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By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

By F. C. Stanford

The work of an engineer is to direct natural forces so that the: bring about the results that he wishes to secure. Heretofore he ha concerned himself chiefly with physical forces and inanimate objects until he has secured a truly marvelous degree of control over them The great problem of the present age is to secure a like degree of know1 edge and control of the human factor. Progress has already been made along this line, but it is only a beginning. Wilhelm Ostwald says tha scientific knowledge enables a man to be a true prophet; but it must be remembered that a good many people do not seem to be able to main tain a high average in prophecy. In short, 'the average of knowledge is not equal to the average needs of the present time, but continually fails to keep pace with it. It has been aptly said that the really essentia need of the period is for more brains; if we only had sufficient knowledg and sagacity we could not only solve all difficulties, but prevent then from arising. This generalization holds good for an industrial organization. Th most vital need of the management is for more brains. The logica course for an engineer in charge of an industrial organization is, therefore to direct whatever forces may be at his command toward the development training, and guiding of all the brains in his organization. This is easie said than done, for it involves the carrying on toward two objective: the maximum of productive work, and the development of the individual who perform it. This is essentially like the rebuilding and enlarging of plant, keeping it in full operation the while. On the other hand, if th aim is merely for maximum production from an organization, withou offering opportunity for development, the final outcome will necessari be like that of a plant that is driven at full capacity without stoppin for repairs or improvements; it eventually becomes so run down th either a complete rebuilding is necessary or else it has to be abandone

Jan 1, 1918

By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By A. C. Watts

FOR several years, a mine in Colorado experienced considerable trouble from small fires caused by the blasting of coal. Although a well-known make of permissible powder was used, it was first thought that the powder ignited gas that might be present and that this, in turn, set fire to line brattices or to the coal. Experiments were, therefore, conducted with another make of powder, but the results convinced the superintendent of the mine, Robt. Williams, Jr., that the fires were not caused by the powder but by the high-voltage electric current used for detonating the shots. The mine "makes" gas very freely, giving off from three-fourths to a million cubic feet of methane per 24 hours. The coal is a good grade bituminous of a very free burning quality. Electric shot-firing from the outside after all men and animals were outside had been practiced for a number of years. The shooting circuit was connected with the main power circuit at the mouth of each entry. Shooting circuit switches were mounted in boxes, which were kept locked with the handle of the switch, in open position, showing through the bottom of the box. The door of the box could not be shut and locked when the shooting switch was closed. At the entrance to each room, or working place, a small switch, called the miner's switch, was placed on the shooting line. It was the duty of the miner, when entering his place at the beginning of the shift, to see that this switch was open and that it was kept open until he left the place at the end of the shift to go out of the mine. Grounded return was used for main power lines. The current was 500 volts, direct current, with 100 to 300 amp. The nearest working face was 9600 ft. from the shot-firers' switch outside the mine and the most remote working face was 2 ½ miles. The various working faces were scattered over a wide area between these two points.

Jan 9, 1925

By E. P. Pfleider, O. Rellensmann

In the May 1959 issue of [=] the authors reported on the gyrotheodolite as used for determining azimuths in surface and underground work. Further research has led to the development of a new type of gyro instrument, the band-suspended gyro attachment, which is essentially an upset gyro attached to the top of a theodolite. The new gyro attachment is light enough to be mounted on any angle-measuring instrument if the design of the telescope standard permits. Gyrotheodolite units have been used to transfer meridian lines underground in the Coeur d'Alene mining district, although they have not been used extensively in the U.S. In other parts of the world, however, they have been adopted as the standard surveying instrument by mining engineers.

Jan 3, 1968

By George W. Bain

SOME problems concomitant with commercial exploitation of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service department wants defects rectified and the cause determined to avoid recurrence. The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character. GEOLOGICAL PROBLEMS The geological problems deal almost exclusively with the size of blocks. Size across the deposit is limited by thickness of individual beds, and along the strike by the space between crosscutting joints. Frequently the vertical depth of a block is reduced by exfoliation shells arising from spontaneous expansion. All these factors require consideration in developing a deposit to fill an order. Thickening of Marble Beds The limestone beds that became the marble deposits of the northern Appalachians and of the Yule locality in Colorado were seldom homo-

