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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' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' 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 John Hays Hammond

The Transvaal comprises about 120,000 square miles (nearly • the size of the United States Territory of New Mexico). Besides the famous Witwatersrand, which will here be de scribed in detail, there are two quartz-mining districts of some importance, viz., Lydenburg and De Kaap. The Lydenburg district first attracted attention in 1876, when the alluvial deposits of that section began to be exploited. At a later period vein-rnining was started, and at the present time several companies are operating in that district. The product in 1898 of five companies, running 137 stamps, was 154,560 tons of ore, yielding 108,884 crude ounces of gold (an average of 14.09 dwt. crude gold per ton) valued at £392,378. The De Eaap gold-fields were discovered in 1884. In 1898, seven companies, running 200 stamps, produced 89,760 crude ounces of gold, valued at £314,792. I. Mining Titles in the Transvaal. The mining laws of the Tranuvaal are most excellent in char acter, and while the claims cover every square foot of land for an area of nearly 40 miles long by from 2 to 3- miles wide, there have been practically no conflicts over extra-lateral rights. Notwithstanding the change in the political status of the Transvaal likely to follow the present war, it may be coufi dently assumed that the main features of the mining law of the South African Republic will be retained, and certain op pressive featureu of monopolies, etc., bearing with special weight on the mining industry, will be abolished. The dynamite mo nopoly was one that bore most heavily on the mining industry; and, according to the Reports of the State Mining Engineer, explosives, including fuse and detonators, amounted to nearly 10 per cent. of the total working costs of the mines. Further more, it was impossible to obtain the proper quality for the most economical working, and often 80-per-cent. or 40-per-cent. gelatine had to be used- in many instances where 60-per-cent.

Jan 1, 1902

By J. L. Tokich, A. R. Troiano

INTRODUCTION SINCE 1921, when Hull' discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at temperatures ranging from 400 to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allotropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms of this type of transformation. Table 1 briefly outlines the methods and results of previous investigators of the transformation temperatures of cobalt. MATERIALS AND METHODS The major portion of this investigation was performed with cobalt sheet containing a total of 0.2 pct impurities with carbon present to the extent of 0.1 pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon content analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pct pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below 600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various temperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per sec to greater than 1,000°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The proportion of the existing phases was roughly approximated by visual examina-

Jan 1, 1948

By Arthur Green

A GROUP of 13 cities situated in Los Angeles and Orange counties in Southern California is engaged in constructing an aqueduct to carry water from the Colorado River at a point near Parker, Arizona, to a distribution point sear Riverside, California. The aqueduct will have a total length of approximately 241 miles, and is designed to deliver 1605 cu. ft. of water per second, or a little more than one billion gallons per day. The aqueduct crosses a barren, desert waste and the project includes approximately 91 miles of 16-ft. tunnel. The large amount of tunnel driving that has been done in this country in the past few years has resulted in some remarkable developments in equipment and methods. The building of the Colorado River Aqueduct, with its 91 miles of tunnels, has called on the best engineering knowledge in the country. New and better equipment has been designed for all phases of the work, and this equipment has been coordinated and adapted to the various conditions with a high degree of efficiency. The result has been that records for tunnel driving have been set under adverse natural conditions that exceed the estimates for progress under good conditions. All of the tunnels in the main aqueduct, except the Valverde and Bernasconi at the western end, have a finished diameter, inside the concrete lining, of 16 ft. Fig. 4 shows a section of the tunnel with the concrete lining in place. Fig. 5 illustrates the finished tunnel in three typical sections. The standard tunnel grade is 3.432 ft. per mile in the 16-ft. tunnels, but the Valverde and Bernasconi tunnels have a steeper grade and a finished diameter of 15 ft. 3 in. The rough bore of the large main aqueduct tunnels averages 12.95 solid cubic yards of material per foot of advance in timbered sections and 10.76 solid cubic yards per foot in unsupported sections.

