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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'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'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' 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.' 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'~-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'~ 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

By Kenneth Seaver

(San Francisco Meeting, September, 1915) INTRODUCTION IT is rather gratifying that in the field of the manufacture 'of refractories, in which, as a whole, foreign practice has surpassed us, the United States stands pre-eminent in the making of silica brick. In some instances European manufacturers have refused point-blank to credit the possibility of making to such specifications as are common with us, until the actual 'completed shapes were shipped for inspection. But both the manufacturer and consumer in foreign lands are now frankly learning from us, and benefiting by our advanced practice in this field, as is evidenced by the orders placed here and the efforts put forth abroad to come up to the standard of American-made material. In no metallurgical operation has the employment of silica brick spread with. such leaps and bounds as in the building of plants for the carbonization of coal, particularly in the byproduct coke oven. Today, in practically all types of oven, the structure above the floor level (except the facings) is of silica, while in the recuperative and in some regenerative types, its use is extended to that portion of the oven below the floor as well. By reason of the fact that there are a number of classes of refractories of higher silica content than the usual so-called fire-clay brick, there is sometimes a misunderstanding as to the class of material referred to as "silica" brick. We here refer only to a brick having a silica content of 94 per cent. or more and made usually from quartzite rock with a small percentage of lime as a binder. The term "silica" brick is sometimes rather loosely applied to brick front highly siliceous clays, or to a quartzite refractory of mingled fire-clay and quartz rock; but such products are not considered in this discussion.

Jan 9, 1915

By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By William Phillips

This paper was prepared at the request of Capt. A. F. Lucas, Chairman of the Institute's Committee on Petroleum and Gas, as a preliminary discussion of the fuel oils which are used-in the Southwest, giving their composition, uses, prices, etc. Should it afterward be found desirable, these observations may be extended over a larger area. In this connection, J suggest that samples of all kinds of fuel oils, including various tars, from all over the country, be collected and sent to some testing laboratory for examination. We would be glad to extend the facilities of the laboratory of the Bureau of Economic Geology and Technology, at the University of Texas, for this purpose, and to do the work free of all expenses. After such examinations are made and the results classified and studied, it would be possible to suggest specifications under which fuel oils should be purchased, and to arrive at some conclusions respecting the uniformity of such specifications, with due allowance for climatic and other more or less local conditions. While such specifications do not now depart from a common standard anything like as much as specifications for illuminating oils do, yet there are discrepancies which should not exist. Some of these discrepancies are of lessening importance, due to the pronounced tendency to distill every crude oil that can be distilled with profit, and to send residues into the market for fuel oil. Residues from the refineries are of a more uniform chemical composition and physical nature than many of the crude oils that go direct into the fuel market. The lower flash-point oils are disappearing from the fuel trade and in place of them we are getting oils that do not flash below 220° F., nor burn under 320° F. In the Southwest, it has not been long since we had fuel oils that flashed at as low as 110° F., and the average flash point over a considerable period was 151° F. Now we are using oil that flashes at about 30° lower than the former burning point, which was 256° F. In other words, the flash point has risen, on the average, 100°; and the burning point about 75°.