Jan 1, 1940

By J. W. Rutter, K. T. Aust

The temperature dependence of the rate of grain boundary migration was measured in bicrystals of zone-refined lead containing from 20 to less than 1 ppm by wezght of tin. The apparent activation energy in the temperature range from 320" to 200oC is markedly dependent upon the solute tin concentration and upon the orientation relationship of the grains adjacent to the grain boundavy. The quantitative experimental observat~ons are compared with the predictions of various theories of grain boundary migration. In previous work.&apos;?&apos; the mobility of individual grain boundaries was studied as a function of impurity concentration and type of boundary. Grain boundary migration occurred at the expense of dislocation arrays which were introduced into the specimen during solidification. Boundary mobility in zone-refined lead at 300°C was markedly decreased by small additions of tin. 0.004 wt pct being sufficient to decrease the rate of grain boundary migration by a factor of 1000. The mobility of grain boundaries having polar orientation relationships near 38 and 22 deg about <Ill>, and 28 deg about <100>, was much less sensitive to tin concentration in the range studied. As a result, these boundaries have relatively high mobilities. The present paper is a continuation of the above study. Data are now presented on the temperature dependence of the motion of individual grain boundaries in zone-refined lead as a function of solute tin concentration and orientation relationship of adjacent grains at the grain boundary. The experimental observations are compared with the predictions of a number of theories of grain boundary migration3-8 which, prior to the present experimental investigation, could not be critically evaluated. EXPERIMENTAL PROCEDURE The striation or lineage structure of melt-grown single crystals of zone-refined lead, containing various additions of tin, was utilized to provide a driving force for grain boundary migration, as previously described.1,2 Each grain boundary under study separated the striated single crystal from another grain which was introduced by localized plastic deformation and recrystallization of a small region of the sample. The speed of migration of grain boundaries in dilute alloys of tin in zone-refined lead was investigated as a function of 1) tin concentration from < 0.0001 to 0.002 wt pct, 2) temperature in the range of 200" to 320°C, and 3) orientation relationship of the adjacent grains at the grain boundary. The substructure driving energy available for grain boundary migration was estimated to be about 4000 ergs per cu cm, within a factor of two, from specimen to specimen.&apos; The specimen dimensions, and growth and alloying procedures for the preparation of striated single crystals of lead of known tin composition, were as described previously.&apos; Each bicrystal was carefully wrapped in aluminum foil, and annealed in a well-stirred salt bath consisting of 50 pct NaNO2 and 50 pct KNO3, for known periods of time at a series of constant temperatures (*2°C). The grain boundary positions, before and after each anneal, were determined by etching lightly in a solution of 5 pct nitric acid in methyl alcohol, in order to follow the motion of the boundary and determine its rate of migration. Thus, the rate of motion of the grain boundary in a single specimen was measured at various temperatures. The above procedure was carried out for each grain boundary in seventeen different bicrystal specimens.

Jan 1, 1960

PRESIDENT AND DIRECTOR SCOTT TURNER WASHINGTON, D. C. PAST PRESIDENTS AND DIRECTORS WILLIAM H. BASSETT WATERBURY, CONN. ROBERT E. TALLY JEROME, ARIZ. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1932

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400&apos; to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400&apos; and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400&apos; to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400&apos; and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By Blamey Stevens

(Butte Meeting, August, 1913.) THE following paper aims to make a full explanation of the phenomena of rock jointing: It may be unnecessary to give any general description of what are termed joints in rocks, but Professor Geikie&apos;s clear and faithful generalizations are so illuminating that no excuse need be given. for introducing the following and other quotations into this paper "Almost all rocks are traversed by vertical or highly inclined divisional planes termed joints. These have been regarded as due in some way to contraction during consolidation (fissures of retreat) ; and this is no doubt their origin in innumerable cases. But, on the other hand, their frequent regularity and persistence across materials of very varying texture suggest rather the effects of internal pressure and movement within the crust." 1 General Explanation.-In this paper I show that the phenomenon of jointing may to a large extent be accounted for by the pressure of the water contained in the pores of the rock. To understand this, each constituent grain of the porous material may be considered to be separately compressed by the water which submerges it. As all the grains are held together by cohesion, the whole mass is contracted by this pressure. In an indefinitely extended mass, however, there must be a limit to the possible contraction without rupture, because the material is restrained from moving freely by other material around its boundaries. The mass of rock thus becomes broken up. This phenomenon is known as &apos;" shrinkage " jointing. The term " shrinkage " is an apt one, if it be understood that the shrinkage of the rock is often brought about by change of stress. Stresses.-The compressive component of water stress on the individual grains is evidently the same as that of the water with which it is in contact. This is so, both before and after the jointing is formed. Before the jointing is formed there is, however, a tensile stress in one or more directions which keeps the material from contracting. .

