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By J. Skrove, C. R. Boardman

In situ permeability of the rock outside the Hardhat chimney was determined by pressurization of long holes with air. Experimental data indicated a remarkable difference between fracture permeability of the rock near the chimney and that at a considerable distance. Although permeable fault zones were known to exist in the granite stock, the measurements of background permeability were quite low, on the order of tenths to several millidarcies. The observed difference is about two or three orders of magnitude above this background in the region 125 to 215 ft radially from the shot point, or 80 to 165 ft radially from the vertical axis of the chimney. The presence of a collapsed drift immediately beyond this region precluded measurements which could have defined the maximum extent of the zone of high permeabilily. INTRODUCTION Previous exploration has revealed that contained nu-clear explosions create cavities which generally collapse, resulting in rubble-filled chimneys and annular fractured zones. These geometries have been shown to result in complex flow regimes which should increase the production rate from hydrocarbon reservoirs.' Empirical scaling equations have been developed for estimatina chimney radii and heights for a variet; of rock media.' The exten; of the annular fractured zone has been documented and associated permeability changes have been observed qualitatively for several explosions. This study was begun to establish the nature and magnitude of the permeability of the latter region. It is anticipated that results will be useful in estimating permeability changes and consequent production stimulation which might ensue from a contained explosion in a hydrocarbon reservoir. The post-shot environment of the Hardhat event (a 5-kt contained nuclear explosion in granitic rock) was c'hosen for the experimental measurements. The Hardhat device was detonated at a depth of 939 ft, and subsequent exploration revealed a chimney of broken rock with a radius of 65 to 70 ft and a height above shot point of 281 ft.' BeFore the explosion, the Hardhat medium was highly jointed and fractured (Fig. I). Jt was expected that differential rock motion along these and other weaknesses induced during cavity growth and collapse would significantly alter the permeability of the rock mass. EXPERIMENTAL METHOD Initially, three 2-in. diameter holes (Nos. 10, 12 and 19) were drilled about 25 ft outward through the walls of the 500-ft level drift (elevation 4,253 ft, Fig. 2). One was drilled near the chimney and two holes, one vertical and the other horizontal, were drilled near the shaft. Order-of-magnitude differences in permeability obtained by pressurization measurements indicated further: investigation was warranted. A series of 3-in. diameter holes was then drilled with water as a coolant into the walls and roof of the drift (Fig. 2). An 11-in. long packer was set from 1 to 8 Et inside each hole and air was injected at measured Row rates. Hole pressures were monitored at the collar. Permeability was low enough in the holes near the access shaft that pressure could be maintained long enough to obtain good pressure decay rates. In the vicinity of the chimney, however, permeability was so high that this was not possible and air was injected under steady-state conditions. About one year later, these same holes were retested to