Jan 1, 1936

Jan 2, 1966

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

By Thomas Wilson

IN a single-crystal cube of iron the arrangement of the atoms is that characteristic of iron at room temperature: the body-centered cubic lattice. X-ray investigation has shown this structure to be characteristic of iron, as it has shown the atomic arrangement of other metals to be characteristic of those metals also. Rarely do substances have more than one characteristic atomic arrangement. Many physical properties of metals are directly connected with their atomic arrangements, so that changes of arrangements produce changes of properties. Only chemical change influences atomic arrangement. If a difference in the physical properties of a metal is caused by a process which involves no chemical change, the cause of the difference in properties must be sought elsewhere than in the atomic arrangement. Frequently this cause can be traced to alteration of crystal orientation. The orientation of a crystal may be defined as the relationship which the crystallographic axes bear to some quantity of reference. A cube of iron appears cubic whether it is regarded from a face, an edge, or a corner. Yet these three positions represent three different orientations of the cube with respect to the observer. It is evident that the orientation of this cube of iron, unlike the atomic arrangement, is not characteristic of iron but is entirely dependent on the previous history of the cube. Most of the processes of metal working, such as wire-drawing, rolling, and bending, change the orientation of the crystals present in the worked metals. These processes usually tend to produce rotation of the crystals into positions approaching a mean. Specimens of metals show-ing this characteristic are said to possess a preferred, orientation. Tensile strength, ductility, and many other properties are influenced by orientation changes; therefore two specimens of the same metal may show different values of these quantities. In metal specimens possessing a narrowly limited preferred orientation, these quantities will vary in magnitude in different directions throughout the specimens. The investigation of the influence of manufacturing operations upon crystal orientation, and hence upon physical properties of metals, is an important

Jan 1, 1929

By W. H. Brandt

THERE has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidence. Particularly noteworthy among the empirical work is that of Grossmann,12 who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.1-5 They have shown that formation of pearlite proceeds by a process of nucleation and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to fill in a small part of the gap. A method was presented recently14 for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eutectoid steel was calculated, using linear extrapolations of the ferrite and cementite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and V, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1945

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612' F. (322' C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,

By J. J. Van Nouhuys

THE economics of aerial survey and the technical processes by the aid of which vertical and oblique aerial photographs are turned into line maps showing the most profuse topographical detail such as contours, rivers, roads, plantations, habitations and cultivated lands do not concern us here. They have been ably and exhaustively described in the publications of the British War Office, handbooks on surveying methods and on photogrammetry and in the South African mining, engineering and geological press. Suffice it to mention that for geological interpretation vertical photographs are used on such scales as 1/5000 to 1/10,000, overlapping each other by 55 to 60 per cent in the direction of flight and some 10 to 20 per cent sideways on to the next sequence or strip. Through this duplication in the overlap the stereoscopic examination becomes possible. The standards by which monochrome aerial photographs are interpreted can be grouped under the following headings: 1. Continuity.-The continuity of topographic relief not obtainable on the ground owing to the smallness of man relative to that relief. Here lies the greatest value of aerial survey with relation to geology. An immediate alignment can often be made of drainages running in different directions on each side of a hill; saddles and gorges in the mountainsides; abrupt termination of outcrop or indubitable signs of faulting. Most conclusive evidence is thus often obtained about faults which may be perfectly visible at one place on the ground but cannot elsewhere be identified because of decreased throw. Similarly, dikes can often be followed notwithstanding frequent interruption and disappearance under the soil. Scattered outcrop in scrub-covered or bush-covered country can be compared with field work. The same applies to geological contacts. Once these have been 3stablished at a few points on the ground, the intervening stretches can be drawn in.

