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By Enrique Hauser

Discussion of the paper of ENRIQUE HAUSER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 521 to 534. GEORGE A. BURRELL, Pittsburgh, Pa. Mr. Hauser determined the influence of inert gases on the properties of fire-damp mixtures, and one might take some issue with his work on the effect of hydrogen, on those mixtures. It is valuable information to have, but as far as the practical application of it goes, it is not of much significance, because one does not find it in mines, at least not in any appreciable amount. The same Fig. 1.-APPARATUS FUR DETECTING COMBUSTIBLE GASES IN AIR. thing can be said of ethylene. Ethylene is formed in considerable quantities as a product of heat reaction, but normally, in the coal mines, as a result of a great many analyses we have made at the Bureau of Mines, we cannot say that ethylene is a combustible gas found in the fire-damp in coal mines.

Jan 5, 1916

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

By A. A. Toprac

The recurring problem of joint failures in ofjshore structures, coupled with the catastrophic collapse of many of these structures during Hurricane Hilda (1964), hay forced reconsideration of techniques presently used to design sfuctural joints. This paper presents results of studies conducted for this reconsiderat?on. Only right-angled T-joint,s and cross-joints where a brace was welded directly to the undisturbed surface of another tube (the chord) were considered. Tests were performed on seven T-joint and 12 oross-joint specimens of two types which were designed to give a broad but practicd range to the geometrical parameters believed to be of significance to the problem. These paramefers were expressed in dimensionless form. Each specimen of the T-joints was instrumented wirh both electrical resistance strain gauges and deflection dials. After the elastic tests were concluded, each specimen was loaded to failure by applying an axial tensile load to the brace. The cross-joints were tested to failure without measuring elastic strains. Theoretical solutions for the stresses in a cylindrical shell due to a distributed radial load over portions of its surface were numerically evaluated. The experimental results are compared with calculated values obtained using Bijlaard's and Dundrova's theoretical analyses. INTRODUCTION During the last IS years a large number of structures were built for the offshore exploration of oil both in the Gulf of Mexico and dong the Pacific Coast.' In all these offshore platforms, the tubular shape was extensively used since this shape provides outstanding strength in proportion to its weight, compared to other shapes, when all directions (x, y, z) are considered. Past use of tubes was hampered because of connection details. But with the advent of welding, it became no more difficult to connect tubular shapes than to connect rolled shapes. However, some problems have been encountered in actual construction in making welded joints that are adequate and yet economical. In trying to connect tubular members, designers have used a varied number of methods; consequently, some of the joints seem to be very expensive in detail while others appear weak and underdesigned. An inspection of offshore platforms owned by different companies indicates the use of a large number of joint arrangements and configurations. Such a variety of joint types in current service indicates the wide divergence of opinion that exists on how such joints should be designed, stiffened and strengthened. Fig. 1 shows the various types of connections that have been used in practice. This paper reviews the present state of art on tubular joints of the T and cross type, and presents results of experimental and analytical work being conducted at The U. of Texas and elsewhere. It is believed that such information will be of great help to designers for the formulation of proper design procedures for joints. CONNECTION PROBLEM Recently, cracks have been observed in several welded connections in offshore structures. Fortunately, until about 1 1/2 years ago, these failures have been localized and have not resulted in the collapse of structures or loss of life. For example, one platform installed in Louisiana during 1955 in about 60 ft of water had been subjected to four tropical hurricanes. This platform successfully withstood these forces and was later removed because operations at this location had been completed. Many joint failures were observed during the removal.

