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(The following-list contains the names of those members of the Institute of whose connection with military service we have only recently. become acquainted.) ADAIR, ARTHUR C., Corporal, 4th Co., 1st Tr. Bn., 154th D. B., Camp Meade, Md. BATCHELOR, STILLMAN, 1st Lieut., Co. 6, E. 0. T. S., Camp Humphreys, Va. BATES, BENNETT R., 1st Lieut., Engineers, Co. 3, E. 0. T. S., Camp Humphreys, Va. BJORGE, GUY N., Co. 3, E. 0. T. S., Camp Humphreys, Va. BOAS, Ross, H., U. S. A. BRADLEY, . H., JR., Capt., 408th Engineers, Camp Cody, N. M. BRINTON, OWEN F., Capt., Engineers, U. S. A. BROWN, HAROLD C., 2d Lieut., A. S. A.P.

Jan 1, 1919

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By Gregory L. Gullord

In September, 1975, production was begun at the new milling facility of ASARCO Incorporated, the Young Mill. The mill is located adjacent to the Young Mine 35 km (22 miles) east of Knoxville, Tennessee. The Young Mill replaced the obsolete Mascot Mill which had been operating since 1913. The basic flow sheet of Mascot was retained for the construction of the Young Mill, with a 20% increase in capacity included in the design. The Young Mill is capable of processing 7710 - t/d (8500 stpd) of crude ore from three underground mines (Young, Immel and Coy) yielding 300 - t/d (330 stpd) of 63% zinc concentrate. The Young Mill is unique in that 92.5% of the ore milled is recovered as saleable products, including zinc concentrate, construction aggregate, sand and agricultural limestone. Processing at the Young Mill is divided into five basic stages: two-stage crushing, heavy media separation, grinding-flotation, concentrate filtering and drying, and limestone by-products recovery. The ore bodies are located in the Knox formation, which consists of primary dolomite, secondary dolomite and limestone with silicas in the form of chert and jasperoid. The zinc mineralization occurs as an exceptionally pure sphalerite. The ore contains an occasional abundance of pyrite and traces of fluorite and barite. TWO STAGE CRUSHING Ore enters the crushing section from two points. The Young Mine ore is hoisted into a 816 ton (900 st) bin which feeds a 1.52m (60 in) conveyor via a 1.52 m (60 in) vibrating feeder. The Immel ore is trucked 10 km (6 miles) by an independent contractor and weighed on automatic recording truck scales at the entrance to the property.

Jan 1, 1977

By Claude P. Heiner, Carl S. Westerberg

OBSERVATION of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging was accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. CASTLE GATE D SEAM Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah and thence in semi-circular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,000 ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. 1). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 6o to 8o ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed. Fig. 2 is a graphic generalized vertical section, compiled from physical exposures

Jan 1, 1941

By James Douglas

Discussion of the paper of James Douglas, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 29, May, 1909, pp. 439 to 451. JAMES DOUGLAS, New York, N. Y. (communication to the Secretary*) :-In my paper on the Conservation of Natural Resources, I referred to the slow replacement of bee-hive ovens by the by-product ovens as a most notable instance of waste. And I quoted from Mr. Parker's report for .1906 an explanation given by him in accounting for the small production of by-product coke. It was that the markets for the by-products of the coke-ovens was so limited that some of the ovens constructed were out of operation. His report on the manufacture of coke in 1908 1 does not record an improvement, and attributes the strange fact that we alone, of all the industrial peoples, delay the adoption of this cardinal improvement from the continuance of the same almost inexplicable cause. To quote again from his report, lie says (p. 241): "The year 1908 was not marked by any notable gain in the construction of by-product coking plants, though some new work was done. There was a net increase of 115 in the number of completed ovens in 1908 over 1907, the totals for the two years being, respectively, 3,892 and 4,007. The additional equipment consisted of 140 Koppers regenerative ovens built at Joliet, I11., by the United States Steel Corporation, but this increase was partly offset by the dismantling of Y5 Semet Solvay ovens at Sharon, Pa., the net gain being 115 ovens. Included in the total of 4,007 completed ovens in 1908 are 152 Newton-Chambers ovens at Vintondale, Pa., but as no recovery of by-products was made at this plant in 190S, the production of coke is included with that from beehive ovens. The 56 ovens of the same type at Pocahontas, Va., have not been in practical operation since they were first. installed. In addition to these there was one other by-product plant of 120 ovens. Oat. was not operated during the year. The number of retort ovens producing coke in 1908 was 3,679, as compared with 3,811 active ovens in 1907." In describing the anomaly he says (p. 249): It has been contended that the development of the by-product coking industry would have shown more rapid progress if markets for the by-products were * Received Feb. 2, 1910. Mineral Resources of the United States for 1908, Part I1., U. S. Geological Survey (1909).

