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By F. Weinberg, L. MacAulay

DAVIS,' in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"', was determined with the

Jan 1, 1970

By J. L. Gillson

The word "other" in paragraph 4, line 11, column 1, page 205, should read "over;" the correct version of reason 2, this paragraph, is: 'L. . . 2) to evaluate the usefulness of certain geo-chemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and over veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; ...9 On page 206, in the top left hand corner of Fig. 1 (in the area bounded by 47°35' and 116°10), the reference to Fig. 3 is incorrect. The area of Pine Creek, South Fork Coeur d'Alene River, and portion of Big Creek (the area which includes, from left to right, Kingston, Pinehurst, Smelterville, and Kellogg) should be identified as that of Fig. 2A. The headings for columns 1, 3, and 4, Tables I and 11, page 209, column 2, were reversed when the paper was printed. The corrected tables are:

Jan 1, 1961

By A. R. Denison

The area discussed in this report comprises a group of 38 counties lying in the northeast corner of Texas. It covers all, and extends beyond, the borders of what is commonly described as the East Texas Basin. It includes two major oil fields, Van and East Texas; two major gas fields, Bethany and Waskom; and a number of fields, both oil and gas, of lesser importance. All commercial oil production comes from beds of Upper Cretaceous age and almost exclusively from the basal member, the Woodbine sand. Gas is produced from both Upper and Lower Cretaceous beds with the newer production from the older beds. East Texas Field This field continued as in 1932 and 1933 to dominate the drilling and production situation throughout the oil business. A total of 3681 producing wells was completed in this field during 1934. This is an increase of 1215 over the 2466 producers completed during 1933. Total wells

Jan 1, 1935

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By Rudolph G. Wuerker

THE Krupp-Renn Process,[1] has been successfully used to treat low-grade iron ores, laterites, titaniferous sands, and other minerals, and before World War I1 25 units were built by the Krupp-Grusonwerk, Magdeburg, Germany. J. J. Howard[2] has shown theoretical advantages of the pyro-metallurgical treatment over conventional approaches; and the process was described by R. Durrer[3].

Jan 1, 1951

Jan 1, 1968

Jan 1, 1968

By C. D. Thurmond

Jan 1, 1968

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

Jan 1, 1959

By R. W. Raymond

THE sudden death of Dr. Drown, on Nov. 17, 1904, brought to multitudes the pang of personal loss. Of all those who, as students at Lafayette College, the Massachusetts Institute of Technology and Lehigh University, were brought under his influence, not one can have forgotten him, and all will now acknowledge, with an unfading gratitude, what they owe in professional equipment to his wise, clear, skillful guidance, and in character to his sympathetic, stimulating personality. Outside of this wide circle, the experts of both hemispheres will lament the departure of one who, in his department of scientific inves¬tigation, both knew what work was needed, and how to do it so that it needed not to be done again. The older members of the American Institute of Mining Engineers will remember with gratitude the part he took, as Secretary from 1873 to 1884, in promoting the interest of that organization, and in shaping the plan and policy which it has followed with such noteworthy success. And, in addition to all these (though partly included among them), there are a host of friends; who can scarcely think of the public loss by reason of their own. Thomas Messenger Drown was born March 19, 1842, at Phil¬adelphia, Pa. His parents were natives of New England; and. he was the youngest of their three sons. He received his preliminary education in the public schools and the High School of Philadelphia, from which he was graduated in 1859. Be-

Jul 1, 1905

By G. L. Oldright, T. B. Brighton, C. M. Dice

The base bullion from the lead blast furnace contains varying amounts of the impurities left in the smelter feed by the concentrator, regardless of the method of smelter operation. These impurities may be held in part in mechanical suspension rather than being present as true alloys. However, usually there is little free space in the crucible in which to separate these drosses before the bullion is taken from the lead well. When such a dross is melted in a laboratory crucible and allowed to cool, the products obtained are lead bullion, speiss, and matte in well separated layers. Typical analyses of layers are: Analyses. Per Cent Element Bullion Speiss Matte Pb.............................................. 92.0 41.2 38.3 Cu.............................................. 2.4 36.3 40.6 As............................................... 4.0 16.5 4.3 Sb............................................... 0.7 0.2 0.4 S................................................ 0.6 1.9 13.1 Fe............................................... 0.0 0.0 0.0 Totals......................................... 99.7 96.1 96.7 The absence of iron in these products drossed from the blast-furnace bullion proves that the impurities for the greater part are not simply finely divided blast-furnace speiss or matte that has been dissolved or dispersed in the lead, but are held in solution by the liquid metal and rise to its surface as infusible compounds when the temperature of the bath is lowered. In general, the drosses made locally are metal sulphides and arsenides and not oxidized compounds. The large content of metallic lead also does not seem to be retained because of oxidized compounds