Jan 1, 1967

By C. Elbaum

Specimens consisting of several crystals, each with a prescribed geometry and a controlled orientation with respect to both the extermally intposed stress and the highboring crystals, werer deformed in tension at room temperature. It is shown that the influence of a grain boundary on the plastic defolrmation of a mullicrystal depends on the extent to which the presence of the grain boundary, contributes to the necessity 01. multiple slip in the component crystals. MANY investigations were carried out in the past on the plastic deformation of aluminum single crystals, bicrystals, and polycrystals. The various studies of bicrystals aimed primarily at elucidating the influence of grain boundaries on the mechanisms of plastic deformation. In the earlier studies the emphasis was placed primarily on finding the "strength" contributed by a grain boundary. In more recent investigations it became apparent that the grain boundary does not contribute any strength per se but rather acts by influencing the mechanism of plastic deformation in the adjoining grains. The concept thus emerged of the plastic properties of a bi-crystal, and by extension of a polycrystal. depending solely on the mechanism of deformation prevailing in each grain. The contribution of the grain boundaries thus becomes limited to the type of restrictions imposed on each grain by its neighbors. The present investigation of the behavior of specimens consisting of more than two crystals was designed for the purpose of studying the influence of the grain boundary in simple aggregates. The findings of this study further support the concept that the restriction imposed on a deforming crystal by its neighbor constitutes the predominant factor in the plastic deformation of polycrystals. The term "multicrystal", in contrast with single and polycrystals, is used to describe specimens consisting of several crystals. Each one of the component crystals has a prescribed geometry and a controlled orientation with respect to both the externally imposed stress and the neighboring crystals. Two groups of multicrystals were prepared. All the component crystals of both groups of multicrystals had the axial orientation (isoaxial multicrystals) shown in Fig. 2, with the primary slip plane and slip direction both at 45 deg to the specimen axis. In the first group (hereafter referred to as group I) the component crystals were symmetrically oriented with respect to the plane of the grain boundary; the primary slip plane and slip direction were respectively at an angle of 60 and 30 deg to this plane. For the second group (group 11) the axial orientation remained the same and the relative positions of the primary slip plane and slip direction are shown in Fig. 3. EXPERIMENTAL METHODS The material used was aluminum 99.993 pct pure, according to the manufacturer. The specimens were produced by growth from the melt in a horizontal graphite container. In order to maintain the prescribed geometry of the individual crystals of a multicrystal, a technique described elsewhere was used.' The specimens were grown under a small, positive pressure of helium at a rate of approximately 1 mm per min. annealed in air for 24 hr at 640°C and cooled over a period of several hours to room temperature. All the multi-crystals were rectangular in cross-section, 6 by 18 mm (see Fig. 1) and from 150 to 170 mm long. In each group bicrystals, tricrystals and quadru-crystals were prepared as shown in Figs. 1 and 4.

Jan 1, 1961

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6' gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6' gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964

By M. C. Fuerstenau, A. M. Gaudin

A homogeneous suspension is viewed by X-rays. The radiation density seen, affords a measure of the extra absorption due to the solids contained. This radiation density, at a predetermined depth, varies with time. The chart of this relationship gives the desired determination. s it is frequently necessary to know the distribu-rt tion of particle sizes in various products used in industrial applications, a number of means have been devised for these determinations. Some of them include direct microscopic measurement, screening of product, extraction of samples from a settling slurry, air and liquid elutriation, adsorption of gases and liquids, and light absorption. The absorption of light as a means for particle size analysis has been known and employed for some time. X-ray absorption has not received the attention that light has enjoyed primarily because of the complex and costly instrumentation involved with X-rays. In 1954, Brown and Skrebowskil suggested the use of X-rays for this type of determination but did not supplement their suggestion with experiment. In 1958, the authors conducted size analysis experiments on suspensions of quartz with the Trans-viewer: an X-ray unit specifically adapted for sedimentation research, and Rossa conducted experiments in a similar manner in 1959 with a stable gamma emitter, AmZ4l, on suspensions of uranium oxide. To illustrate the applicability of X-ray absorption for analyzing particle size distributions, an essentially mono-energetic and well collimated X-ray beam was used as a source. The beam was made mono-energetic by placing a zirconium filter before the counting window together with feeding the pulses from the proportional counter into a reverter, a device capable of discriminating against pulses of various heights. The sketch in Fig. 1 shows the collimation arrangement in more detail. As shown, the X-ray beam was collimated by inserting a 3/8-in. ID pipe into one of the ports of the X-ray tube and further by two small steel plates with slits 3/32-in. wide and 1/2-in. long placed in front of the window of the Geiger-Mueller (G-M) tube. One of the plates was located 1/2 in. and the other 2 1/2 in. from the window of the counter; both plates were contained in an aluminum holder mounted on the box containing the G-M tube. This type and degree of collimation should eliminate any intensity due to scattered radiation; the transmitted intensity would then be solely a functior. of the absorption by the suspension at that level. Experimentally, homogeneous suspensions of finely ground quartz were prepared, Daxad (a sulfo-nated compound made from wood) was added as dis-persant, and the transmitted X-ray intensity measured as a function of time at a fixed depth in the suspension. In more detail, the experimental procedure involved the following: 1) measuring the transmitted X-ray intensity through the Daxad solution at a predetermined position or settling depth in the absence of solids, 2) placing a known amount of dry solids into the vessel and agitating thoroughly, 3) measuring the transmitted X-ray intensity at time zero (i.e., immediately upon cessation of stirring), and 4) measuring the transmitted X-ray intensity as a function of time (a 10-sec counting interval being chosen and counting being started 5 sec before the desired time). Since a linear relationship exists between percentage solid in a slurry and the logarithm of transmitted intensity for a homogeneous material, the cumu-