Apr 1, 1910

By HOMER L. WILLIAMS

WHILE some of the mining companies have been pumping a small amount of water for some time, it is only in recent years that large quantities of water have been encountered in the Tonopah district. The water appears to be in different zones or belts so that the draining of one property does not necessarily affect the one adjoining. Consequently, each company has its own pumping plant and its own conditions. The companies panes handling the largest amount of water are the Tonopah Extension Mining Co., Halifax Tonopah Mining Co., West Tonopah Consolidated Mining Co., and Great Western Consolidated Mining Co. The Halifax shaft is on the eastern end of the district and the other three properties on the western. The ore-bearing formation occurs at greater depth on -the eastern and western ends, hence the water problem in these properties.

Jan 1, 1921

By Herman Van Fleet, Frederick W. Neil, O&apos

The object of this paper is to describe the present status and possil~ilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. 3. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Kitherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 1, 1927

By Wayne E. Hall

The Darwin mining district of California, 160 miles north of Los Angeles, has yielded an estimated $45 million in lead, silver, zinc, and copper since 1875. The deposits are in silicated limestone of Pennsylvanian and Permian age close to a stock of horn- blende-biotite-quartz monzonite. Steep left-lateral strike-slip faults that strike N 50" 70" E served as feeder channels for the ore solutions, and minor folds, favorable beds, and faults close to the feeder channels localized the orebodies. The orebodies are irregular, steep, pipe-like replacements that cut across bedding, bedding replacements, and fissure fillings in a calc-silicate country rock consisting mainly of wollastonite, grossularite-andradite garnet, idocrase, and diopside. Near surface the ore consists of a soft, crumbly mass of cerussite, hemimorphite, jarosite, limonite, and some secondary copper minerals. The primary ore consists of galena, sphalerite, pyrite, pyrrhotite, and chalcopyrite with smaller amounts of andorite, matildite, scheelite, tetrahedrite, and a high silver- lead-bismuth-selenium-bearing galena.

Jan 9, 1959

By Herbert Banks Johnson

DURING the past 10 or 12 years very little information has been made generally available concerning the commercial possibilities of separating materials by means of static electricity; and yet during that same period important improvements have been made in various branches of the science of electricity, which, when taken together, and applied to electrostatic separation, have resulted in important improvements in that art as well. For example, much improvement has been made in high-voltage electrical equipment such as full-wave vacuum-tube rectification and improved mechanical rectification. Great strides have likewise been made in the development of insulators for high-voltage work, not only in the materials used but also in the design of the insulators themselves. Again, in another field, the development of air-conditioning equipment has improved the technique of controlling the surface condition, through drying or humidifying, of the various materials that are passed through the electrostatic separator. In many authoritative publications and textbooks, the electrostatic separation process is declared to require a balance far too sensitive for general commercial application. For example, one publication1 in the past has referred to an unfavorable effect on the process caused by varying atmospheric conditions such as humidity. Some2 have even gone so far as to state that sunlight and shadows may seriously affect the separating efficiency of the process. Such statements may have been true in the early development of the art, when the source of static electricity was derived from a friction disk machine, such as the Wimshurst. The Blake Mosher equipment and the work of Huff in applying motor- generator sets, transformers and mechanical rectification overcame much of this kind of objection to the commercial application of the electrostatic separating process. Another objection made periodically is that it is generally considered necessary to feed the particles into the electrostatic field in a stream that