Jan 1, 1937

By AIME AIME

[SECRETARY&apos;S NOTE.-Since the Committee on Publication of United Engineering Society, will issue a memorial volume re¬porting these proceedings in full, an outline only will be here given. The sessions were held in the Main Auditorium.¬R. W. R.] COMMITTEES. EXECUTIVE.-J. W. Lieb, Jr., Chairman; C. W. Rice, Secretary; John Hays Hammond, Chas. Wallace Hunt, F. R. Hutton, Charles Kirchhoff, T. C. Martin, E. E. Olcott, Chas. F. Scott, Samuel Sheldon, Ambrose Swasey. INVITATIONS.-R. W. Raymond, Chairman; Charles Kirchhoff, Secretary; A; C. Humphreys, Robert W. Hunt, L. B. Stillwell. PROGRAM.-A. R. Ledoux, Chairman; C. W. Rice, Secretary; Theodore Dwight, Chas. Wallace Hunt, T. C. Martin, Ralph W. Pope, Joseph Struthers. WAYS AND MEANS.-James Douglas, Chairman A. R. Ledoux, Secretary; H. R. Brown, J.-M. Dodge, C. L. Edgar, John Hays Hammond, W. M. McFarland, E. E. Olcott, Samuel Sheldon, J. G. White. HISTORICAL AND PUBLICATION PRESS.-T. C. Martin, Chairman; Albert Spies, H. H. Suplee.

May 1, 1907

By J. B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method&apos; was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about 1/2-in. water pressure. No loss of air was evident. Fig. 2 presents typical data for a standard Denver sub-A 24x24-in. unit cell operated at impeller speeds from 0 to 710 rpm. Each plotted point represents the average for five readings distributed over the entire cell surface. Readings were taken with only water passing through the cell. Results of this type have been used in a study of the influence of operating variables on cell performance and in detecting inherent differences in the operating characteristics of cells of various kinds. Although the information presented in Fig. 2 resulted only with water passing through the cell, the apparatus is suitable for use during flotation of coal when various reagents are present. Possible modi- fications that might prove convenient under special circumstances include varying the size and shape of the receiver and substituting a calibrated, inverted, water-filled carboy or other gas-measuring device for the wet-test meter. If such modifications result in excessive back pressures, some form of draft should be applied at the discharge end of the measuring system.

Jan 1, 1959

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly&apos; suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10&apos; to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By AIME AIME

WITH the example of the steel open-hearth men and their round table conference before the copper men, the query naturally arose "Why cannot we do likewise?" The advantage of pooling and comparing knowledge on smelting in the copper reverberatory furnace seems particularly pertinent at this time when all metallurgical economies possible must be rigorously enforced. A great deal of data had also been obtained and filed during the period of litigation over the Carson patent, and it would naturally be available with the cessation of further suits. With these ideas in mind, H. Foster Bain took up the advisability of holding such a conference directly with the heads of all the companies in the United States operating copper reverberatories, and found a nearly unanimous response. The mining companies appointed representatives directly, or indicated to the heads of various metallurgical operations what members of their staffs should be sent to such a conference.

Jan 1, 1930

By K. S. Seljesater

SINCE the development of dispersion-hardenable lead-antimony alloys1 in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. EXPERIMENTAL In order to-study the effect ,of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per FIG. 1..-CHANGE OF MICRO-BRINELL HARDNESS WITH TIME OF 1 PER CENT. LEAD-ANTIMONY ALLOY. cent. lead). The alloys were cast into bars 1 ½ in. wide by ¾ in. thick and cold-rolled to about 1/8 in. thickness. Three samples of each composition were annealed 1 hr. at 225° C. and quenched in water. One set was aged at room temperature, one at 50° C., and the third at 100° C., the

Jan 1, 1929

Jan 1, 1967

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p&apos;robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI&apos;U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts&apos; wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.&apos; This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d&apos;~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU&apos;~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968