Jan 1, 1961

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958

By J. R. Cahoon, H. W. Paxton

The mechanical properties of unidirectionally solidified A1(rich)-Mg and A1(rich)-Cu castings containing up to 15 wt pct solute have been determined with re -spect to the volume fraction of interdendritic eutectic. Pioperties were determined in the directions pumllel and Perpendicular to that of solidification; the volume fraction of eutectic was varied between the "as-cast" and equilibrizcm amounts by approperiate heat treatment following solidification. The principles of fiber strengthened composites and dispersion strengthened materials are adapted to explain the mechanical properties of these castings. It is generally accepted that castings often have inferior mechanical properties when con~pared to wrought products. However, there is little quantitative data available concerning the factors which make apparently sound castings weak and/or brittle. The relative ease and inexpensiveness of the casting process have always been attractive and, therefore, an understanding of the factors which contribute to the mechanical properties of castings would seem desirable. Such an understanding may lead to an improvement in the mechanical properties to an extent where castings would become competitive in applications where presently only wrought products are considered to have the requisite properties. Such an understanding could also improve the reliability of present cast products. Much of the recent research on castings has centered about determining the extent of segregation in cast alloys. Macrosegregation, particularly inverse segregation, has been studied in some detail 1-8 and a considerable understanding of microsegregation has been obtained.9&apos;10 The effect of solidification rate on dendrite spacing and on the amount of interdendritic eutectic in binary alloys has been established, particularly for Al(rich)-Cu alloys.""0 However, the extension of these ideas to relate the amount of interdendritic eutectic, concentration gradients, micro-segregation, dendrite spacings, and so forth, to the rnechanical properties has been limited. Dean and spear" have related the mechanical properties of an Al-Si-Mg alloy, A356-T62, to the dendrite spacing and have shown that the mechanical properties improve with decreasing dendrite spacing. Passmore et al.12 have shown that annealing at high temperature improves the mechanical properties of Al(rich)-Cu al- loys and Archer and Kempf 13 have shown that an Al-1 pct Mg-1.75 pct Si alloy behaves in a similar manner. Ahearn and Quigley 14 have shown that high temperature homogenization also enhances the mechanical properties of an SAE 4330 steel. However, in the above investigations, no underlying reasons were suggested for the improvement in mechanical properties. The purpose of the present investigation is to relate the mechanical properties of castings to some of the solichfication variables and to derive some equations by which calculations of the mechanical properties may be attempted. In particular, the effect of the amount of interdendritic eutectic and the effect of stress direction with respect to that of solidification on the mechanical properties will be considered. The Al(rich)-Mg and Al(rich)-Cu binary alloy systems were chosen for study. The A1-Mg system was chosen because its constitutional relationships are such that large volunles of eutectic (up to 24 vol pct) may be obtained in the as-cast condition and then be completely dissolved by subsequent heat treatment at about 440°C. This allows a comprehensive study relating the mechanical properties of castings to the amount of interdendritic eutectic. Also the Al(rich)-Mg eutectic is almost a single phase 15 which should make the experimental results more amenable to theoretical interpretation and calculation. The A1-Cu system was chosen for study because of the large amount of related information available concerning segregation, dendrite spacing, and so forth. Unidirectionally solidified castings were used throughout the investigation so that the effect of solidification direction with respect to the direction of applied stress could be determined. THEORETICAL It is well known that upon solidification of binary alloy castings, the nonequilibrium amount of eutectic which forms is given by 10 where fe o is the weight fraction of eutectic, Cs is the solid solubility of solute at the eutectic temperature, k is the equilibrium partition coefficient, and C, is the average composition of the alloy. In the development of Eq. [I], it is assumed that the effects of inverse segregation and diffusion in the solid are negligible, and that no porosity is present. If the casting is homogenized at a high temperature for a long period of time, some (or all) of the eutectic is dissolved and the amount of eutectic for this "equilibrium" condition may be calculated directly from the constitutional diagram. By appropriate intermediate annealing, the