Jan 6, 1914

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By W. J. Sharwood

The assay or estimation of the total gold content of an ore presents little difficulty, when circumstances permit of securing a thoroughly representative sample. The general practice has been fairly standardized, and such errors as occur in the results obtained are for the most part attributable to the methods of sampling rather than to those of assaying, while duplicate assays made by skilled workers usually agree closely. When it is a question of estimating the "free" or amalgamable gold of an ore, as opposed to the total gold, there is but little uniformity in the methods employed by different workers, and often equally little in the results obtained when duplicate determinations are attempted, no satisfactory standard method having been generally adopted. The methods in use are of two general types—"panning" and "amalgamation." Panning For the estimation of the value of the visible gold by panning or washing, a weighed sample may be taken, ranging from an ounce to several pounds; a kilogram or 2 lb. is a favorite quantity for laboratory tests, while a prospector often uses a full miners' pan, say nearly 20 lb. or 10 kg. In the case of rich quartz, ground to about 30 or 40 mesh, a Mexican horn is convenient, using 1 to 8 02;. of material, and a 6-in. frying pan is favored by many prospectors in dry districts. Bateas, plaques, and dishes of various patterns are used for the same purpose. With these, fairly close results may be obtained by using for ocular comparison standards consisting of weighed amounts of gold of similar character as regards purity, fineness of division, and the general shape of the particles, which standards are preferably obtained from gold of the same locality, or the same deposit, as the ore or gravel being tested. Men working in one particular district sometimes become surprisingly expert in thus judging the value of an ore by the eye, the weights of both ore and gold being guessed. On the other hand, many have been led to overestimate the value of ore and gravel from unfamiliar localities, where the gold has been very finely divided or of unusually high silver content, and a novice may

Jan 1, 1916

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By C. Dalton, H. L. McGill

The purpose of this study was to develop a method for predicting the time delay created by metering a fluid through an annular restriction with translational motion of the boundaries. This time delay is utilized to control the opening of valves in various down-hole oilfield tools and forms the basis for the "hydraulic jar". The hydraulic jar is used to give upward impact forces to tubing or other tools that become lodged down-hole. The design of these jars has primarily been by trial and error; varying the clearances, fluid viscosities and dimensions of the jar until a satisfactory time delay was achieved. Obviously, a better understanding of the fluid flow characteristics is required to produce designs that are satisfactory and to eliminate the trial-and-error approach. Previous studies of flow in annular spaces were based on constant length of the annular restriction. Any motion of the boundaries of the annular space was confined to a rotational motion, like that encountered in journal bearing design. Consideration of the effect of translational motion of one boundary with respect to the other was necessary in applying this previous work to a time delay device. A prediction method was developed that takes into account this relative translational motion. Equations were developed to predict the relative velocity, the flow rate, and the time delay in a concentric annular space. The effect of eccentricity also was included. Experimental data were obtained and closely correlated with the prediction method. This correlation is presented graphically in terms of predicted and actual relative velocities for various annular clearances and pressure drops. This extension provides design equations which predict the performance of the hydraulic jar, thereby eliminating trial-and-error solutions and reducing the development time required for satisfactory designs. INTRODUCTION The design of down-hole oilfield tools which use hydraulic delay systems based on flow through annular orifices with relative motion of the boundaries is usually a trial-and-error process. The annular clearances, fluid viscosities and dimensions of the mechanisms were varied until satisfactory delay times were obtained. The development of these tools has been expensive, and a better understanding of the characteristics of annular flow with relative motion of the boundaries could result in superior and less expensive designs. The purpose of this investigation was to provide a method of predicting the performance of down-hole tools which use annular flow and, in particular, the performance of a down-hole tool known as the "hydraulic jar". The hydraulic jar is used to free pipe, packers and other tools that become lodged down-hole. The jar, located in the tubing string between the surface and the object which is stuck, releases the object though the repeated application of upward impact blows. The jar is basically a slip joint that is restrained in a collapsed condition until the desired tubing tension has been developed. The slip joint is then released and accelerates rapidly until it shoulders, delivering an impact blow or jar to the object. The delay obtained by metering the fluid through the annulus formed by the jar valve and housing provides the time delay necessary to stretch and apply tension to the tubing or pipe. Fig. 1A gives a schematic diagram of the hydraulic jar and brief details of its operation. The metering of the hydraulic jar begins when the tension force being applied to the jar by the pipe creates a pressure differential across the valve that is approximately equal to the force divided by the displacement area of the valve. This pressure differential induces flow through the annular restriction formed between the valve and housing. The valve moves with respect to the housing as the