Jan 7, 1913

By George S. Koch

Since 1882, world zinc production has increased. In contrast, US zinc production rose until about 1915, but since then has remained nearly constant, with a slight tendency to decrease. Production from the Tri-State district, the largest early source of zinc in the US, has gone down steadily; this decline has been balanced by a growth in the rate of other districts. These changes in US production are due to economic, not geological, factors. Recent exploration has located large minable ore bodies: additional deposits will undoubtedly be found in the stratabound carbonate rock and volcanogenic environments. A statistical analysis of the exploration effort in the Middle Tennessee district indicates that new discoveries can be expected there. Thus, the US is in an early stage of the production cycle for zinc. Of major mining districts in the US, only the Tri-State is exhausted under current economic conditions; large zinc resources of low-grade material, which would repay mining at higher prices or improved technology, are known to exist in that district .

Jan 1, 1982

By Philip Wilson

THE genesis of some orebodies has been explained by the mingling and chemical interaction of water solutions of different compositions and the consequent precipitation of the mineral load of one or both solutions at their confluence. While this process can be proved in the laboratory, rarely can a positive demonstration be found in nature, for the conditions at the time an ore deposit is being worked are usually entirely different from those that existed when the orebody was formed. For this reason, the present deposition of copper carbonate in the southern end of the Briggs Mine of the Calumet and Arizona Mining Co. near Bisbee, Ariz., is of great interest. The developed orebodies in the Calumet and Arizona mines are roughly confined to two broad parallel zones separated at the north by a wedge of. Copper Queen ground and at the south by an undeveloped block of Calumet and Arizona ground about 2000 ft. (610 m.) wide. The more westerly zone includes the Irish Mag, Oliver, P. and D., and Cole mines, none of which have been operated since 1919. Much of the water from this division is carried from the 1400-ft., or bottom, level at the southern end of the Cole mine in a long water drift through the undeveloped block to the 1300-ft. level of the Briggs mine at the southern end of the more easterly zone.. Most of this water comes originally from outlying areas in the P. and D., mine, passing through parts of the lower levels of the Cole mine, which are heavily mineralized with iron and copper sulfides. This sulfide zone has been opened up and slowly oxidizing for years. Originally a pure, potable water, the analyses of which are shown under A in Tables 1 and 2, on its way through the mineralized area in the Cole mine it gathers copper, calcium, magnesium, iron, and aluminum sulfates, a load of dissolved mineral salts almost four times as great as that which it formerly carried; analyses B

Jan 7, 1922

Lester Guttman (General Electric Research Lab-boratory)—Seybolt has measured the thermodynamic activity of silicon in dilute solution in a iron. The anomaly which appears at 800 °C in the approximate range 1 to 6 wt pct Si is most naturally attributed, as Seybolt has done, to the existence of a region of

