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By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By M. J. Sinnot, J. C. Shyne

Low-frequency mechanical damping measurements were made to investigate internal friction in Fe-A1 alloys. The atomic ordering of the Fe-A1 system strongly influenced the stress-induced ordering internal friction. Magnetoelastic damping was also encounteyed and was shown to be reduced by the application of a static stress. THIS paper describes some damping experiments made on alloys of Fe and Al. Stress-induced ordering internal friction was measured with samples containing from 9.8 to 31.3 at. pct Al. Aluminum is soluble in a-Fe to about 50 at. pct and forms at least two long-range ordered structures, Fe3Al and Feu.' Stress-induced ordering internal friction is known to occur in many substitutional solid solutions, but few measurements of this damping effect have been made with alloy systems that have pronounced ordering tendencies. LeClair and Lomer developed expressions relating the relaxation strength of the damping process to the degree of atomic ordering and predicted that stress-induced ordering internal friction would be zero with complete ordering.' This concept was confirmed experimentally by Lulay and Wert using the system cd-Mg It is also consistent with the weak stress-induced ordering peaks observed in P -brass by Artman and in 16 wt pct Al Fe-Al by bert.' It was expected, therefore that the ordering characteristics of the system Fe-Al would strongly influence the stress-induced ordering internal friction exhibited by the experimental alloys. SAMPLE PREPARATION The alloys used in this investigation were induction melted under vacuum using high-purity melting stock. The iron was electrolytically refined Plastiron 101 which contained 99.85 wt pct Fe. The aluminum was a special 99.95 pct pure grade supplied by Alcoa. The only other raw material was spectrographically pure graphite which was used in small quantities as a deoxidant. The amount of carbon used was slightly in excess of the amount required to completely deoxidize the melt; this resulted in residual carbon contents of 0.01 to 0.02 pct in the finished alloys. The vacuum cast 2 1/2-in. diam ingots were hot rolled to 5/8-in. diam round bars. Portions of these bars were hot swaged and hot drawn to 0.050-in. diam wire. Straight pieces of the hot drawn wire were slowly heated to a temperature of 1300°C in a He atmosphere. After holding for 4 hr, the samples were allowed to cool in the furnace. This annealing treatment resulted in grain growth in the samples, the final grain size being about the same as the wire diameter. The grain boundaries were oriented perpendicularly to the wire axis, giving a bamboo grain structure. The existence of a preferred orientation could not be detected in these coarse grained samples. If the samples had a fiber structure, this probably would have been the same in all samples because of similar processing, thus the influence of crystal orientation on the relaxation strength would have been similar in all samples. The aluminum contents of the alloys are listed in Table I. EQUIPMENT The principle of the torsion pendulum was used for the internal friction measuring device. The