Jan 1, 1938

By W. N. Lacey, R. H. Olds, B. H. Sage

The volumetric behavior of five mixtures of black oil and natural gas and of two mixtures of condensate and natural gas from a field in the San Joaquin Valley was experimentally established. This work was carried out at roo°, I9o° and 250°F in the pressure interval between 400 and 5000 psi. The viscosity of the liquid phase of four mixtures of black oil and natural gas was experimentally measured in the above-indicated temperature and pressure intervals. The effect of methane upon the precipitation of bitumen from the black oil was studied at 230°F. Introduction The solution of a number of the economical and technological problems which arise in connection with petroleum production is dependent upon the availability of the necessary quantitative information covering the materials involved. This requires data concerning physical properties of naturally occurring hydrocarbon mixtures at the pressures and temperatures characteristic of underground petroleum reservoirs. The experimental determination of the desired data for each situation encountered is relatively time-consuming. However, it is considered to yield results sufficiently more reliable than those obtained from correlations to justify the effort. For these reasons there was undertaken a laboratory investigation of the viscosity of the liquid phase and the volu- metric and phase behavior of mixtures of oil and gas samples obtained from wells in a field located in the San Joaquin Valley. Terminology The nomenclature of petroleum engineering is not at present entirely standardized. Many commonly used technical terms are not everywhere given the same meanings. For the purposes of this paper the following definitions will be adopted: Black oil refers to the dark-colored, hydrocarbon liquid obtained when the producing horizon of the well lies partly in the condensed hydrocarbon phase of the reservoir. Condensate is the term applied to the relatively volatile, pale yellow or amber-colored hydrocarbon liquid that is often obtained from the surface separator system when the producing horizon of the well lies in the gas cap of the reservoir. The gas obtained from the surface separator system is called natural gas regardless of whether the well is producing black oil or condensate. As might be expected from the multi-component character of naturally occurring hydrocarbon materials, the compositions of black oil, condensate and natural gas are subject to considerable variation depending upon the temperatures and pressures prevailing in the surface separator system as well as upon the overall composition of the material produced from the reservoir. In order to obtain samples capable of reproducing the total hydrocarbon material produced by the well, all oil and gas mixtures used in this investigation were com-

Jan 1, 1949

By J. L. Bray

ACCELERATED programs, as discussed in this paper, refer to the year-around operation of a college or university with three sixteen-week or four twelve-week terms per year, with pauses between sufficient only to allow the administrative group to perform their functions. In most engineering schools, under such conditions, the conventional four-year course can be condensed to two years and eight months. These accelerated programs of study, which now exist in most of our technical institutions, were forced upon us under the influence of the outburst of wartime patriotism, perhaps one might go so far as to call it hysteria. Many of us felt and hoped that these programs were temporary expedients, but the cold hard threat of permanency now rears its head; consequently we should examine the merits and shortcomings of the new order, and evaluate its effect on our educational system, since it may persist in some form in the postwar years, because of the changing political and financial situation. Many engineering students are being educated in state supported institutions

Jan 1, 1944

By F. C. Stanford

THE work of an engineer is to direct natural forces so that they bring about the results that he wishes to secure. Heretofore he has 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 knowledge and control of the human factor. Progress has already been made along this line, but, it is only a beginning. Wilhelm Ostwald says that 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 maintain 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 essential need of the period is for more brains; if we only had sufficient knowledge and sagacity we could not only solve all difficulties, but prevent them from arising. This generalization holds good for an industrial organization. The most vital need of the management is for more brains. The logical 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 easier said than clone, for it involves the carrying on toward two objectives, the maximum of productive work, and the development of the individuals who perform it. This is essentially like the rebuilding and enlarging of a plant, keeping it in full operation the while. On the other hand, if the aim is merely for maximum production from an organization, without offering opportunity for development, the final outcome will necessarily be like that f a plant that is driven at full capacity without stopping for repairs or improvements; it eventually becomes so run down that either a complete rebuilding is necessary or else it has to be abandoned.