By H. S. Martin

The Phosphate Recovery Corporation operates three flotation plants, Nos. 1 and 2 concentrators about three miles northeast of Mulberry, Florida, and No. 3 plant at Wales, Tennessee. These plants represent the first commercial phosphate flotation operation and are also believed to be the largest nonmetallic flotation operation in the world at the present time. The details of this paper will be confined to plant No. 2, this being the newest and largest concentrator in Florida, and the flow sheet being practically the same as at plant No. 1. The No. 3 plant has been operated but a short time and has been shut down since December, 1932, on account of the decrease in phosphate rock production. The phosphate washers usually are located centrally on a known deposit so that about two hundred acres of ground can be mined economically to each washer location. The washers are moved to new areas when the distance becomes too great for economical pumping. The flotation plants are built either adjacent to a washer, so that current debris may be utilized, or on the site of a former washer where there is sufficient accumulated debris available for mining, and the flotation plants must also be moved from time to time. Most of the water used in the Florida flotation plants is recovered after passing through a circulating system where most of the fine suspended matter is settled out, but some make-up water is obtained from deep wells near the plant. Power is obtained from the Tampa Electric Co. through the distribution facilities of the International Agricultural Corporation. Flotation concentrate is hauled from the plant by trolley over the International Agricultural Corporation's trolley system, to the drying plant at Prairie, one mile northwest of Mulberry. Ore Treated In the pebble phosphate district of Florida, the phosphate mineral, or collophane, is usually found in horizontal beds of varying thickness

Jan 1, 1935

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By Jasper L. Stuckey

PYROPHYLLITE, first identified as soapstone,1 later as agalmatolite,2 and finally as pyrophyllite,3 has been known to occur in North Carolina for more than 130 years and has been produced intermittently in commercial amounts for the past 100 years. Pyrophyllite mining, however, has become a major industry in North Carolina only during the past 25 years. North Carolina and California are the chief producing states. Current annual production averages 125,000 tons, of which slightly more than 90 pct comes from North Carolina. Distribution and Geologic Setting: All known pyrophyllite deposits in North Carolina are associated with rocks of the Carolina Slate Belt,4 which is composed of a vast series of metamorphosed volcanic and sedimentary materials, occurring as two zones extending in a northeast-southwest direction across the state. The larger of these zones, lying in the central Piedmont region, varies from 8 to 50 miles wide. The smaller zone lies along the eastern edge of the Piedmont region and is partly covered by coastal plain sediments.

Jan 1, 1958

By M. R. J. Wyllie, Michael A. Torcaso

With the continued deep drilling of today, increasing numbers of high pressure and high temperature gas-condensate reservoirs are being discovered. Correspondingly, the ranges of properties of gas-condensate reservoir fluids are also being increased. The literature1*'." contains several excellent reviews of the property ranges in presently known condensate reservoirs. When one examines these property ranges, it becomes apparent that the need for reliable data is great if the engineer is to evaluate properly or appraise a gas-condensate reservoir. It is the purpose of this paper to present phase-behavior data that will point out some of the important variables that influence recovery from gas-condensate reservoirs produced by pressure depletion. All these variables may be resolved into two major categories: the hydroc:arbon composition of the reservoir fluid and the physical properties of the reservoir. But the variables which we will consider are those which are usually determined from well tests shortly after discovery and are, consequently, readily available to the engineer. They are as follows: (1) the producing separator gas-stock-tank liquid ratio, (2) stock-tank liquid gravity, and (3) reservoir temperature. Laboratory depletion studies have been performed on several reservoir fluids to illustrate the effect of changes in the cronsidered variables upon ultimate recoveries. The deviation factors, Z, of a series of reservoir fluids were determined experimentally to illustrate their order of magnitude and their effect upon the calculation of in-place reserves existing at high pressurcs and temperatures. The procedures followed in conjunction with the performance of these studies and their associated calculations are illustrated in Fig. 1. For the purpose of this paper, the depletion recoveries are expressed only in terms of pcr cent of initial stock-tank liquid, with the abandonment pressure assumed to be 500 psig. VARIATION OF RECOVERY WITH INITIAL PRODUCING SEPARATOR GAS-STOCK-TANK LIQUID RATIO The producing separator gas-stock-tank liquid ratio has long been one of the principal criteria in assumptions and generalized correlations' used for the estimation of ultimate recovery from gas-condensate reservoirs. Fig. 2 presents a plot of the cumulative recovery of stock-tank liquid at abandonment as a function of the initial producing separator gas-stock-tank liquid ratio. The graphical illustration represents the results of 44 laboratory depletion studies performed on actual gas-condensate fluids. These data are presented not only to illustrate the general trend of ultimate recovery increase with initial producing ratio increase but to emphasize the considerable variation in possible recovery at any given producing ratio. Table 1 presents the properties of two actual reservoir fluids chosen to illustrate the approximate extremities of producing ratios for gas-condensate systems. The fluids designated as A and B exhibited initial producing ratios of 3,400 and 114,000 scf/bbl, respectively. Fig. 3 presents a graphical comparison of the cumulative stock-tank liquid recoveries, calculated from the well-stream compositions and produced volumes for each fluid during depletion. It is to be noted that Fluid A exhibited a recovery of only 16.5 per cent when produced to an assumed abandonment pressure of 500 psig while the corresponding recovery for Fluid B was calculated to be 62.2 per cent. This difference in recovery, which exemplifies the general trend of recovery increase with initial producing ratio increase, is readily explained by consid-