Jan 1, 1961

By A. R. Gregory, A. L. Podio, K. E. Gray

Dynamic elastic properties of dry and water-saturated Green River shale samples were computed from compressional- and shear-wave velocity measurements. P- and 5-wave velocity measurements were made in three mutually perpendicular directions with respect to the bedding planes. Measurements were also made in several different directions by varying the angle between the bedding planes and the direction of propagation of the wave for angles of 0, 30, 45, 60 and 909 The oriented samples were subjected to both confining pressure and axial loads, in excess of the confining stress, in the direction of propagation. In general, P- and S-wave velocities increased with increasing stress levels, with a corresponding increase in Young's modulus. Water saturation caused the P-wave velocity to increase and the S-wave velocity to decrease. Elastic moduli decreased upon saturation, except for Pois son's ratio, which increased, indicating some degree of weakening of the material. The samples showed a moderate degree of anisotropy; this was to be expected from the laminated nature and shallow occurrence of Green River shale. INTRODUCTION This paper presents some results of an experimental determination of the elastic coefficients of anisotropic materials (in particular, finely layered rocks and minerals such as Green River shale) from measurements of dilatational and shear-ultrasonic-wave velocities. Ultrasonic techniques have been used extensively in nondestructive testing. Several methods have been proposed by Mcskimmin, 1 and some of these have been used successfully to measure ultrasonic velocities in rocks. Hughes and Cross, 2 Wyllie et al., 3 and Birch 4,5 developed pulse first-arrival techniques for the measurement of dilatational and shear velocities. Williams and Lamb 6 used the method of cancellation of a traveling wave, which was later modified by Myers et al.' and perfected by McSkimmin. 8 Although this method is highly accurate, it has not been used as widely as the pulse-transmission methods recently reported by Jamieson and Hoskins 9 King,10 and Mattaboni and Schreiber. 11 It has been common practice to use some form of crystal transducers, either quartz or ceramic, that has been cut or polarized in different directions in order to generate either compressional or shear waves. However, accurate determination of shear wave velocities has been difficult due to problems that arise in obtaining a pure shear wave from cross-polarized crystals, which usually also generate a small amount of compressional energy. As reported by Gregory, 12 this energy can be seen as a long precursor preceding the sharp break of the shear first arrival. The need for generating pure shear waves led to interest in mode-conversion techniques, which are based upon conversion of the mode of vibration through wave reflection or refraction at a discontinuity. Arenberg13 showed that for certain materials and for certain angles of incidence it is possible to generate pure shear modes by reflection at a boundary. Jamieson and Hoskins 9 used a pyrex glass-air interface for generating pure shear waves, and King 10 used this method successfully for measuring shear-wave velocities in rocks. Gregory l4 arrived at a similar result by refraction of a wave at an aluminum-oil interface. A plane compressional wave, traveling in the oil phase, is incident on the aluminum at an angle larger than the critical angle for compressional waves, and thereby generates a purely transverse, plane-polarized wave in the aluminum. During the last few years methods have been developed that allow the simultaneous determination of shear and compressional velocities in solids.

Jan 1, 1969

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center's Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

By C. Scala, M. Gondouin

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

By R. K. Datta

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

Jan 1, 1968

By J. L. Gregg

RECENTLY there has been considerable interest in the production and use of, extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wire-drawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names. No performance data are given and no inference as to the inferiority of one alloy as against any other is made K Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification.

Jan 1, 1929

By V. G. Mooradian

THE diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distor-tion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-

Jan 1, 1935

By Robert Rhea Goodrich

This research was done partly in the non-ferrous laboratory of the Department of Metallurgy of Columbia University, under the direction of Dr. Edward I?. Kern, and completed elsewhere. Acknowledgment is due to Prof. Arthur L. Walker, Dr. Edward F. Kern and Dr. William Campbell of the Department of Metallurgy, for their kind advice and for the inspiration derived from their instruction. This report is given under the following heads: Petrographic Description (Microscopic Study); Sampling and Preparing Ore for Treatment; Chemical Analysis; Treatment of Ore. Petrogeaphic DescRiption Texture: variable. Fine to medium mixed aggregate. Original Structure: Obscurc. Secondary structure: Fractured; healed. Mineralogy (Minerds are grouped for interpretation purposes and are arranged, in each group in approximate order of abundance)

Jan 1, 1916

By Earl W. Palmer, Cyril Stanley Smith

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By Cyril Stanley Smith, Earl W. Palmer

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By C. W. Clark, J. H. Schloen

Two papers have been written previously concerning operations at the Montreal East plant of Canadian Copper Refiners Limited. The first one,1 written in 1932, described silver-refinery operations at the time for producing silver and gold bullion from tankhouse anode slimes; the second,2 published in 1933, consisted of a description of the entire plant. Since publication of these papers the refinery has become the world's largest producer of refined selenium. The first selenium was produced in August 1934. Tellurium production on a commercial scale followed in October 1935. This paper will deal with selenium and tellurium production and also with present operations in the silver refinery. Blister cakes from Hudson Bay Mining and Smelting Co., Flin Flon, Manitoba, and commercial anodes from Noranda Mines Limited, Noranda, Quebec, are refined at Montreal East. Both these bullions have unusually high gold, selenium and tellurium content. The average assay of raw slimes produced from domestic and Noranda anodes is about 40 per cent Cu, 3600 oz. per ton Ag, 800 oz. per ton Au, 22 per cent Se and 3.7 per cent Te. EARLY SILVER-REFINERY OPERATIONS From the start of operations in 1931 until July 1934, the raw slimes were oxidize-roasted at 700° F. in a Nichols-Herreshoff furnace, acid¬leached with tankhouse discarded foul electrolyte (20 per cent H2SO4), filtered and charged directly to the doré furnace for refining to doré metal. This is the customary method for treating tankhouse anode slimes but was not suitable at the Montreal East plant because of the high selenium and tellurium content of our slimes. In the acid-leaching process about 50 per cent of the selenium and tellurium in the roasted slimes was dissolved in the electrolyte. These elements were recovered with the copper as a sludge in a small electrolytic