Jan 1, 1937

By S. Leber, R. F. Hehemann

Diffusion coefficients for the Cb-W system were measured using couples prepared from poly crystalline, commercially pure metals. The diffusion coefficients, measured in the temperature range between 1700° and 2300°C, decreased exponentially as the tungsten concentration was increased from 0 to 50 at. pct, then decreased abruptly at higher concentrations. A decrease of two orders of magnitude was observed over the entin? compositional range. The diffusion coefficients were in the range defined by the self-difiusion coefficients of the individual elements, indicating their general validity. An activation energy of 60,500 cal per mole was measured for the 20 pct W composition. Such low values, when compared with energies over 100,000 cal per mole for the pure constituent elements, indicated that transport mechanisnzs more rapid than volume diffusion were contributing substantially to inter dijfusion. Difference should, therefore, be expected between these data and the intrinsic diffusion coefficients. These differences should be significant in the kinetics of 'transport phenomena in practical systems. CONSIDERABLE attention has been devoted in recent years to the mechanical behavior and other properties of the refractory metals and their alloys. The Cb-W system has been of special interest as a base for the development of more complex compositions of commercial interest. In spite of the importance of mass transport to all aspects of elevated-temperature behavior, and especially to the production of alloys by powder-metallurgy techniques, little attention has been paid to diffusion in the Cb-W system. Results from a previous study of this system1 appeared to be anomalously high. The present investigation is, therefore, an attempt to obtain more accurate diffusion coefficients in this system. Intrinsic diffusion coefficients, of primary importance from the theoretical viewpoint, can only be obtained accurately from studies utilizing compositional gradients approaching zero. However, many practical problems involve diffusion under significant concentration gradients. The diffusion coefficients determined in this investigation were, therefore, obtained from couples prepared from elemental metals. The data obtained should be of value in the analysis of problems such as homogenization during powder-metallurgy alloying or reactions between base and clad in coated structures. In this vein, the investigation was conducted on poly crystalline materials of commercial purity. PROCEDURE Diffusion couples were prepared by sandwiching a columbium sheet between two sheets of tungsten. The composite was welded around all edges, the tungsten forming a protective can for the columbium. The composite was soaked for 4 min at 1600°C in a hydrogen-atmosphere furnace, quickly forged to 40 pct reduction in thickness, and then rapidly cooled to room tempera-

Jan 1, 1967

By J. H. Yang, K. E. Gray

Results of single-blow bit-tooth impact tests on saturated rocks under elevated confining pressures and zero pore pressure were reported in a previous publication.1 This paper presents an extension of the earlier work to include a study of crater formation during tooth impact on both gas- and liquid-saturated Berea and Bandera sandstones at elevated confining and pore pressures. The basic data obtained were force-time, displacement-time, velocity-time and force-displacement curves during crater formation. Crater volume was also measured and the mode of crater formation determined. Bit tooth geometry, depth of penetration and velocity of impact were held constant. Results indicate that, with pore fluid present in the rock, failure trends from brittle to ductile as pore pressure is increased at constant confining pressure (pore pressure and borehole pressure were equal) For a given rock type, the mode of crater formation was dependent not only upon the nominal effective stress, but also upon the fluid which saturated the rock pore space. When confining pressure and pore pressure were equal (zero nominal effective stress), bit-tooth impact resulted in brittle failure for nitrogen-saturated Berea, and brittle to transitional failure for nitrogen-saturated Bandera; when saturated with liquid both rocks failed in a ductile manner at zero nominal effective stress. INTRODUCTION Dynamic wedge penetration tests have been conducted by investigators in several fields, but the failure mechanism of rock under dynamic stresses is not understood completely. The complex action of drilling bits, even considering the action of a single tooth, may be considered as a combination of drag bit and rolling cutter action. Thus, as a first step in understanding rock breakage in oil well drilling, single chisel impact and rock planing are of fundamental importance. For example, Gray 2 and Crisp3 studied drag bit cutting action at brittle stress states. Simon4 and Hartman5 studied the reaction of rocks to vertical impact by means of drop tests. The depth of penetration, crater volume and force-vs-time curves during crater formation were observed. The significance of indexing single-bit impacts has been noted.4,6-8 Gamer et al,9 reported impact tests on impermeable Leuders limestone at atmospheric and elevated confining pressures. In all cases the tests were accomplished on dry rock and pore pressure was considered to be zero. The importance of both confining pressure and pore pressure on the failure characteristics of rock was described. 10-12 It was found that the yield strength and ductility of porous rock depend on the state of stress under which the sample is tested. The importance of pore pressure on drilling rate in microbit experiments was noted by Cumingham and Eenink. l3 Robinson 12 also pointed out that in drilling the most important parameter in rock failure is the effective stress, where effective suess is defined as confining pressure pc minus pore pressure pp. The effect of pore pressure and confining pressure on rock strength was also noted by Serdengecti and Boozer 14 in strain rate tests, and by Gardner, Wyllie and Droschackl5 in elastic wave studies. Until recently all reported wedge impact studies under simulated wellbore stress states have been conducted on dry rock. Maurer 16 reported impact tests on samples saturated with deaerated water. Borehole and formation fluid pressures were equal in these tests except when mud was used in the borehole. With mud in the borehole and a high borehole-to-formation fluid pressure differential. Maurer observed "pseudoplastic" crater formation. Podio and Grayl reported impact tests on Berea and Bandera sandstone saturated with pore fluids having wide ranges in viscosities. In Podio and Gray's tests, confining pressure was elevated, but pore pressure and borehole pressure were held fixed at atmospheric pressure. The presence of