Jan 1, 1970

By Joe O. Ledbetter

INTRODUCTION Health physics as a profession really got a significant start during the Manhattan Project of World War 11. The Health Physics Society has recently published its 25th anniversary issue of the journal (June 1980). There was concern over radiation exposures during and after uranium production, especially about radium and its daughter products [Jackson 19401 and, as evidenced by the frequency of articles in the literature, there still is. The reason for this concern was expressed by Harley as "Workers engaged in the mining and pro- cessing of radium-bearing materials are exposed to dusts of the parent, to radon, and to the radon daughter products. In- haled radioactive particulates may be retained in the lung or redistributed to other organs of the body. Relatively minute de- posits of radioactive substances, particularly alpha emitters, have been clearly shown to be the etiological factor in a variety of injuries to industrial and re- search workers. " [Harley 1953] Emphasis in measurements has been placed on radium in water and radon in air, since these are the principal mobilized phases; however, it should be kept in mind that radium-containing particles do become suspended in air as aerosols and radon absorbs in liquids. Much of the uranium mining and production is being carried out aboveground. The principal difference between underground and surface (pit or leach) mining of uranium is the reversal in the relative importance of roles for the types of radiation dose. For aboveground the major radiation exposure is external gamma ray, whereas for underground it is internal alpha; for aboveground, the whole body penetrating is of greater importance than the lung alpha dose. AS a result of the politics involved and the law- suits for any and all diseases as being occupationally- caused, today , more than ever before, the successful performance of the activities connected with uranium production--before-, during-, and after-the-fact-- must include the provision of first class radiation protection. Such protection can be achieved by good measurements, thorough risk evaluations, and adequate controls. Meeting the ALARA (As Low As Reasonably Achievable) philosophy necessarily entails the determination of what is reasonable exposure. The necessary and sufficient elements of radiation safety under the ALARA dictum require a hard look at the dose versus effects data. There are times when the health physicist needs to make decisions of judgement rather than compliance with a well-defined regulation value. In order to facilitate such decisions, the real world must be separated from opinions that are merely artifacts of statistical variation and from the unprovable "what ifs" that are slanted to question the morality of any non-Luddite. UNITS VOCABULARY FOR DOSIMETRY There have been many radiation quantifying and dosimetric units introduced in the past. Fortunately, most of them did not catch on enough to become required knowledge for reading the health physics literature. The unit definitions necessary for our purposes here are the following: -curie (Ci)--unit of radioactivity equal to 3.7 x 10 10 disintegrations per second Webster&apos;s 19711 or the quantity of radionuclide that undergoes 3.7 x 10 nuclear transformations per second. Environmental levels of radioactivity are usually measured in picocuries (10-l2 Ci) per cubic meter for air and in picocuries per liter (pCi/~) for water and sometimes for air. .roentgen (R)--exposure dose of x or gamma rays that gives 1 esu of charge (either sign) to 1 cc of dry air @ STP. The roentgen is equivalent to an energy absorption of 86.7 ergs/g of air [Gloyna and Ledbetter 19691. .rad--radiation absorbed dose of 100 ergs per gram of absorber. The SI unit for absorbed radiation dose is the Gray; 1 Gy = 100 rads. orem--radiation absorbed dose of 1 rad times the quality factor (QF) for that radiation. The QF is 1 for x rays, gamma rays, beta rays, and posi- trons. For heavy ionizing particulate radiation, QF is a function of the amount of energy trans- ferred per unit length of travel, i.e. , the linear energy transfer (LET); the values of QF:LET in keV/um are as follows: 1:<3.5; 1-2:3.5-7; 2-5:7-23; 5-10:23-53; and 10-20:53-175 [Morgan and Turner 19 671 . For radiobiology, relative biological effectiveness (RBE) is recommended for use instead of the quality factor above that is for radiation protection: the RBE is the ratio of the dose of 200 kVp x rays to the dose of radia- tion in question (both in rads) to cause the same