Jan 1, 1969

By ZJ. H. Brophy, A. L. Prill, H. W. Hayden

The effect of Group VIII transition-element additions on the sintering of tungsten powders is shown to be dependent on the phase relationships of the particular tungsten-Group VIII metal alloy system. The acceleration of sintering with nickel additions is diminished by alloying nickel with copper which is known to diminish both the tungsten solubility in nickel and the solid-vapor surface energy. In work previously published on the effects of additions of Ni, Pd, Pt, Rh, Ru, and Ir, which form solid solutions or intermediate phases of wide composition width with tungsten, sintering behavior is independent of element concentration beyond that concentration necessary to form a continuous layer on the surface of the tungsten powders employed. The sintering behavior of tungsten with additions of iron or cobalt, which form intermetallic compounds with tungsten, is highly dependent on addition-element concentration. Additions in excess of amounts necessary to form continuous layers lead to successively decreased sintering rates. The effects of certain Group VIII transition metals on the sintering rates of tungsten at temperatures below those at which a liquid phase would be predicted have recently been investigated by the present authors1-4 It was found that small additions of palladium, nickel, rhodium, platinum, and ruthenium accelerate the rate of tungsten sintering. Additions of iridium decelerated the rate of densification compared to that of pure tungsten in the same temperature range. In all cases the rate of densification changed with increasing amounts of these additions, up to those compositions at which a continuous layer was formed on the surfaces of the tungsten-powder particles. The rate of densification was then independent of further increases of the compositions of any of these addition elements. These observations were consistent with a sintering model in which the addition element formed an interface with tungsten in which tungsten dif-fusivity was either greater or less than its grain boundary self-diffusivity. Kinetic analysis of this model indicated that linear shrinkage should vary according to the relation:

Jan 1, 1964

By Nathaniel Arbiter

In attempting to assess the contributions of Antoine Gaudin to the profession which he illuminated for almost a half-century, we will need to examine a very broad canvas. He was active in three significant areas: as a teacher; in research, both through his own endeavors and those of his students; and as a consultant to the mining industry and to the Government. Beyond these specific contributions, there was the major personal influence he had on scores of students, friends, and colleagues in the profession. If a single measure of the man's contribution is to be found, it will be the extent and direction in which he influenced the practice of his profession. To find this we should examine the state of miner- al processing when he began his activities in the 19201s, the progress which has taken place over the past half-century, and the part his activities played in this advance. However, there is a provocative and broader examination which I have chosen to make instead. This is to examine the past century in mineral processing through the lives of three men who, by common agreement, stand on the heights, both in teaching and in their contributions to industry: Robert H. Richards, Arthur F. Taggart, and the man whose memory we honor this evening, Antoine M. Gaudin. Their careers, by coincidence, cover just a century. This is also AIME's first century, and the first century of mineral industry education in the United States. In fact, mineral processing itself on any significant scale in the country encompasses only a century and a quarter. BEGINNINGS OF PRACTICE IN THE U.S. Before the 1840’s, U.S. mining, except for coal and iron ore, was on a small scale and was confined to the eastern states, with processing practically nonexistent. The 1840's saw the beginning of Michigan native copper production, including ore dressing; the 1850’s, iron ore production in Minnesota; and the 1860’s, lead production and processing in Missouri. But the most explosive event was the California gold rush after 1848, which not only brought tens-of-thousands of fortune hunters to the West, but also catalyzed broad mining activities and processing within the following decades. This was not only in California but, after the first fever of the gold rush subsided there,

Jan 1, 1976

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:' This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By C. O. Swanson