Continued Discussion of the papers of Van Hise, Emmons, Weed and Lindgren, Bans., xxx., 27, 177, 424, 578. See also the papers of Vogt, Kemp, Rickard, Blake and Lindgren, at pp. 125, 169, 198, 220, 226, and also the final contribution of Prof. Van Hise, p. 284 of the present volume. All the foregoing, together with the discussion here following, are included in the special volume, "The Genesis of Ore-Deposits," issued this year by the Institute. H. Foster Bain, Des Moines, Iowa (communication to the Secretary):* The zinc- and lead-deposits of the Mississippi valley, which it has been my fortune to study, give particularly good examples of many of the principles of ore-deposition formulated by Prof. Van Hise. Perhaps there is nowhere clearer evidence supporting his fundamental tenet., that ore-bodies are to be regarded as a result, and as merely one of the phases, of the work of underground waters. The facts regarding the mines of the upper Mississippi valley have been given in some detail for Wisconsin by Prof. Chamberlint and, more recently, for the mines west. of the Mississippi by the Iowa Geological Survey.‡ Fortunately, also, the processes of underground water-circulation have been studied in some detail in connection with the investigation of artesian waters throughout the region.$ In Missouri and Arkansas the mines and ore-bodies have been much studied ; but the general problems of the circulation of underground waters have been neglected. During the season just closed the writer has been engaged in a re-study for the United States Geological Survey of the zinc- and lead-deposits of the Ozark region, with special reference to those of the . Joplin area; and his full report is now in preparation. It has been interesting to note how fully the statement that the orebodies result from the general action of underground waters is

Jan 1, 1902

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.' The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.' Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others' found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer' found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By B. J. Shaw, R. Kossowsky, W. C. Johnston

