Search Documents

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By S. W. Ross

In 1936 a description of the plant (Fig 1) and process employed by the Electrolytic Zinc Co. of Australasia Ltd. for the recovery of zinc from zinc concentrate by the electrolytic process was prepared. † During the twelve years which have elapsed since the preparation of the earlier paper, several major changes in the metallurgy of the process have been introduced. It is the purpose of the present paper to give a general description of these changes and thus to bring up to date the description of the plant and process. Summary The major changes in Risdon practice since 1936 have been: 1. Replacement of two stage roasting by a preliminary roast followed by the flotation of all the leach residue and the roasting of the flotation concentrate. 2. Screening of all calcine fed to the pachucas. 3. Continuous leaching of calcine and improved classification of pachuca discharge. 4. Close control of hydrogen ion concentration during purification for iron removal. 5. Recovery of cobalt as a good grade oxide. 6. Production of part of the zinc output in the form of "four nines" metal (99.99 pct purity). 7. Closer spacing of electrodes thus increasing the potential output of cathode zinc per cell by 50 pct. Changes which are in prospect and for which construction work is proceeding at the present time involve the starting up of: 1. Two suspension roasters. 2. A contact acid plant to produce 150 tons‡ of acid per day and replacing the existing Mills Packard chamber plant. 3. Extra power station capacity to permit greater current flow to existing cell room units. This will increase the output of cathode zinc from about 245 to 290 tons per day. Plans for the future envisage the building of an ammonium sulphate plant, the first unit of which will produce about 50,000 tons per year, and improved treatment of zinc plant residue for the recovery of zinc, lead and other metals. At the end of this paper tables of metallurgical data are presented relating to the year ending June 30, 1948. Details of Changed Practice Output In 1936 the production of cathode zinc amounted to about 200 tons per day. This has since been increased to about 245 tons per day while plant extensions are practically complete which will permit of an output of about 290 tons per day in the near future. Roasting Division ROASTING POLICY A major change has occurred in the roasting policy. Twelve years ago the method in use was to carry out a two stage roast in the first stage of which sulphide sulphur was reduced to about 6 pct. The pre-roast calcine was re-roasted in modified Leggo furnaces using coal as fuel, sulphide sulphur being reduced to about 0.8 pct. The whole procedure was described on pp. 482491 of the earlier paper. Although this roasting procedure had certain advantages it possessed some distinct disadvantages. For instance, it appeared uneconomical to heat up the entire input of pre-roast calcine to roasting temperature by the expenditure of fuel in order to oxidise a few percent of sulphide sulphur. It was argued that if the pre-roast calcine were leached and a process could be developed for the recovery of a zinc sulphide concentrate from the leach residue, this concentrate, small in weight compared with the pre-roost calcine, would probably roast autogenously, thus virtually eliminating the expenditure of fuel as well as greatly increasing the weight of sulphur oxidised per square foot of furnace hearth area. The obvious method of producing a suitable concentrate from leach residue was by flotation. It will be recalled (see p. 495 of the earlier paper) that when two-stage roasting was practised the leach residue was classified, the granular fraction was ground and floated while the slime fraction was thickened, filtered and dried ready for shipment to a lead smelter. This process worked quite successfully. However, when trials were made of leaching a calcine carrying several percent of sulphide sulphur the granular fraction still floated well, but the slime fraction carrying 8-10 pct sulphide sulphur yielded very poor results when subjected to flotation. This fact held up the application of "pre-roast" leaching for many years. However, successful flotation of the slime fraction of leach residue was finally achieved and in August 1940 the slime flotation plant began operation, while the leach-

Jan 1, 1950

By K. Stout, E. Van Eeckhout, L. Friel

Previous research at the Montana College of Mineral Science and Technology indicated that it is practical and economically feasible to place stiff back- fill in a cut-and-fill stope. This backfill would reduce wall closure and high stress buildup in pi1llars, thus alleviating rockburst potential. Three ;topes from the Sunshine Mine, of the Coeur d’Alene Mining District, were chosen for a test verification of this concept. Although the first stope was lever mined beyond the initial cut (for economic reasons), some vibrating wire stressmeter results were obtained and found to compare favorably with numerical predictions. Some other instrumentation devices were built and tested, but never installed .