Jan 1, 1980

By Adam L. Wesner, A. C. Richardson

DURING World War II the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pet iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pet of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The -10 +35 mesh fraction was found to be the most promising feed for producing the low-ash [ ] content coal. A batch of 30 tons of -3/8-in. coal was screened at 10 and 35 mesh; the yield of -10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the -35 +48 mesh range. A representative portion of the -10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pet ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1952

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki&apos;s phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki&apos;s data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By O. J. Neslage, R. W. Jenkins

MINE operators today are paying increased attention to the mechanization of drilling operations as an important factor in increasing efficiency and decreasing costs. Recent progress in the design of drill jibs for mounting on drill carriages, or jumbos, has done much to advance the mechanization of mining methods. This progress has introduced new opportunities in the application of "jib jumbos" that are worth serious consideration. An attempt will be made here to classify the various types of jumbos and drill mountings available for level development and flat stope work, t6 indicate applications, and to measure their effectiveness in relation to their cost. The data here are based on a wide variety of field usage, and are offered only to point up, in a general way, the relative efficiency in proportion to cost. It should be remembered that any contemplated jumbo installation must be studied to determine what type of installation is most suitable, considering ground conditions, loading, timbering and haulage equipment, service available, and attitude of manpower. Early Drill Carriages: The advantages of some sort of a drill carriage were recognized at the time rock drills were introduced. In drift or heading operations where a fairly standard drill round and cross section were anticipated, as well as in flat bedded deposits where standard slabbing rounds were used, track and crawler-mounted drills found an early application. These first drill jumbos were little more than drill carriers, designed locally and manufactured with materials at hand. Of comparatively simple construction, function, and low capital cost, they usually consisted of a hinged column which supported one or more drills on arms or universal bars. When the column was pivoted vertically, the drills were moved into position. Screw jack extensions reached from the column to the roof and floor to hold the drill rigid. In some cases, particularly in tunnel jumbos, enough weight was carried that rail clamps or roof jacks were sufficient. Many of these column and arm-type jumbos, usually equipped with air and water manifolds, steel racks, and staging for drillers, are still in use today. Some have employed air or hydraulic extensions for securing the columns. They offer the equip-saving advantage of having all the necessary out, ment together, and they un be moved i and t. set up and torn down as a unit. Boom-type Jumbos: When the advantages of to column-type jumbo were seen, operators could to realize the further gains possible. More time could be saved with mechanical assistance to position api drill vertically. A rack on the column and a pinion on the arm for raising and lowering the drill in the manner of a quarry bar were tried with some success. The most outstanding solution to the vertical handling problem was reached with the boom-type of jumbo. Here two or more machines were mounted on a cross arm at the end of a boom that was pivoted at the rear of the track. This was raised and lowered by various mechanical aids. Occasionally air or hydraulic power was used. Nearly all of today&apos;s wagon drills use this boom-type principle. Boom jumbos represent a savings in time and physical effort expended in raising and lowering the drills. The boom must be balanced by the roof of the truck which is secured by rail clamps or type jacks. The most successful application of areawhere this of jumbo has been in the Tri-State area where multiple long-feed machines are used on caterpillar-mounted, boom-type jumbos for slabbing

