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Robert T. Hill, Washington, D. C.: Having studied very minutely the geology of the district referred to by Prof. Branner, I beg to state that his quotation of my classification of the Cretaceous deposits of Arkansas is not the one which I originally gave,* nor is it the one which has since been published and is now generally accepted.? I did not assign ally of the Cretaceous formations of Arkansas to the " middle Cretaceous,"

Jan 1, 1898

By E. M. Wise, T. E. Kihlgren, N. B. Pilling

SYSTEMATIC data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541.

Jan 1, 1935

By T. A. Read, H. K. Birnbaum

STRESS-induced twin boundary motion in the AuCd ß'phase (52.5 at. pct Au 47.5 at. pct Cd having an orthorhombic structure (space group D h)' was discussed for the case of transformation twins.' Mechanical twinning, i.e., introduction of new twin orientations by the applied stress was sometimes observed in the ß' phase which contained two transformation twin orientations. (See Ref. 2 for experimental details.) The transformation twins terminated at the mechanical twin boundary; the two initial orientations having been twinned to the new orientation as shown in Fig. l. In a "hard" tensile instrument, formation of each mechanical twin was accompanied by a sharp drop in load (and an audible click) resulting in a typical serrated load-extension curve. The mechanical twins increased in width and additional twins were nucleated as the load increased until the entire specimen was occupied by the mechanical twin orientation. A restoring force2 caused the mechanical twin and transformation twin boundaries to return towards their initial configuration on releasing the load. In a stabilized specimen* the total strain introduced by mechanical twinning was recovered on releasing the applied stress. Initial and final microstructures were identical. After decreasing gradually to a critical width, mechanical twins suddenly disappeared accompanied by audible clicks and sharp increases in load (measured at a constant rate of crosshead motion in a "hard" machine). Mechanical twins could be stabilized in any position by maintaining the applied load for a sufficient time, indicating a decrease in restoring force with time similar to that observed for transformation twins.' Orientation relationships for mechanical and transformation twins were determined and are shown in Fig. 2. The mechanical twin, T3, was twin related to transformation twin, T,, by reflection in (1ll), and twin related to transformation twin, T2, by reflection in (111)T, . T, was related to T, by reflection in(ll1)T1 . The "average" mechanical twin composition plane lay several degrees from (1ll), . In every specimen which mechanically twinned, orientation T3 was most highly favored by the applied stress, i.e., it was the twin orientation which provided the greatest change in length compatible with the direction of applied stress

Jan 1, 1961

By Eli T. Conner

My connection, under a commission from the Councils and Board of School Control of the city of Scranton, Pa., with a recent investigation of mine-caves and the resultant damages to surface-improvements, has led to the preparation, at the invitation of our Secretary, of the present paper. It is notorious that there are, in the anthracite-fields, frequent subsidences of the surface, due to the removal of the coal beneath. No particular attention is paid to such occurrences, unless they happen to injure surface-improvements. Many caves have happened in Scranton and its viciuity, which hare excited but little remark, since they have generally caused no serious damage. In August, 1909, a cave occurred in the Hyde Park section of the city, generally known as the West Side, which nearly destroyed school-house No. 16 and considerable adjacent property. Fortunately, there were no pupils in the building at the time; but the thought of the possible result, had the usual number of pupils and teachers been present, aroused the public to the gravity of the situation; and the School Board employed engineers to investigate the case. Two reports were made by separate sets of engineers, which differed in some particulars. These differences were pointed out in the public press and magnified, and the consequent agitation of the subject was taken up and greatly exaggerated by some of the metropolitan newspapers, giving to uninformed people the very erroneous impression that the whole city of Scranton was in danger of sinking into the bowels of the earth. All this tended to affect the credit of the city and to depress real-estate values. The matter was considered at a joint meeting of the Board of Trade, the Councils, and the School Board. The Hon. J. Ben. Dimmick, a former Mayor, suggested that it