Jan 1, 1984

By A. C. Fraker, H. H. Stadelmaier

WIENER and Bergerl reported the existence of the nitrides Fe3NiN and Fe3PtNwith a cubic L1'2 structure. The present note shows that a similar nitride Fe3PdN can be observed and that the composition range between the iron nitride Fe4N and the nitrides Fe3NiN, Fe3PdN, and Fe3PtN is occupied by single-phase cubic nitrides with structures intermediate between L1' and L1'2. The materials used in this investigation were electrolytic iron of 99.9 pct purity, carbonyl nickel of 99.7 pct purity, sponge platinum of 99.95 pct purity, and palladium sheet of 99.8 pct. purity. Binary alloys of the transition metals were induction-melted in a crucible of fused alumina, powdered, and screened to a particle size of - 200 mesh. The powders were nitrided at 600°C in a gas mixture of ammonia and hydrogen, and the crystal structure was determined with the aid of a Wilson powder camera. The results are compiled in Table I together with information from the paper of Wiener and Berger.1 The compound at the nominal composition Fe3PdN has a diffraction pattern with prominent reflections of a face-centered cubic lattice (h2 + k2+l2 = 3, 4, 8, 11, 12, 16) and weaker superstructure lines (h2 + k2 + 12 = 1, 2, 5, 6, 9, 10, 13, 14). With decreasing palladium content the superstructure lines become weaker and approach the intensity of those of Fe4N. No analysis was made of the intensities, but it can be assumed that the structure is that found by Wiener and Bergerl in Fe3NiN and Fe3PtN, namely L1'2 (perovskite structure) with both palladium and the interstitial nitrogen fully ordered. The dependence of the lattice constant upon the solute atom (Ni, Pd, Pt) content can be explained tolerably well by simple lattice expansion due to subsequent work confirms this suggestion, it will be of significance to order-disorder theory. The author is grateful to Lester Guttman for discussions on this topic.

Jan 1, 1961

One Hundred and Twelfth Meeting of the Institute, Monday, February 14, to Thursday, February 17, inclusive, 1916 COMMITTEE ON ARRANGEMENTS DAVID H. BROWNE, Chairman. BRADLEY STOUGHTON, Vice-Chairman. LAWRENCE ADDICKS, BURR A. ROBINSON, P. E. BARBOUR, E. M. SHIPP, G. D. BARRON, JOSEPH STRUTHERS, J. V. N. DORR, E. B. STURGIS, J. R. FINLAY 'R. H. VAIL. L. D. HUNTOON, Hotel Accommodations.-The Committee on Arrangements is canvassing a number of hotels in New York City, securing .wherever possible special rates to members and guests for the clays of the meeting. It is possible to secure good accommodations on very reasonable terms in New York City if one knows where to look for them. A list of hotels and rates will be published in the final announcement of the meeting, which will go to the members about the middle of January, in order that those who desire to secure good hotel accommodations at a reasonable mice may have the information.

Jan 1, 1916

By R. E. Hobart

The development of the Hauto power plant and the claims made by various engineers that electricity was more economical than steam for power purposes in and about the mines, led the Lehigh Coal and Navigation Co., in 1911, to conduct a test to ascertain the consumption of power used by a large steam hoisting engine. The question being one on which no reliable information could be found, and the opinion of various engineers differing to such an extent, it was decided that a test under actual operating conditions was necessary. This was arranged for at one of the collieries. The engine selected was 2 30 by 60-in. (76.2 by 152.4-cm.) piston-valve engine of modern type, and comparatively new. The boiler plant from which the hoist received its power was about 600 ft. (182 m.) from the engine, the latter being fed by a 10-in. (25.4-cm.) steam line insulated with magnesia pipe covering. Two batteries of the boiler plant, aggregating 1200 hp., were cut off and fed into a separate steam line leading direct to the hoist engine. Steam auxiliaries, consisting of feed-water pump and blowers, were fed by the boilers in test, and their consumption charged against the hoist. A barrel weighing device was installed, as it was felt that this would be the most accurate way of determining the consumption of water. The fuel, No. 3 buckwheat, was carefully weighed, and every precaution was taken to make the test accurate in every particular. The test was run for 1 week, or a total of 168 hr. A record was kept of the number of trips hoisted or lowered, and continuous indicator cards were taken. One particular set of cards was taken with the hoist operating balanced, and also with the hoist operating with no counterweight other than the empty cage, the coal in the car being weighed. The speed of the hoist was taken by means of a graphic recording instrument which registered the number of revolutions every 5 sec. From this record, speed-time curves were plotted.