Jan 1, 1951

By R. W. Jenkins, O. J. Neslage

MINE operators today are paying increased attention to the mechanization of drilling operations as an important factor in increasing efficiency and decreasing costs. Recent progress in the design of drill jibs for mounting on drill carriages, or jumbos, has done much to advance the mechanization of mining methods. This progress has introduced new opportunities in the application of "jib jumbos" that are worth serious consideration. An attempt will be made here to classify the various types of jumbos and drill mountings available for level development and flat stope work, t6 indicate applications, and to measure their effectiveness in relation to their cost. The data here are based on a wide variety of field usage, and are offered only to point up, in a general way, the relative efficiency in proportion to cost. It should be remembered that any contemplated jumbo installation must be studied to determine what type of installation is most suitable, considering ground conditions, loading, timbering and haulage equipment, service available, and attitude of manpower. Early Drill Carriages: The advantages of some sort of a drill carriage were recognized at the time rock drills were introduced. In drift or heading operations where a fairly standard drill round and cross section were anticipated, as well as in flat bedded deposits where standard slabbing rounds were used, track and crawler-mounted drills found an early application. These first drill jumbos were little more than drill carriers, designed locally and manufactured with materials at hand. Of comparatively simple construction, function, and low capital cost, they usually consisted of a hinged column which supported one or more drills on arms or universal bars. When the column was pivoted vertically, the drills were moved into position. Screw jack extensions reached from the column to the roof and floor to hold the drill rigid. In some cases, particularly in tunnel jumbos, enough weight was carried that rail clamps or roof jacks were sufficient. Many of these column and arm-type jumbos, usually equipped with air and water manifolds, steel racks, and staging for drillers, are still in use today. Some have employed air or hydraulic extensions for securing the columns. They offer the equip-saving advantage of having all the necessary out, ment together, and they un be moved i and t. set up and torn down as a unit. Boom-type Jumbos: When the advantages of to column-type jumbo were seen, operators could to realize the further gains possible. More time could be saved with mechanical assistance to position api drill vertically. A rack on the column and a pinion on the arm for raising and lowering the drill in the manner of a quarry bar were tried with some success. The most outstanding solution to the vertical handling problem was reached with the boom-type of jumbo. Here two or more machines were mounted on a cross arm at the end of a boom that was pivoted at the rear of the track. This was raised and lowered by various mechanical aids. Occasionally air or hydraulic power was used. Nearly all of today&apos;s wagon drills use this boom-type principle. Boom jumbos represent a savings in time and physical effort expended in raising and lowering the drills. The boom must be balanced by the roof of the truck which is secured by rail clamps or type jacks. The most successful application of areawhere this of jumbo has been in the Tri-State area where multiple long-feed machines are used on caterpillar-mounted, boom-type jumbos for slabbing

Jan 1, 1951

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By S. J. McCarroll

Fig. 1—The belt shown at right carries filter cake to mixing station over calciner. Crude ore conveyors appear in right background. THE Three Kids mine, some six miles east of Henderson, Nev., is in a typical southwest desert area, with high dry summer heat and cool to cold winter seasons. The manganese deposit was located during World War I.&apos; During this period 15,000 to 20,000 tons of ore assaying up to 41 pct manganese were shipped. Interest in the deposit was not revived until the middle thirties, when experiments on the ore were initiated. Test work indicated possible recovery of only 70 pct by flotation, but in 1941 additional work was done at the Boulder City pilot plant of the U. S. Bureau of Mines and also by M. A. Hanna Co. As a result, the Manganese Ore Co. was formed and a plant utilizing the SO2 process was constructed. Numerous operation difficulties ensued, and the plant. was closed when the manganese situation in the country eased. In 1949 Hewitt S. West initiated negotiations to acquire the plant. In 1951 Manganese, Inc., was formed and contract entered into with the General Services Administration to supply 27 million units of metallurgical grade manganese in the form of nodules to the national stockpile. A second contract was made to upgrade 285,000 tons of stockpile ore. Test work was undertaken by the Southwestern Engineering Co. and likewise by the Boulder City pilot plant at the U. S. Bureau of Mines. Results obtained indicated the commercial feasibility of the flotation process. Construction of the plant, which is shown in Figs. 1 and 2, was started in June 1951, and operations on a break-in basis began in September 1952. Apart from the usual starting difficulties two major disasters caused serious setbacks, one a kiln failure in February 1953, and the other a fire that destroyed the flotation building in June of the same year. The nodulizing section of the plant resumed operation in November, and the flotation section in January 1954. The ore minerals are chiefly wad,* with minor amounts of psilomelane, and occur in sedimentary beds of volcanic tuff. The ore is overlain with beds of gypsum which outcrop or may be covered with surface gravel. Intermediate beds of red and white tuff occur frequently with lenses of red and green jasper and stringers of gypsum and calcite. Small amounts of iron are present; lead content averages about 1.0 pct and minute amounts of copper and zinc are found. Barite, celestite, and bentonite are present. Since these are made up of minute asicular crystals, moisture content is very high, averaging about 18 pct. Ore reserves have been estimated at 3 million tons averaging 18 pct Mn2 and up to 5 million tons after grade is dropped to 10 pct Mn. A good part of the orebody was stripped of overburden by the previous operating company . Approximately 50 pct of the ore, representing more than 60 pct of the manganese, can be mined by open-cut methods. A system for underground min- . ing has not yet been decided on. Open-cut mining with benches of 20 ft has proved satisfactory. Although the ore is soft and appears dry and dusty it has a certain resilience, probably due to the porosity and moisture which makes drilling and fragmentation difficult. Wagon drills have been abandoned in favor of the Joy 225-A rotary drill which will put down a 43/4 -in. hole at the rate of 2 ft per min. Holes are spaced in a pattern with 8 to 9-ft centers. Forty percent powder has been used, but better breaking to 2-ft size is obtained with low velocity bag powder of 30 pct strength. Loading is done with one 21/2-yd shovel, and cleanup follows with one D-7 bulldozer. The ore is hauled with Euclid trucks about 1000 ft from the pit to a blending pile, where the daily mine production is spread in layers by bulldozing until approximately one month&apos;s mill feed is accumulated. A new pile is then started and mill feed is drawn from the first pile by one 13/4-yd shovel and Euclid trucks, with a haul of approximately 500 ft. Mining is performed by an independent contractor with engineering and supervision by the company staff. Early test work indicated that the manganese could be floated with soap, a wetting agent, and fuel oil to give a recovery of better than 75 pct with a grade of 43 pct Mn. The concentrate when nodulized with coke would upgrade to 46 pct Mn or over, and the lead volatilized to 0.6 pct residual.