By Sir Robert Hadfield

SINCE the writer has been intimately connected with the development of manganese steel for many years, some remarks upon the early work with regard to the rolling and forging of this material might he of interest, and particularly as to the question of rails of special quality and of superior wearing qualities. In a paper on Iron Alloys, with Special Deference to Manganese Steel, read before this Institute at the International Engineering Congress in Chicago in 1893,1 the writer mentioned that, about 20 years ago, his firm in Sheffield produced railroad material, such as tires and axles, of forged and rolled manganese steel, thus showing that this product could be manipulated and worked up into the various required forms. The tires illustrated in the paper referred to above formed a particularly difficult class of work to produce in a special steel, but no special obstacles were met with Although there was no difficulty at that time in making and producing manganese steel in various forms, forged, rolled or pressed; nevertheless, on account of its higher expense, sufficient encouragement

Jan 2, 1914

By D. E. Stephenson. Discussion by R. G. K. Morrison, L. Obert

R. G. K. Morrison (Chairman, Dept. of Mining Engineering and Applied Geophysics, McGill University, Montreal, Que., Canada) - The discing of drill core has been a recognized pressure phenomenon for many years but only recently has an interest been taken in the mechanism involved. The work of Jaeger and Cook is referred to in the text. The authors have now advanced the study to establish, within certain loading limitations, a direct relationship between axial and radial stress at failure. This is an important contribution. In mines generally, where pressure conditions result in the spalling of openings, the faces of drifts and crosscuts, on scaling, usually show a concavity with respect to the opening very similar to the face of the drill hole after the separation of the stub. The same holds for shaft sinks. This suggests a similarity between the mechanism of the discing of core and that of the spalling of an opening, under pressure, to develop a more stable outline. The latter, commonly regarded as shear, is the most conspicuous type of failure observed in

Jan 1, 1967

By E. L. Affleck, W. G. Stevenson

In both Canada and the United States, a company making a public offering of securities must comply with regulations which have been passed by Federal, State and/or Provincial Legislatures. These regulations usually require the distribution of an acceptable prospectus which provides essential background information about the issuer, the project and the share offering. when the public offering has been accepted, the unlisted company may then seek a listing of its shares for trading on a Stock Exchange. Once listed, the company will be subject to rules of the Stock Exchange. This paper will deal with the specific information required for inclusion into a prospectus being submitted for a resource company and particularly those parts of concern to mining engineers and geologists.

Jan 1, 1985

By I. H. Van Horn

IN the development of the incandescent electric lamp one aim of the investigators has been to establish the fundamentals of lamp design, so that the performance of any new lamp may be accurately predicted. The study of the temperature relations in lamps has done much toward establishing these fundamentals. Fig. 1 gives the typical FIG. 1.-ARRANGEMENT OF PARTS IN MAZDA B AND MAZDA C LAMPS. arrangement of the lamp parts in both the Mazda B (vacuum) and Mazda C (gas-filled) lamps. The outstanding differences are the filament form and the bulb shape. The ideal lamp is one in which the filament operates at a uniform temperature throughout its length. In practice, it is necessary to disturb this uniformity by the introduction of supports and terminals. The amount of cooling at the supports and terminals affects the over-all efficiency of the filament as a light producer. The life of the lamp is ordinarily proportional to the maximum and not to the average filament temperature. The Holborn-Kurlbaum type of optical pyrometer has