Jan 1, 1918

By Eugene McAuliffe

The term "mechanical mining" carries an ambiguity which justifies a preliminary word of explanation. . All mining activity conducted in this day is more or less mechanical; that is to say, power expressed in the form of electricity, steam or compressed air is used in some portion of practically every mining activity of consequence. "Mechanical loading" is more nearly correct than "mechanical mining" in reference to present practice. The first substantial effort made in the direction of mechanical mining, subsequent to the application of steam for hoisting and underground pumping purposes, was that of substituting for hand labor undercutting and shearing by power-driven machines. The undercutting of coal by hand represented at one time the most arduous task confronting the miner. Occupying a kneeling position in the thicker beds, or lying on his side in the thinner coal, the task was tedious and exhausting. The first attempt to substitute crude air-driven, and later electrically driven, "punchers," as the percussion type of machine was called, met with much the same opposition on the part of the workers as was expressed by workers in the other industries when any innovation, whether labor-saving or otherwise, was introduced. We should not be too critical of this attitude of mind shown by the mine workers. The peculiarly isolated character of the work carried on in semidarkness by a class of men who to a large extent lived and held themselves aloof from the other branches of society led long ago to the development of a craft consciousness which they have found difficult to surrender. It was not until 1891 that a definite record of the results obtained by the use of undercutting machines of all types was made available, the quantity undercut in that year totaling 6,211,732 tons of bituminous coal from all American mines. The volume of bituminous coal undercut by machines in 1928 totaled 369,687,007 tons, or 73.8 per cent. of the nation's production. In the light of this experience, we can properly feel that the work of introducing the coal-loading machine as a substitute for hand shoveling is making substantial progress.

Jan 1, 1931

Correlation between Metallography and Mechanical Testing By H F MOORE (Henry Marion Howe Memorial Lecture Trans, vol 120 11,000 words ) The lack of effective correlation between metallography and mechanical testing from the days of Reaumur to the present is noted, and two general problems of such cor¬relation are stated (1) the correlation of qualitative test results with quantitative, and (2) the correlation of average results with maximum or minimum results Some correlation has been achieved, notably in the field of heat-treatment and in the study of elastic strength of metals Correlation is in the process of being developed in several other fields, including the quantitative study of the effect of grain size of metal on mechanical properties, of grain size and type of crystalline structure on the sensitivity of metals to weakening at holes, notches and other "stress raisers," and in the study of the starting phases of spreading, "fatigue" cracks Correlation of mechanical test results and metallographic study is needed in the study of such problems as the various theories of failure of metals, the meaning of and tests for service ductility of metals, and the relative damaging effect of defects inherent in metals, such as minute cracks and segregation, as compared with the damaging effect of "imposed" stress raisers, such as screw threads, sharp shoulders, etc The neces¬sity for more correlation of metallography and mechanical testing during student days is emphasized, and also the need of a better understanding on the part of engi¬neers of the significance and limitations of metallographic apparatus and results and of X-ray diffraction This should be matched by a better understanding on the part of metallurgists of the significance and limitations of mechanical tests of metals, of testing machines and strain-measuring apparatus

Jan 1, 1937

By Lyle L. Marsh, David L. Douglas

CORRELATION was made between the heat treatment and hardness of three U-Ti alloys ranging in composition from 8.5 to 50 atomic pct Ti. The following important observations were made: 1) A direct quench of y U-Ti solid solution resulted in the formation of a hard martensitic phase in low-titanium alloys. 2) Subsequent tempering initially increased the hardness by the precipitation of a fine dispersion of U2Ti; further precipitation of U2Ti with tempering time eventually resulted in softening. 3) High-hardness levels were obtained also by isothermal transformation of an 8.5 atomic pct Ti alloy at 400º and 500°C. 4) The crystal structure of the phases present at the solution-treating temperature (one region in the phase diagram excepted) and the temperature within a given phase region affected the hardness of both quenched and isothermally transformed alloys. Introduction It has been known since 1887 that the mechanical properties of metals were dependent upon their microstructure. Sorby pointed out in that year that annealed gray iron castings were softer than chilled iron castings by virtue of the graphite which had replaced hard cementite in the microstructure. Over the years, interest has increased in the effect of microstructure on the mechanical properties of metals, and now high-strength levels may be achieved by bringing about the dispersion of a second phase or by other microstructural adjustments. The nature of a second phase in an alloy strongly influences the properties. For example, the size, shape, amount, and distribution of a second phase plays a very important role in the ultimate properties of an alloy. Microstructural control is achieved by heat treatments. Hence, any alloy system of potential use should be understood in terms of its response to heat treatment and the resultant effects upon the properties.