Jan 2, 1918

Jan 1, 1951

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

Jan 1, 1958

By Rustum Roy, E. F. Osborn

THE investigation discussed in this paper concerns phase equilibria in the alumina-silica-water system. Studies in this system are part of a re¬search project sponsored by the Geophysics Branch of the Office of Naval Research2 directed toward increasing knowledge of the stability relations of metamorphic mineral assemblages. Inasmuch as metamorphic rocks consist largely of aluminosilicate struc¬tures, many of them hydrated, the system alumina-silica-water is a logical starting point for the systematic laboratory study of metamorphic mineral systems. Although logical, this is not, however, an easy approach to the problem because of the very great difficulty of obtaining transformations among structures in response to changes in temperature, pressure, and con¬centration. Commonly equilibrium among the phases in this system is exceed¬ingly difficult to attain. New laboratory techniques are required to produce certain structural rearrangements, such as inversion of diaspore to boehmite or the transformation of alumina-silica mixtures to andalusite or kyanite. Phase equilibrium data for the alumina-silica-water system are consequently only partly complete, and only a summary progress report is presented here. Crystalline phases in the alumina-silica-water system are numerous and many are common minerals. The oxide components exist as: quartz, tridymite, cristobalite, corundum, water, and ice. Binary compounds occurring naturally are: sillimanite, andalusite, kyanite, and mullite in the alumina-silica system and gibbsite, boehmite, and diaspore in the alumina-water system. The most abundant among the ternary compounds is the composition A12O3.2SiO2.¬2H2O, existing in the four structural modifications, kaolinite, nacrite, dickite, and halloysite. The hydrated form of halloysite, A12O3.2SiO2.4H2O, is here called endellite. Pyrophyllite, A12O3.4SiO2.H2O, is the third ternary compound of natural occurrence. In addition to these minerals, two other ternary crystalline phases have been encountered in this study. The first is a structure resembling montmorillonite and corresponding perhaps to the pure aluminian end member of the beidellite series. The other has a composition approximating A12O3.2SiO2.H2O but its composition and structure are still in doubt. LABORATORY PROCEDURE In these laboratory studies, a starting material such as an alumina-silica gel or one or more of the crystalline phases is wrapped in platinum foil,

Jan 1, 1952

By Dr. O’Neil Thomas J., Donald W. Gentry

There are mines that make us happy, There are mines that make us blue, There are mines that steal away the tear-drops As the sunbeams steal away the dew. There are mines that have lost the ore chute faulted, When the ore's forever lost to view, But the mines that fill my heart with sunshine, Are the mines that I sold to you. -Anonymous INTRODUCTION The preceding chapters have discussed, in various degrees of detail, the primary considerations necessary to perform a cash flow analysis of a mining-related investment opportunity. Although the previous discussions regarding the manipulations, calculations, and interrelationships of the various components of the pro forma income statement were illustrated in the text, many individuals are un- familiar with the format and appearance of a final spread sheet for the evaluation of a mining property. As a result, it seems appropriate to conclude this book with an abbreviated case study of an actual mine property (currently in production) showing the cash flow analysis and some back-up data. Obviously all of the supporting data and calculations for the case study presented cannot be provided; however, reference is made to the major assumptions utilized and to the appropriate procedures employed in the calculations, as described elsewhere in the text. The problem associated with using any case study for illustrative purposes is that one tends to be overwhelmed by detail. For instance, specific costs, prices, expenditure timings, and other variable values may be challenged because they either do not conform to one's expectations or are not consistent with specific operating experiences. When this occurs the instructional value of the problem becomes obscured. The purpose of most case studies, and particularly the one presented in this chapter, is to expose the student to the methodology, procedure, and format associated with performing a cash flow analysis of a mining property. It is not to laboriously wade through the specific details associated with operating and capital cost development, mine plans, or equipment schedules. It should be noted, how- ever, that the values represented in this case study result from specific mine plans, operating procedures, equipment spreads, manpower requirements, and other en-

Jan 1, 1984

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964