Jan 1, 1955

By J. E. Powell, F. H. Spedding

WHILE rare earths are reported to be widely distributed in nature and are not really rare," in practice, there are only a few minerals which are sufficiently rich in rare earths to serve as practical sources. Perhaps the best known of these is monazite which is a phosphate mineral containing rare earths and thorium. This mineral occurs as a dense brown sand in gravel beds and is particularly rich in the light rare earths of the cerium subgroup. This mineral is processed commercially for its thorium, cerium, and lanthanum content, and, consequently, furnishes rich concentrates from which neodymium, praseodymium, samarium, europium, and gadolinium may be obtained. Unfortunately, monazite is rather lean in rare earths heavier than gadolinium. A second mineral which is rich in the light rare earths is bastnasite, a fluoro-carbonate. Extensive deposits of this ore have been discovered in the western United States and have received considerable newspaper publicity in recent years. While bastnasite is very rich with respect to cerium, lanthanum, and neodymium, it contains even less heavy rare earths than does monazite. One of the better sources of heavy rare earths of the yttrium subgroup is gadolinite, a black silicate rock from which the rare-earth content can be extracted readily by acid leaching. It is obtained chiefly from Norway at the present time, although there are known deposits in the United States. Other sources of heavy rare earths include fergu-sonite, euxenite, and samarskite which are refractory tantalo-columbate ores. These minerals require caustic fusion or reduction to carbides with carbon before the rare-earth content can be extracted. All of the minerals which are rich in the heavy rare earths contain yttrium as a major constituent. After the rare earths have been extracted as a group from an ore by chemical means, it is generally convenient to precipitate them from acid media with oxalic acid in order to eliminate certain non-rare-earth impurities such as iron, beryllium, etc., which are usually present. The oxalate can then be readily ignited to R2O3. The oxide can be dissolved in acid and is the starting point for subsequent separation into the pure components. Perhaps the principal reason why the rare earths have not been studied as extensively as other elements of the periodic table, whose natural abundances are comparable, is that they are extremely difficult to separate from each other by the usual chemical means. Prior to 1945, the separation of one trivalent rare earth from another was a laborious process. All separations were based on repeated fractionation processes, i.e., fractional precipitation, fractional decomposition, fractional crystallization, etc. These processes were repeated from a few hundred to many thousands of times in order to obtain individual rare-earth salts of reasonable purity. Of course, mention should be made that, in the few cases where a rare earth could be oxidized or reduced to a valence state other than three, more conventional chemical means could be utilized to separate the oxidized or reduced ion from the other normally trivalent rare earths. The ionic states which deserve special mention are CeIV, SmII, Eu11, and Yb11. When it is possible to remove an element of the series efficiently, due to an optional valence state, its immediate neighbors also become easier to isolate. For example, binary mixtures of lanthanum and cerium, and praseodymium and cerium can be obtained by a relatively small number of fractional operations. The tetravalent state of cerium then allows the complete resolution of the binary mixtures by ordinary chemical means. Although the tetravalent state of cerium has been known for a long time, the divalent states of samarium, europium, and ytterbium were not used extensively in separations prior to 1930 because they are relatively unstable in aqueous media.&apos;-" No attempt will be made to give a comprehensive review of the extensive literature dealing with the separation of rare earths. Rather, this paper will be confined to a review of those methods which have been developed at Iowa State College during recent years, and which have proved extraordinarily successful for the isolation of highly pure rare earths in quantity. It was obvious that, if pure rare earths were to become generally available, methods would have to be developed wherein the thousands of fractional operations made necessary by the similarity of rare-earth properties could be performed automatically. The development of chromatographic techniques and ion-exchange resins appeared to offer a mechanism by which this objective could be accomplished. A number of early attempts were made to separate rare earths by these means; for example, Russell and Pearce12 passed a mixture of rare earths through a cation-exchange column and reported