Jan 1, 1958

By C. K. McArthur

THE subject of classification is so broad that this discussion is con-fined to what the author believes is of prime importance in connection with proper grinding and classification. The years passed have witnessed many noteworthy changes in fine grinding and classification, which have been accompanied by a readjust-ment of ore-dressing flowsheets for the preparation of better ground and/or sized products at an expenditure of less. power, steel and main-tenance than formerly. Nowhere in the industry is more being done in the way of experimental work to lower costs than in grinding circuits, because, at best, grinding costs are high. Recent years have indicated that, on the average, finer grinding has a real application. Without careful preparation of the process feed, no operation can be highly efficient or successful. In an earlier paper, the findings of an extensive survey at representa-tive concentrators were presented1. Also, in the year of 1935, a technical discussion was given by Dr. J. V. N. Dorr (Some Notes on Classification Trends in America) before the Chemical, Metallurgical and Mining Society of South Africa. In both papers mentioned, much has been said regarding flowsheets, grinding and classification. The author is very familiar with these papers, having had considerable to do with the actual operation of the flowsheets, as well as large mills and classifiers in the work described. Some data from the second paper have been included in the following discussion.

Jan 1, 1937

By V. F. Swanson

At the AIME meeting in Tampa in Oct. 1966, an empirically developed equation was presented which allowed the calculation of free settling velocity for any sized particle: 1 [ ] This equation requires the use of two parameters a and p which are coefficients derived from boundary layer theory.2 It was possible to develop values of a and p for several minerals by back calculation of published data. The original equation had one major flaw. When the fluid density exceeds the density of the solids, the solution to the equation becomes imaginary. A flaw was indicated also by the fact that galena and sylvite both having cubic cleavage, did not have similar values for a and b. Galena gave calculated values of a = 1.082 and g = 3.11, while sylvite gave values of a = 1.870 and p = 2.56. These flaws prompted further study of the equation, resulting in the following empirical modification: [ ] It is obvious a real solution of the equation is possible for all values of ps and p. When PL > PS, V is negative, indicating that the particles will rise against the attraction of gravity. The validity of the modification is borne out by the fact that when values of a and p were back calculated for galena and sylvite using the modified equation, both minerals gave values of a = 1.038 and p = 3.01. With the modification shown in Eq. 2, Newton's friction factor becomes [ ]

Jan 1, 1976

By F. Bahnemann

IN discussing the problem of abnormal magnetic polarization, C. A. Heiland1? emphasized the unfortunate fact that our knowledge of the geological and physical conditions relating to such occurrences is very limited and that a more detailed insight into their physical causes would be extremely valuable for interpreting measured anomalies. He also pointed out that to arrive at quantitative physical formulas that would express the conditions that cause abnormal polarization many more occurrences of the kind would have to be recorded. The first part of this paper is a contribution to such descriptions.

Jan 1, 1935

By P. P. Gregory

Natural petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the "pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the controlled methods of production and drilling, a portion of this gas is produced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grow rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures wereincreasing. Determination of Gas-oil Contact and Thickness of Gas Cap The gas-oil contact can be conveniently located in the process of drilling a well and by electrical logging. However, very little can be found in the petroleum literature concerning methods of predetermining gas-oil contacts in producing reservoirs. Therefore, the writer feels justified in describing briefly a simple, workable, and inexpensive method of determining gas-oil contacts and outlining the limits of gas-cap areas in a field where such knowledge may be essential for efficient production and development operations. The method involves the determination of the following data: (I) Structural data, such as the depth or elevation of the top' of "pay" horizon; (2) reservoir pressures; (3) tubing and casing pressures at the well head; (4) static oil-pressure gradient; (5) static gas-pressure gradient. These data can be secured with a minimum of expense, inasmuch as the

Jan 1, 1938

DISCUSSION, M. Cohen presiding A. H. Geisler and D. L. Martin (GeneTal Electric Research Laboratory, Schenectady, N. Y.)—We were rather interested to note the author's conclusion that the cubic to tetragonal transformation may be of the second order, for we have been able to show that the order-disorder transformation in an analogous alloy system is a first-order transformation with a discon-

Jan 1, 1952

By John M. Cummings, Warren. Harry V.