In the iron ranges of northern Michigan, magnetic data have been used as an aid in geologic field work since the time of the earliest surveys. The presence of complex structures containing magnetic formations, and the general scarcity of exposures, guided the early work into this line of attack, and later field studies tended to place more and more emphasis upon this geophysical relationship, until, at present, the collection of magnetic data is a matter of routine in any areal survey. At first, horizontal deflections of the compass needle were the only data collected. In subsequent surveys, greater dependence was placed on dip-needle readings, which record variations in the intensity and inclination of the earth's magnetic field. Recently the trend has been toward adjusting the instrument so as to reduce the influence of changes in inclination, and using a more sensitive modification, called the Superdip,' in weakly magnetic areas. To a minor extent, the magnetometer has also been employed. The object of this paper is to present the writer's experience with magnetic data in this region. The conclusions are based on work covering a period of 10 years, and spread over nearly all of the iron ranges and a large part of the intervening areas. The viewpoints expressed are purely geological ones. In other words, any opinion as to the usefulness of a certain relationship is based upon the writer's experience with it as a guide in interpreting the structures of this region, and not upon its soundness theoretically, nor its usefulness under other conditions. A very brief summary of the conclusions is as follows. The most important step is that of collecting the magnetic data. This requires a suitable adjustment of the dip needle, and sufficient readings to accurately portray the variations in the magnetic field, which are apt to be irregular. Once the readings are taken and plotted in some clear fashion, the interpretation of them is usually merely a matter of observing their relation-

Jan 1, 1934

By J. F. Myers, S. E. Sharp

The safety data presented in this paper are based upon replies to a Questionnaire sent out to representative mining companics. The authors feel that it is a fair cross section of the milling industry, in that the 17 companies, of the United States and Canada, reporting on 22 mills, are scattered from the Hudson Bay to the Mexican border and from coast to coast. These data concern the accident records of the various plants from 1939 to 1944, inclusive and the six years are divided into two periods. The first period (1939, 1940 and 1941) represents something of a normal operating condition. The second period (1942, 1943 and 1944) represents the period of time that was most affected by war conditions. During the second period there was a high labor turnover, inexperienced workers were numerous, women replaced men in many kinds of work, a labor shortage existed more or less throughout the industry, and supervision was pushed for peak production. All of the companies reporting compiled their accident experiences for these six years in accordance with the standards set up by the American Standards Association (New York, N. Y.), consequently the tabu lated data presented herein are comparable. The authors of this paper feel that the industry as a whole is greatly indebted to the personnel of the companies that furnished these data, which make this study possible for presentation. This survey covers a total exposure of 74,528,880 man-hours, with 105,471 man-days of lost time from 870 accidents. Safety Records In Table I, the safety record is shown of the various mills reporting. The severity rate is usually conceded to be the most vital statistical figure in safety parlance, therefore the participating companies are listed in order of their severity rate for the combined six-year period, under size of organizatiori. The table also shows the frequency rate as well as the frequency-severity ratio (F/S). As noted in Table I, most of the companies suffered an increase in both severity and frequency rates during the second period; only six of the 22 enjoyed an improvement. From correspondence with the various plants, it seems that a few had very little labor shortage or turnover, and these were not greatly affected. A few plants, anticipating the situation, strengthened their training facilities and actually were able to show a better experience during the second period. This gives great credence to the value of organized training in any safety program. The frequency-severity ratio (F/S) shown in the last column of Table I offers