Jan 1, 1912

By A. F. Melcher

The present paper is a progress report on an investigation of the physical factors of oil and gas and especially of their sands,' such as pore space, size of pores or permeability, retentivity, viscosity of the oil, temperature, pressure, thickness and area of the pay sand, water relations, and capillarity. The purpose is to determine as many of these physical factors as possible, and to ascertain the relations existing, directly or indirectly, between these physical factors and the production of oil and gas. As yet only pore space2 and size of grains of pay sands have been investigated, although an apparatus has been designed to determine the permeability of a sand to oil, water, or gas under definite drops of pressure between the entrance face and exit face of the sample. Messrs. E. W. Shaw, R. Van A. Mills, D. Dale Condit, G. B. Richardson, G. C. Matson, and C. H. Wegemann collected the samples upon which the physical determinations were made. Acknowledgment is made to my colleagues of the United States Geological Survey for many suggestions and criticisms; to Mr. Mills for the production data given of the oil wells from which some of the samples were collected; to Mr. A. W. McCoy of the Empire Gas and Fuel Co., Bartlesville, Okla., for many ideas. Determining Pore Space of Oil and Gas Sands In selecting a method for the determination of pore space, two objects were kept in mind: First, the method must not only be sufficiently

Jan 1, 1921

By Richard H. Mote

The endlessly changing pattern of mineral supply and demand offers opportunity to the alert and can bring disaster to the unwary. The discovery of ore bodies, the invention of extractive processes, the provision of new transport facilities, the political stabilization of underdeveloped areas, and many other changes can increase supply dramatically. Such new outpourings of mineral wealth from ore bodies bring fortunes to their developers, and consumers frequently find their competitive positions decidedly improved by new and cheap sources of supply. On the other hand, operators of marginal properties can find competition from newly opened high-grade mines intolerable. Consumers that have depended on the products of nearby, high-cost mines may find new, remote, low-cost supplies advantageous only to their competitors. The invention of new prospecting methods can have spectacular effects. Shortly after World War I the discovery rate of petroleum pools began to decline. The leading prospecting technique of that day, the projection downward of surface reflections of geologic structure, was proving less rewarding. Prophets foretold an oil shortage in the near future. But at that very moment scientists were perfecting the application of seismic waves to reveal underground oil-bearing geologic structures. As these geophysical methods were put into commercial use the whole outlook changed-the problem of the 1930's became how to cope with the surplus from discovery, not how to meet the ever rising demand. Many lead mines were being abandoned as unprofitable about this same time because the penalties charged by smelters for the zinc in the ores and concentrates more than counterbalanced the payments for lead and silver. Then selective flotation (at the time called differential flotation) appeared,

Jan 1, 1964

TO THE. BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN Submitted herewith are the report of the Treasurer for the year 1945 and reports for the same year of the following committees: Membership, Admissions, Papers and Publications, Mining and Metallury (Magazine), and Library. In this review of the year by the Secretary reference frequently will be made to the "Paul" Committee and to the "hotter" Committee. The first is the special committee on Divisional Relationships and the second the special Committee on Ways and Means. These two important committees, appointed by President Harvey S. Mudd under authorization of the Board of Directors on March 21, 1945, were composed as follows:

Jan 1, 1946

By G. Ansel, J. O. Betteron

THE PURPOSE OF THIS PAPER is to give a brief picture of present day magnesium rolling practice, to elaborate on laboratory and development rolling experiments; and finally, to discuss the possible Future rolling of magnesium. The present production practice is so varied between various mills that it can only he concluded that no single producer is now using a process that is outstandingly superior to others. In view of this, only the general features of present day production practice have been presented and attention is focussed on the results of laboratory find development rolling of magnesium-base alloys as indications of the Future trend of magnesium rolling. MAGNESIUM ROLLING LITERATURE The literature relating to magnesium rolling is divided into three groups: the deformation mechanisms of the hexagonal magnesium crystals, the metallurgical aspects and laboratory type experiments in rolling, and finally, the articles on production rolling methods. This literature was reviewed and is summarized below. In the first group of references, the existence of basal slip in magnesium single crystals was shown by Schiebold and Siebel1 and of {102} twinning by Mathewson and Phillips2, Schmid3 predicted and partially established {101} slip at hot working temperatures. Bakarian and Mathewson4 confirmed the above and eliminated {101} twinning as a probable deformation mechan-

Jan 1, 1948

By M. C. LYNN

RECENT completion of a $40,000 lubricating oil plant will make it possible for students in the School of Petroleum Engineering at the University of Oklahoma to carry out on a large scale the entire process of refining crude oil, from the time it is received in tank cars and pumped through the 1/4-mile University pipe line to storage tanks on the campus until the various products appear in finished form. This plant is part of a $100,000 expansion program which this school has been carrying out during the past year. Two years ago the Oklahoma State Legislature appropriated $50,000 for the School to use in improving its laboratory facilities. A few months later a $30,000 PWA grant was ob-