High purity (99,95) Ni-51 wt pct cr eutectic alloy was unidirectionalty solidified at rates of 0.1 to 8 in. per hr. The resulting material was characterized by large grains, approximately 0.5 mm in cross section and extending through almost the entire length of the specimen, parallel to the growth axis. The eutectic structure of specimens the growth at -1/3 The per hr consisted of a continuous nickel-rich phase and chrome -rich lamellae approximately 2 thick, spaced about apart. Specimens were tested in compression at temperatures ranging from —196 to 850"C over which range the 0.2 pet yield strength dp -creased from 160,000 p si to 35,000psi, respectively. Swaging to 40 pet reduction in area, followed by a 30-min anneal at 1000c to remove residual cold work, increased the 0.2 pet yield to 260,000 psi at -196°C, dropping to 35,000 psi at 850°C. The increase in strength was attributed to a residual cell structure. The strength of the alloy could be rationalized by the simple rule of mixtures if one assumed that additional strength is derived front a size effect characterized by is petch equation IN recent years there has been increasing interest in dispersion and second phase strengthening in materials needed for high-temperature applications. inm role of structure on the mechanical The of such alloys has been well established of such some extent accounted for theoretically. and to of how the strengthening mechanisms due to fibers and lamellae operate has been reduced to its fibers form by the fabrication of composites of strong rods unidirectionally aligned in a From work on tungsten-fiber-reinforced copper, for example, it was established that the "Rule of Mixtures" could explain the strengthening.12 " some what more sophisticated technique for introducing strong fibers into copper matrix was used by Hertzberg strong Kraft3 who unidirectionally solidified the copper-chromium eutectic. The use of unidirectionally fied eutectics has advantages in that there are no matrix-fiber wetting problems and fine fibers are automatically aligned and uniformly fiber However, one Is restricted to a specific volume fraction of the second phase. Nevertheless, even though the volume fraction is fixed, the rod or lamella thickness, , can be varied by controlling the freezing interface velocity. Alternatively, the grown material may be worked down by swaging or rolling. Embury and Fisher, " using this approach, drew down pear lite in iron and studied the mechanical properties iron and that the yield strength, oy, was properties.proportional They that d was the wire diameter. It could be inferred that was also proportional to but the work hardening had to be taken into consideration at the same time. By varying the growth rate of the cadmium-zinc lamellar eutectic, Shaw'1 showed that was proportional to without the introduction of work hardening and suggested that the lamellar interface itself contributed to the strengthening of the composite. In this investigation we have evaluated the mechanical properties of the unidirectionally solidified fec-bec eutectic Ni-Cr. This eutectic was selected because it presented the possibility was selected beca temperature, and high corrosion resistant alloy, and also represented a hard-soft phase combination with two completely different slip systems. Specimens were tested in compression and tension up to 850°C and a detailed study of the micro structure as a function of plastic strain and temperature was carried out by light and electron microscopy. It was shown that the composite strength tested in compression can be accounted for by the simple rule of mixtures if one allows for an additional term representing the effect of Intereprese EXPERIMENTAL PROCEDURE 1) Unidirectional Solidification. Fig. 1 is a schematic drawing of the apparatus used to produce 0.2 in. diam by 12 in. long alloy ingots. The crucible tube is alumina, containing the charge which has been is swaged, or machined to 0.195 in. diam. The lower end of the tube is immersed to 0 .195in in.d iam. The upper end is supported by a 10 mil nichrome wire which lowers the crucible mil nic hr the] wire at a prescribed rate. Surrounding the furnace is a graphite susceptor into which a control thermocouple is inserted. The furnace is insulated with fiberfrax and enclosed in a quartz tube. There is a sliding seal at the bottom around the crucible and one on the top so that an atmosphere may be used for the sample and suscep tor. The power for the furnace is supplied from a 10-kw, 450 kc generator. The skin depth (the skin depth at which the field falls to l/e of its value at the outer surface) for graphite (p = 10 (j-ohm-cm) is 0.1 in. at this fre-

Jan 1, 1970

By Joseph S. Malesky

The discovery and development of explosives mark one of the most important findings in the history of civilization. Without explosives our vast economic enterprise concerning the mining of coal, copper, iron, aluminum, and various other ores could not function. Explosives are used in all kinds of construction works, in the razing of old buildings, blasting of trenches, driving of tunnels, and in many other instances common to our everyday life. For these reasons explosives are rightfully referred to as the forerunner of progress. An explosive may be defined as a substance (usually a mixture) that, when flame or shock is applied, yields readily to rapid combustion or oxidation, accompanied by the formation of such relatively large quantities of gases as to produce much violence and pressure which, in turn, react against their surroundings and cause what is termed an explosion. By their very nature the action of explosives is destructive and disruptive of adjacent materials. Decomposition of explosives can occur through deflagration, which is rapid burning or combustion, as in the case of black powder, or through detonation, which is an almost instantaneous disruption, as in the case of dynamites and blasting agents. HISTORY OF BLASTING WITH EXPLOSIVES At one time workmen obtained stone blocks for building by grooving the rock with crude picks, driving wooden wedges into niches in the rock, and pouring water on the wedges; the swelling of the wood forced out the blocks. As late as the 17th century, fires were placed against the face of rock to crack it, and water was sometimes dashed on the heated rock to shatter it by sudden cooling. The progress of our country is synonymous with advancement of the improved manufacture and extended use of explosives. Coal had been

Jan 1, 1981

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963