Jan 1, 1938

By W. B. HILLHOUSE

AN excerpt from the Alabama State Mining Law, pertaining to, transporting men' into and out of the mines, reads as follows: "A trip of empty cars may be operated for the purpose of taking employees into and out of the mine, where the distance to and from their work exceeds one mile." The State Mining Department of Alabama includes in its inspection the transportation of men into and out of the mines, also studying and noting improvements, or progress made, that would tend to create a greater assurance of safety in this practice. Everyone is familiar with the original safety methods employed in man-trip transportation, such as passing a rope around the trip of cars, or through the cars, fastened in the conventional manner, and with the usual "clog," commonly called a drag, on the rear end. Also there is a more advanced method of transporting men, such as the double-rope system, which is feasible on slopes used exclusively for this purpose, and is very satisfactory. However, for the past eighteen months; the Republic Steel Corp. and the Tennessee Coal, Iron & Railroad Co. have adopted a practice that shows

Jan 1, 1935

By Albert Wiggin

THE copper-bearing sulphide ores from the mines in Butte, Mont., which are for the most part concentrated at the Boston & Montana duction Works in Great Falls and at the Washoe Reduction Works in Anaconda, contain the following minerals of economic value: Chalcocite, Cu2S; enargite, Cu3AsS4; cupriferous pyrite; bornite, Cu3FeS3; covellite, CUS; tetrahedrite, 4 CuS2Sb2S3; and tennantite, Cu8AsS7;. All of the ores carry a high percentage of pyrite. Many of the above sulphides are argentiferous and also carry from 10 to 20 cts. per ton in gold. The gangue is quartz and highly altered granite, with sphalerite and galena and more rarely barite and hubnerite as accessory minerals. An average chemical analysis of the second-class ore concentrated at Great Falls and Anaconda would be as follows: Copper 3.2 to 3.4 per cent. Silver 2. 3 to 3.0 oz. per ton. Gold 0.0-1 to 0.15 oz. per ton. Si02.. 55 to 60 per cent. FeO 12 to 15 per cent.. Sulphur 12 to 1.5 per cent. Al2O3, S to 10 per cent. CaO 0.5 to 0.8 percent. As203, 0.5 to 0.6 percent. Lead 0.2 to 0.3 percent. Before describing the Great Falls flow sleet as installed, at Anaconda, a brief history of the Great Falls concentrator will be given, including a description of the various concentrating machines and systems which have been tested in the search for a flow sheet which would give a higher recovery of copper.

Jan 8, 1913

By C. A. Wright

The average lead and zinc content of the ores mined and milled in the Joplin district is low as compared with that of other lead and zinc deposits throughout the United States. Because of this fact and of the high grade of the concentrates, the ratio of concentration is unusually high. Most of the operating companies have aimed to produce as high a grade of concentrate as possible in order to obtain the highest price for their product. They have done this at the sacrifice of the percentage of zinc recovered. The average percentage of zinc recovery is from 60 to 70 per cent. For percentage of recoveries from actual mill tests, see tables. The concentration is commonly effected by crushing the ore to ½-in. (12.7 mm.) size and subjecting it to a roughing and cleaning over two or more large Cooley jigs, of the Harz type, the finer sands being treated on the usual types of sand and slime tables. The treatment of slimes by flotation is being tested at several of the larger mills. Coarse Concentration When the ore has been hoisted from the mine it is dumped onto a chute leading to a grizzly made of iron bars, usually heavy rails, spaced 4 to 5 in. (101 to 127 mm.) apart. The oversize is caught on the grizzly, the mineralized pieces are broken with sledge hammers so as to pass through, and the boulders that are practically barren are sorted out by hand and trammed to the waste-rock pile. The proportion of waste rock thus sorted out varies from a fraction of 1 per cent. to 15 per cent., depending on the nature of the rock. Crushing The undersize material, 5 in. (127 mm.) or less in diameter, passes through the openings of the grizzly into the mill hopper below. From

Jan 1, 1918