Jan 1, 1937

By Arthur A. Brant

Let us start back as far as possible, to the beginnings of this universe, some 5 billion or more years ago. This is a time interval that can be crudely underestimated by the moon-earth tidal friction effects that have increased the length of the day by about 1/1000 second per century-from a 5 to 7 hour day to its present 24-and have moved the moon away at 5 inches per year to its present 240,000 miles. The oldest stony meteorites from interplanetary space give an age dating of some 4.6 billion years, approximating the time of formation of our earth. Further, certain stars pulsate, the period of pulsation being related to their absolute brightness. Measuring apparent brightness and comparing, gives the distance away. Thus Hubble and Shapley of Harvard, from 1925 on, were able to show that the universe reached as far as our telescopes could scan. The Doppler shift of the hydrogen red lines could only mean that the nebulae, or galaxies, were moving away at velocities increasing with their distances, by 180 km/ sec velocity increase for every million light year's distance. In short, the universe is expanding like an exploded bomb.

Jan 4, 1964

By J. Ruzicka

IN creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently bear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addi-tion to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabri-cated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment.

Jan 1, 1937

By W. B. Plank

THE figures on enrollment in the engineering schools of the United States and Canada indicate that the total number of students in these schools for the current year, 1949-50, is about 10% less than it was a year ago. This year, 226 - 533 undergraduates and graduate students are studying engineering in the United States and Canada as compared with. 249,913 students last year. These figures are taken from advance data in the Journal of Engineering Education for February 1950.

Jan 1, 1950

By C. H. Mathewson

(New York Meeting, February, 1916) DURING the past year considerable work dealing with the mechanical properties and microstructure following the anneal under uniform conditions of certain types of commercial rolled brass has been done in this laboratory. Since these experiments were conducted with the active cooperation of the Bridgeport Brass Co., involving free use of its product, and have thus furnished information which is characteristic of some of its special mixtures, full publication of the numerical relationships and comparative results encountered does not seem justifiable. Some of the more general features of this work are, however, available and it is our present purpose to use the material in question, along with some results of special tests, in discussing the characteristics of recrystallization as related to the degree of hardening by strain and the ordinary annealing variables. We desire to make acknowledgment of the many courtesies extended by Mr. Charles Ferry, Metallurgist of the Bridgeport Brass Co., and the value of his cooperation, which has greatly stimulated the study of brass in this laboratory. A clear and systematic presentation of the principal relations between temperature and time of anneal, the changing physical properties and microstructure and the degree of previous reduction by cold-rolling, was first made, in the case of rolled brass and copper, by the French engineer, C. Grard,1 in 1909, although much fragmentary information of this general character had appeared earlier and the main facts involved were undoubtedly known to many brass specialists through their own private research. From this work, it appears that in the cartridge mixture (67 per cent. copper, 33 per cent. zinc) the properties imparted by cold-working within the limits, 13 to 75 per cent. reduction of area by rolling

Jan 1, 1916

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.' The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