Jan 1, 1960

CONTENTS PAGE HESSE, A. W,-Safeguarding Coal-mining Operations against Danger from Oil and Gas Wells. Discussed by A. W. Hesse, T. G. Fear, George H. Ashley, George S. Rice, W. E. Fohl, R. V. Norris, S. A. Taylor, F. B. Tough, C. W. Gibbs, A. Hurlburt, S. W. Meals 1 DAWSON, THOS. W.-Belt Conveying of Coal at H. C. Frick Coke Company Mines. Discussed by F. F. Jorgensen, Thos. W. Dawson, Graham Bright, A. W. Hesse 13 OTTO, HENRY H.-Ultimate Recovery from Anthracite Coal Beds. Discussed by R. V. Norris, S. A. Taylor, Henry H. Otto, Douglas Bunting, Graham Bright, Howard N. Eavenson, J. B. Warriner 15 HOSLER, Rush N.-Schedule Rating Coal Mines in Pennsylvania for Compensation Insurance Rates. Discussed by E. A. Holbrook, W. W. Adams 17 ARCHBALD, HUGH.-Application of Gaussian Curve to Mining Industry. Discussed by Donald A. Laird, T. T. Read 19 ASH, SIMON H.-System of Coal Mining in Western Washington. Discussed by Eli T. Conner, Simon H. Ash 21 MILLER, J. S.-Method of Mining a Steeply Pitching Anthracite Vein by Successive Skips. Discussed by Eli T. Conner, J. S. Miller, J. B. Warriner 22 HARRINGTON, GEORGE B.-New Orient, an Unusual Coal Mine. Discussed" by George S. Rice, Eli T. Conner, John A. Garcia, George B. Harrington, F. F. Jorgensen, Graham Bright, W. M. Hoen, George N. Simpson, W. C. Adams, R. W. McNeill, Chas. C. Whaley, Carl Scholz, E. T. Gott, Andrews Allen 23 PERROTT, G. ST. J.-Properties of Liquid-oxygen Explosives. Discussed by George S. Rice 48 Safeguarding Coal-mining Operations against Danger from Oil and Gas Wells Discussion of the paper of A. W. HESSE, presented at the New York Meeting, Feb-ruary, 1925, and issued, as Paper No. 1412-F, with MINING AND METALLURGY, February, 1925. A. W. HESSE.-The well under investigation, No. 101, Fig. 2, was started about Sept. 5, 1921, and drilled-in in November. The first hole was started with a 13-in. bit and reached the Pittsburgh coal at a depth of 563 ft.; at 602 ft. the 10-in. casing was run in and the well was continued with a 10-in. bit and 1400 ft. of 8-in. casing was put in. It was then continued to a depth of 1770 ft. and 6-in. casing put in; then continued to a depth of 2555 ft. where the gas was struck. As the well produced only about 100,000 cu. ft. per day. 2-in. tubing was used to conduct the

Jan 6, 1925

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2&apos;3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

By Eugene N. Cameron

Graphite is the hexagonal form of crystal-line carbon. It is found in nature locally as tabular crystals but occurs mostly as disseminated flakes, foliated, platy, or fibrous masses, or microcrystalline compact to earthy material. Graphite is characterized by its gray to black color, metallic luster, black streak, perfect basal cleavage, softness (H = 1-2) and unctuous feel. It is sectile and flexible and has a specific gravity of 2.1 to 2.3. It is an excellent conductor of heat and electricity and is inert to ordinary chemical reagents. It melts at a temperature of about 3500°C and vaporizes at a temperature of about 4500°C. In the presence of oxygen it oxidizes to CO2 in the temperature range 600° to 700°C, but it is stable at ordinary temperature and markedly resistant to chemical weathering. Although some natural graphite is nearly 100 pct pure carbon, most contains mechanical impurities of various kinds; quartz, biotite, muscovite, pyrite, iron oxides, and feldspars are the most common. Commercial graphite products have a wide range of graphite content, but the better grades contain 80 pct graphite or more. Both natural and manufactured (artificial) graphite are used in industry. Natural graphite products are divided into two broad categories based on grain size. Graphite composed of visible crystals is called "crystalline" graphite, whereas graphite so fine-grained that it is not visibly crystalline is termed "amorphous." The distinction is arbitrary, for all natural graphite is crystalline, and all gradations between the two commercial categories are known. Within the two categories the terminology used in industry is confusing and not entirely consistent. Crystalline graphite comes from two principal types of sources. The first consists of rocks containing disseminated flakes of graphite. This source yields the "flake graphite" of industry. The second comprises vein deposits of graphite, of which those in Ceylon are the most important and furnish the Ceylon graphite of industry. Amorphous graphite comes from any of a variety of sources, including some of those that yield crystalline graphite. Manufactured graphite is made by electric furnace processes, mostly from petroleum coke. Occurrence and Distribution of Graphite Deposits GENERAL Graphite is widely distributed in nature, occurring in igneous, sedimentary, and metamorphic rocks, and even in nickel-iron meteorites. Graphite deposits of economic interest, however, occur mostly in metamorphic terranes. Five principal geologic types of deposits are recognized: 1. Deposits consisting of flake graphite disseminated in metamorphosed siliceous sediments. 2. Deposits consisting of flake graphite disseminated in marbles. 3. Deposits formed by thermal or dynamothermal metamorphism of coal or other highly carbonaceous sediments. 4. Vein deposits of the Ceylon type. 5. Contact metasomatic or hydrothermal deposits in marble. DEPOSITS IN METAMORPHOSED SILICEOUS SEDIMENTS Deposits consisting of flake graphite disseminated in metamorphosed siliceous sedi-

Jan 1, 1960

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947