introduced new types of equipment and new techniques.

Jan 1, 1941

By James Aston

A proper consideration of this subject is not confined to the technical channels of production and metallurgy. It concerns an industry, and should cover economic aspects which are of material importance in any program of development. The discussion may logically be treated under three subdivisions, as follows: (1) manufacture, (2) characteristics related to quality of material; (3) adaptability and exploitation of product. Manufacture of Wrought Iron The manufacture of wrought iron is the most ancient art of the ferrous metal industry. The eighty years or less of existence of processes identified with our modern "Age of Steel" is a relatively brief interval compared with the several thousand years associated with the production of wrought iron by man. From the primitive early methods of production, manufacture for many centuries followed the line of direct reduction. There were developments as experience was gained through the years; but man's needs for a strong, ductile, forgeable product were met by reducing the ore to metallic iron in a single-stage operation. Following the development several centuries ago of what has become our modern blast-furnace operation, manufacture of wrought iron was gradually transformed into a two-stage method of first producing cast iron and then refining this to the desired degree of forgeability; the forerunner in principle of today's scheme of manufacture of steel. The product retained the essential characteristics of highly refined base metal with iron-silicate slag incorporation, which were associated with the material resulting from direct reduction methods. Cort's invention of the puddling process in 1784 is a landmark in wrought-iron manufacture. It consisted essentially in adapting a coal-fired reverberatory furnace to the refining operation; thus lifting the industry out of the slough of

Jan 1, 1935

By W. L. Saunders

It is now generally admitted by experts that at least so far as rapid progress is concerned the Alpine system of tunnel-driving is superior to any other. This is perhaps natural in view of the record of experience in driving tunnels through the Alps. These great mountain-chains cannot be treated in the ordinary way by shaft-sinking and driving headings, thus multiplying the points of attack. The work must be done from the ends only, hence speed in driving is of the utmost importance ; and, as necessity is the mother of invention, the concentration of effort to make progress has resulted in an organization and in mechanical appliances that have produced results so much in excess of the usual practice, even in America, that a discussion of the subject in detail should be of much value to the engineer and contractor. The first Alpine tunnel mas the Mont Cenis, length 7.5 miles, driven with a progress that averaged about 7.75 ft. per day. Next came the Saint Gothard, 9.5 niiles long, 18 ft. per day; Arlberg, 6.5 miles long, 27.25 ft. per day; Simplon, 12.25 miles long, 36 ft. per day. The figures represent progress when driving from two headings, so that by dividing them in two we get the daily single-heading progress. The latest of the Alpine tunnels is the Loetschberg, now being driven. In this work the world's record has been beaten by a single day's record in one heading of 36 ft. and by an average daily record in one heading of 29.5 feet. The Alpine range forms a natural barrier between a large section of northern and southern Europe. This range extends from the southeast of Prance to the frontier of Hungary, betveen Italy and the plains of sonthern Germany. The contour

Jan 1, 1912

By M. G., Corson

1. In addition to the alloys of copper with iron previously found by Hanson and Ford to show an increase in the concentration of the alpha range with increase in temperature the following binary and ternary systems have been found by the author to exhibit: the same feature: (a) Copper-chromium. (b) Copper-cobalt. (c) Copper-silicon. (d) Copper-nickel-silicon and its pseudo-binary section Cu-Ni2Si (formula of compound definitely established). (e) Copper-cobalt-silicon and its pseudo-binary section Cu-Co2Si (formula of compound established with some probability but not as definitely as for Ni2Si). (f) Copper-chromium-silicon; formation of a compound definitely established (compare Figs. 1 and 2). The formula of this compound may be either Cr2Si or Cr3Si. (g) Copper-iron-silicon; presence of a phase containing both iron and silicon established in an indirect way only. No definite microconstituents observed. 2. RANGES OF SOLID SOLUBILITY (percentage at various tempera¬tures). (a) For copper-chromium: 0.8 at 1000° C.; 0.5 at 900° C.; 0.25 at 800° C.; 0.05 to 0.1 at 500° C. (b) For copper-cobalt: 3.4 at 1000'C.; 2.4 at 900'C.; 1.7 at 800'C.; 0.9 at 600°C.; 0.35 at room temperature. (c) For copper-silicon (Fig. 3) : 6.8 ± 0.1. per cent. at 800° C.; 3 per cent. at 400° C. and probably below 2 per cent. at room temperature if sufficiently long annealed. (d) For copper-cobalt silicide: 3.3 at 1000° C.; 2.4 at 900° C.; 1.6 at 800° C.; 0.7 at 600° C.; 0.3 at 300° C. (e) For copper-nickel silicide (Fig. 4): 8.2 at 1000° C.; 5.5 at 900° C.; 3.6 at 800° C.; 1.6 at 600° C.; 0.7 at 300° C.

Jan 1, 1927

By M. R. Geer

THE increase in the number of coal-cleaning plants employing dense-medium processes occurring since 1946 is especially interesting when viewed historically. Both sand and magnetite were introduced as material for heavy mediums at about the same time, sand in the Chance process in 1921 and magnetite in the Conklin process in 1922, but from that point on their records diverge. The Chance process enjoyed a steady growth from its inception, whereas no additional magnetite plants were built in the United States for over 20 years. Then, following the close of the World War 11, magnetite was again introduced, this time with marked success. During the following years some 47 plants employing magnetite medium were built.

Jan 7, 1953

By M. L. Samuels

DURING the period from 1910 to 1920, there was a lively interest in the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth-why and how it occurs-were treated in papers by Howe,1 Jeffries,2 Sauveur,3 Chappell,4 Beilby,5 Mathewson and Phillips,6 McAdam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,10 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size specified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filaments" wherein it is important to prevent "sagging" between consecutive turns of the helix." This practical use of a certain knowledge as to the things that influence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,13 in the hardening treatments of high-speed steels, 14.11 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is predominant no growth at all takes place. Under conditions in which

Jan 1, 1938

By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By H. E. McKinstry

LIKE nearly everything else, mining geology has been reconverting. Many geologists had been in military and other government service. Many more, with mining companies, had been working primarily toward increasing production from known reserves. All of these are turning now toward their normal peacetime endeavor-the search for new ore; for most mining companies, finding themselves with accumulated deficits in development work, are more than ready to go ahead with their postwar plans made a year or more ago but still stalled at the close of 1945 for lack of man power. These plans include not merely development in the old home camp but also wide exploration for new prospects both domestic and foreign. Most of the large concerns have geologists and engineers in the field in the United States, despite the outlook for higher mining costs here, and at least half a dozen strong American companies are already investigating opportunities abroad, notwithstanding past unhappy experiences in certain Latin-American nations which have welcomed capital but later found means of preventing investors from reaping the reward of their enterprise. A few of these new foreign expeditions are following well-planned programs, but too many, in their haste to get any sort of footing, are proceeding without well-considered policy. with the result that their geologists can do little more than desultory scouting.

Jan 1, 1946

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967