Jan 1, 1947

By S. E. Sharp, J. F. Myers

The safety data presented in this paper are based upon replies to a Questionnaire sent out to representative mining companics. The authors feel that it is a fair cross section of the milling industry, in that the 17 companies, of the United States and Canada, reporting on 22 mills, are scattered from the Hudson Bay to the Mexican border and from coast to coast. These data concern the accident records of the various plants from 1939 to 1944, inclusive and the six years are divided into two periods. The first period (1939, 1940 and 1941) represents something of a normal operating condition. The second period (1942, 1943 and 1944) represents the period of time that was most affected by war conditions. During the second period there was a high labor turnover, inexperienced workers were numerous, women replaced men in many kinds of work, a labor shortage existed more or less throughout the industry, and supervision was pushed for peak production. All of the companies reporting compiled their accident experiences for these six years in accordance with the standards set up by the American Standards Association (New York, N. Y.), consequently the tabu lated data presented herein are comparable. The authors of this paper feel that the industry as a whole is greatly indebted to the personnel of the companies that furnished these data, which make this study possible for presentation. This survey covers a total exposure of 74,528,880 man-hours, with 105,471 man-days of lost time from 870 accidents. Safety Records In Table I, the safety record is shown of the various mills reporting. The severity rate is usually conceded to be the most vital statistical figure in safety parlance, therefore the participating companies are listed in order of their severity rate for the combined six-year period, under size of organizatiori. The table also shows the frequency rate as well as the frequency-severity ratio (F/S). As noted in Table I, most of the companies suffered an increase in both severity and frequency rates during the second period; only six of the 22 enjoyed an improvement. From correspondence with the various plants, it seems that a few had very little labor shortage or turnover, and these were not greatly affected. A few plants, anticipating the situation, strengthened their training facilities and actually were able to show a better experience during the second period. This gives great credence to the value of organized training in any safety program. The frequency-severity ratio (F/S) shown in the last column of Table I offers

Jan 1, 1947

By J. F. Myers, S. E. Sharp

THE safety data presented in this paper are based upon replies to a Questionnaire sent out to representative mining companies. The authors feel that it is a fair cross section of the milling industry, in that the 17 companies, of the United States and Canada, reporting on 22 mills, are scattered from the Hudson Bay to the Mexican border and from coast to coast. These data concern the accident records of the. various plants from 1939 to 1944, inclusive and the six years are divided into two periods. The first period (1939, 1940 and 1941) represents something of a normal operating condition. The second period (1942, 1943 and 1944) represents the period of time that was most affected by war con¬ditions. During the second period there was a high labor turnover, inexperienced workers were numerous, women replaced men in many kinds of work, a labor shortage existed more or less throughout the industry, and supervision was pushed for peak production. All of the companies reporting compiled their accident experiences for these six years in accordance with the standards set up by the American Standards Association (Engineering Societies Building, New York, N. Y.), consequently the tabulated data presented herein are comparable. The authors of this paper feel that the industry as a whole is greatly indebted to the personnel of the companies that furnished these data, which make this study possible for presentation. This survey covers a total exposure of 74,528,880 man-hours, with 105,471 man-days of lost time from 870 accidents. SAFETY RECORDS In Table I, the safety record is shown of the various mills reporting. The severity rate is usually conceded to be the most vital statistical figure in safety parlance, therefore the participating companies are listed in order of their severity rate for the combined six-year period, under size of organization. The table also shows the frequency rate as well as the frequency-severity ratio (F/S). As noted in Table 1, most of the companies suffered an increase in both severity and frequency rates during the second period; only six of the 22 enjoyed an improvement. From correspondence with the various plants, it seems that a few had very little labor shortage or turnover, and these were not greatly affected. A few plants, anticipating the situation, strengthened their training facilities and actually were able to show a better experience during the second period. This gives great credence to the value of organized training in any safety program. The frequency-severity ratio (F/S) shown in the last column of Table I offers

Jan 1, 1946

By John Gross

THE deductions drawn in crushing and grinding operations have heretofore been based on a separation of the products into various sizes. A crushed product may be sized by sieving, by elutriation, and by aid of the microscope. To estimate the surface of each size the relation of the surface to the estimated average diameter must be assumed. Such a relation, owing to the irregularity of the particles, may involve two assumptions: First, a factor to convert average diameter to surface for one particular size; and second, a variation in the factor as the diameter of the particle changes. Obviously a surface measurement in which such assumptions and estimates are involved is questionable. In the first paper of this series1 a method has been given by which an accurate measure of surface of quartz can be obtained from its dissolution rate. By the use of this method, surface measurements have been made on a series of sieve sizes of crushed quartz, the results of which are given and discussed in this paper.

Jan 1, 1928