Jan 9, 1919

By Peter F. Weiss, H. Riedler, I. M. Moschitz, A. Olsacher, G. B. Fettweis

CONTENTS : 1. NATURAL FACTORS Geology Petrography and Rock Mechanics Mining System Orientation Rock Bolting System Movability of the Ore Grain Size Distribution Permeability Contamination Value of the Ore Hydrology 2. TECHNICAL FACTORS Height Length and Width Drawing Areas Time Factor Water Predrainage Surf ace Draining Underground Draining Advancing Slitting Sequence of Development Initiation of the Caving Process Drawing Rate 3. SPECIFIC MINING RULES Advancing Development Drawing Rate Interruption of Drawing (Water Distribution, Concentration of Mud, Dilution) Blasting 4. CONTROLS Safety Controls for Operation Computerised Drawing Control Structure of the Computer Program Hard Ware Print Outs 5. SUMMARY 6. ACKNOWLEDGEMENTS 7. REFERENCES Under the heading "Development System for Block Caving under Severe Conditions" a report was presented to this congress regarding a magnesite mine using block caving for several years. On account of the experience gathered in this mine and the results of far reaching exchange of experience, as well as under due consideration of the international literature it is tried to systematically list and briefly discuss the following factors that have to be considered for development and draw control of block caving. 1. NATURAL FACTORS It is self evident that this implies all those circumstances given by nature and which cannot be altered by man. Any mining activity is subjected to those and the success is depending on how far technology can be adjusted to those conditions. Geology Deposits of considerable thickness with rather steeply inclined flat-faced contacts are optimal for block caving. While vertically there is practically no limitation- for the deposit, theoretically, the smallest horizontal basis apt for operating block caving is the minimum area necessary to get the rock to completely cave in by undercutting and drawing. Practically, only consider- ably bigger main dimensions are found, mainly because of technical factors (machinery and equipment) and economic factors (cost ratio of exploration vs. development, danger of contamination).

Jan 1, 1981

By A. Thielen

In experiments for the production of steel the principal problem has always been the introduction into, or removal from, the iron of a definite quantity of carbon. Although the solution of this problem had engaged a more or less blindly and empirically directed effort for a long time, it was only with the development of analytical chemistry that the rôle which carbon plays in the constitution of steel was disclosed in its full significance, and that many of the problems confronting the steel-maker were thereby more clearly defined than before. For a long time, and to a certain extent even to this day, the percentage of carbon in steel has been the controlling means of deter mining its quality and hardness. In many cases the percentage of carbon alone has been relied on for judging large consignments, such as the large deliveries of wire-billets and blooms to America during the past twenty years; and though to-day the influences of the other constituents are recognized and many other considerations are taken into account, and though, moreover, some special steels, such as the Hadfield manganese steel, apparently dispense to a certain extent with the assistance of the carbon, yet fix our Bessemer, Thomas, Siemens and crucible steel the carbon still remains one of the most important constituents, and I venture to say it is indispensable. In order to produce in the Bessemer converter a steel of a certain required percentage of carbon, two methods, as is well known, present themselves. By the one the decarburization process is stopped when the desired carbon limit in the bath has been reached ; by the other the bath is completely decarburizecl, and then a calculated amount of carbon added in the form of spiegel, ferro manganese, etc. In Germany the latter method only was adopted, and it was retained when the Thomas-Gilchrist process for the production of low-Phosphorus steel from high-phosphorus iron eame into use, since from the nature of the new process complete decarburization is neces-

Jan 1, 1891

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By H. Jehn

Like some other Pt-group metals palladium shows a low but considerable solid solubility of oxygen, which was found already from oxidation studies. The oxygen solid solubility of palladium in equilibrium with gaseous oxygen has been investigated at 900 - 1300 °C in oxygen (665 mbar) and air by gassing and analyzing polycrystalline samples. The 0-concentrations range from 40 to 90 ppm and decrease with rising temperature. The isobaric solubility can be represented by the least-squares fit log c0 = 0.5 log p02- 0.32 + 920/T (c0 in wt. ppm, p02 in mbar, T in K). The thermodynamic data of the exothermic solution reaction are calculated to ?H°= -17.6 kJ?mol-1 and ?S° -76.5 J?mol ? K-1. The behaviour of palladium in an oxygen atmosphere is characterized by the simultaneous reactions of the solution of oxygen in the metal and the formation and evaporation of volatile oxides besides the pure metal evaporation.

Jan 1, 1984

Jan 1, 1971

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968