By S. S. Marsden, S. A. Khan

Externally generated foam was injected continuously into short porous media. Both flow rate and pressure drop were measured. Liquid saturation was determined by electrical conductivity. Foam yuality I, expressed as the ratio of gas volume to total volume, was varied from 0.70 to 0.96. As measured with a modified fann VG Meter, apparent viscosity of this foam µa decreases with increasing shear rate but usually falls within the range of 50 to 500 cp. At a given shear rate, µa increases almost linearly with I-. When measured with a Bendix Ultraviscoson, kinematic pa is independent of V but absolute pa increases with T from about 3 to 8 cp. The effective permeability -apparent viscosity ratio ke/µa decreases almost linearly with V for porous media of high permeability, but the rate of decrease becomes less for tighter ones. The relative permeability-apparent viscosity ratio kr/µa us V data does not fall on a single line. The kr/µa ratio increases with liquid saturation in the porous medium and with surfactant concentration. Estimates of pa for foam in porous media vary from 30 to 100 cp. INTRODUCTION Although research on the development of a foam-drive, oil recovery process has been going on for almost a decade, most of the significant publications have appeared within the last several years. This illustrates well the rate at which interest in this process is accelerating. Bond and Holbrook 1 were the first to describe the use of foam to improve oil recovery in their patent of 1958. They proposed that an aqueous foaming agent slug be injected into the formation and that this be followed by gas to produce a foam in situ. Fried 2 studied the injection of foam into porous media which had already been subjected to conventional gas or water drives and found that gas could be used to drive a foam bank which would, in turn, displace additional oil in the form of an oil bank. He attributed the increased oil recovery to the high effective viscosity of foam flowing in porous media. His microscopic observations showed the importance of foam generation and regeneration within the porous medium. By injecting both air and aqueous surfactant solution, Bernard3 generated foams within the porous medium in which oil displacement was being studied. In a separate empirical test, he also measured the dynamic foaming characteristics of the same surfactants in water and/or oil. With some exceptions and for the seyen surfactants studied, there seems to be a qualitative relationship between the efficiency of liquid rlisplacrment and the dynamic foaming testtsed. This relationship was not consistent enough to eliminate the necessity of actual foam flood tests in porous media for surfactant selection. In a study basic to gas storage in aquifers, Bennett4 described the displacement of brine by foam in consolidated porous media. Among other things, he stated that the ability of a surfactant solution to foam is more important than the stability of its foam. The presence of a foam bank between the displacing air and the displaced brine improved both breakthrough and ultimate recovery. In a continuation of this work Kolb5 attributed the great reduction in surfactant solution production rate as displacement by air progressed to a decrease in relative permeability to gas. These several effects reported by both Bennett and Kolb can all be attributed to the high apparent viscosity of foam which was obviously flowing in the porous media. Bernard and Holm6 observed that gas permeability in the presence of foam was much less than in the absence of foam when both were measured at the same gas saturations. This reduction in permeability was proportionately greater for more permeable sands and sandstones than for the less permeable. Viscosities of the surfactant solution and air were used for their calculations rather than apparent foam viscosities. The foam stability increased with decreasing permeability, which was probably due to the natural regenerative properties of porous media, and the permeability reduction increased

Jan 1, 1967

By C. W. Dunham

FOR discharging and diffusing the gases from the reverberatory furnaces and converters the Morenci Reduction Works has been provided with one of the largest reinforced concrete chimneys ever built. It is 612 ft. high from the bottom of the foundation to the cap at the top, and has a minimum diameter of 24 ft. inside the lining near the top and 38 ft. 10 in. at the bottom. Its estimated capacity, at the elevation of 4338 ft. above sea level, is about 1,000,000 cu.ft. of gas per minute at a temperature of 500° F. and an atmospheric temperature of 90°. Under these conditions the draft will be at least 3 in. of water at the flue inlet. The gases enter the chimney through a steel balloon flue 33 ft. high and 15 ft. wide, the bottom of which is 19 ft. above the ground.

Jan 1, 1942

By F. V. Lenel, G. S. Ansell, E. C. Nelson

IRMANN'S' discovery that extrusions of fine alumi-num-flake powders possess remarkable high-temperature strengths has led to the production of a new class of engineering materials whose properties are derived from a fine dispersion of oxide particles in a metallic matrix. A fundamental study of such materials and elucidation of the mechanism whereby the oxide parti-

Jan 1, 1958

By E. M. Wise

IN a previous communications the improvement in strength, harden-ability and color, occasioned by replacing gold in a typical gold-silver-copper alloy by various amounts of platinum, or palladium, was discussed. In the present paper the results of further studies upon the constitution and the nature of the hardening transformation in these alloys are pre-sented. This research may be summarized as follows: 1. The liquidus and solidus have been determined for the alloys of the palladium and platinum series. Cooling curves were utilized for deter-mining the liquidus of the palladium alloys but this method proved unsuitable for the platinum alloys so that a, novel quenching method was utilized for the latter. Both the liquidus and solidus of the palladium alloys increase steadily with the palladium content. The liquidus of the platinum alloys increases rapidly with the platinum content, while the solidus temperature increases with the platinum content up to about 14 atomic per cent platinum, but suffers no further increase with additional increments of platinum up to 20 atomic per cent at least, owing to a peritectic reaction. 2. Palladium, and even more effectively platinum, reduces the rate of grain growth. Owing to this fact and to the increase in the solidus temperature, "overheating" does little or no damage to alloys containing reasonable quantities of these elements. This is confirmed both by tensile tests and metallographic examination. 3. The excess phase present in one of the high-platinum-content alloys has been isolated and chemically analyzed and was found to consist almost wholly of platinum, gold, and copper, evidently derived from the compound AuCu, by the partial replacement of gold by platinum.

Jan 1, 1933

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968