THE Geology Department of the University of British Columbia has undertaken the task of examining the ores from as many as possible of the gold mines of British Columbia. The object of this work is two- fold. First, it is known that detailed mineralographic studies are useful in attacking ore-dressing problems, and these studies are intended to be helpful to mill operators. Second, it is hoped that mineralogical and mineralographical studies will prove useful adjuncts to those of lithology and structure in throwing more light on problems related to the origin of the deposits. The paper shows that gold, for all practical purposes, is not present in an ore mineral in solid solution nor as a eutectic with any mineral; if the latter were true the gold particles would be distributed equally throughout that mineral. The gold occurs either as native gold or as a gold-silver telluride and is not distributed regularly through any mineral or minerals. The relationship between the gold or gold-bearing telluride and the associated minerals affords a means of classification that is not only simple but also appears to be directly related to the geological nature of the deposit, which may be summarized as follows: 1. Disseminated Gold Type.-Precious minerals in extremely small grains, which are distributed without regard to grain size, fractures or grain boundaries: (1) Hedley variety-gold in native form; (2) Surf Point variety-gold predominantly as telluride. 2. Veining Gold Type.-Precious minerals in grains of various sizes, which occur mainly along fractures and grain boundaries: (1) Cariboo gold quartz-goldin native form. (2) Waneta variety-gold as telluride. Application Te Ore Dressing These mineralographic studies have proved to be of value to mill operators, and future studies of a similar nature should prove increasingly useful because every year provides a further opportunity to correlate

Jan 1, 1937

By Herbert Wilson

THIS topic was discussed at the meeting in St. Louis in September, 1917, and at the meeting in New York in February last, but in the interval the war has accentuated in measurable degree the necessity for considering human relationship, not only as between nations, or in the treatment of our returning soldiers, but with respect to the relations between labor and capital in industry. It is my firm conviction that no other subject will have so large a place in industrial and political life during the next decade as this. Heretofore, the employer has been so engrossed with the financial, mechanical, and technical aspects of his business that he, has been willing to muddle through 'his relations with labor as best lie might and, on the other hand, the laborer has been so engrossed in his endeavors to secure a livelihood under whatever living and working conditions might be offered him that he has given little thought to his relations to his employer, until some misunderstanding has ended in disagreement and strike. No thinking man doubts that were the machinery available for friendly, personal, face-to-face consideration of the problems confronting employer and employee, there would he fewer disagreements, fewer strikes, and a better and more settled industrial situation. The necessity for some such medium for exchange of views has resulted in the organization of labor and, in some measure, of capital. Each party, engrossed only in defending its own viewpoint, has generally tried to gain its point by might rather than by right. Gradually, however, the representatives of both elements are beginning to appreciate that when the machinery for bringing them together in friendly communion is available their differences frequently settle themselves. There remain yet vast numbers of employers and of employees who are not organized and to whom the opportunity of friendly discussion of differences is not available; for these the machinery should he provided.

Jan 1, 1919

By Thomas T., Read

SUGGESTIONS that existing schools give instruction bearing on the mineral industry, or that schools for that purpose should be established in the United States, began to be made early, and it would require too much space to catalogue them all. Some of the more important may be mentioned to indicate their general character. In the "advertisement to such parents as have now (or expect to have) children prepared to be educated in the College of New York," which appeared in the New York Mercury of June 3, 1754, Samuel Johnson, the first president of King's College, the predecessor of Columbia, said that it was the "design of this college to instruct and perfect the youth," among other things, "in the arts of Numbering and Measuring of Surveying, and Navigation and Geography. . . . and in the Air, Water and Earth around us, and, the various kinds of Meteors, Stones, Mines and Minerals, Plants and Animals; and in the knowledge of all Nature in the Heavens above us, and of everything useful for the Comfort, Convenience and the Elegance of Life . . . " Though the concept that natural science should be used to enlarge the bounds of human life was thus implicit at Columbia from the very beginning (John Stevens graduated from it in 1768, James Renwick in 1807, Horatio Allen in 1823, and A. W. Craven in 1829), it was only during the period of Renwick's professorship of Natural and Experimental Philosophy and Chemistry (1820- 1853) that much attention was given to applied science.* Among the Austin papers, published by the American Historical Association,2 there is a draft in Stephen F. Austin's handwriting of a proposed memorial from the legislature of Missouri to Congress, not only urging "the propriety and utility

Jan 1, 1941

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970