Jan 1, 1955

By G. F. Bolling

STUDIES of grain boundary migration in zone-refined metals have all shown that the rate of migration is greatly reduced by small added solute concentrations. However, it is apparent that a difference exists between boundary migration during normal grain growth and single boundaries migrating in a bicrystal to consume a substructure. To effect the same reduction in velocity in the two cases, much more solute is required for grain growth than for the single boundary experiments. One case is available for direct comparison; both Bolling and winegardl and Aust and utter&apos; added silver and gold to zone-refined lead to study grain growth and single boundary migration, respectively. For comparable reductions in migration rates, about 500 times more solute was required to retard grain growth than to retard the single boundaries. A reason for this difference is suggested here. The rate of grain boundary migration is dependent on solute concentration and must therefore also depend on the solute distribution; i.e., regions of higher solute concentration encountered by a moving boundary must produce greater retardation and thus could determine any observed rate. A dislocation substructure can be the source of a nonuniform solute distribution since it can attract an excess concentration of certain solutes. In fact, it is probable that the solutes which impede grain boundary migration most would segregate most severely to a substructure for the same reasons. Thus a dislocation substructure present in a crystal being consumed could locally magnify the concentration of solute confronting an advancing grain boundary. In the single boundary experiments a low-angle substructure, within single crystals obtained by growth from the melt, was used to provide the driving force to move a grain boundary; in grain growth, no substructure of this magnitude was present. The increased solute concentration at subboundaries should be given approximately by C, = G e c,/kT, where t, is a binding energy and CO the bulk concentration. To account for the difference between the two experiments in the Pb-Ag and Pb-Au cases, C, must be the concentration impeding the single boundary migration, and a value of t, = 0.25 ev is necessary. This is reasonable, even though calculation on a purely elastic basis gives t, = 0.12 ev. because electronic effects must enter for silver and gold in lead. The compound AuPbz forms3 and the metastable compound AgrPb has been reported to nucleate at dislocations prior to the formation of the stable, silver-rich phase.4 Other observations support the hypothesis that a magnified solute concentration impedes the single boundary migration. For example, some crystals were grown by Aust and Rutter at concentrations of ~ 0.1 wt pct Sn and 2 x X at. pct Ag or Au which exhibited a cellular substructure, and in these crystals no boundary migration was observed. It is therefore evident that the higher concentrations at cell boundaries drastically inhibited migration. Inclusions would not have been responsible for this inhibition since according to recent work on cellular segregation,5 no second phase should have occurred in the segregated regions at the cell boundaries for the conditions of growth used, at least in the Pb-Sn system. In the purest lead, only the "special" boundaries observed by Aust and Rutter gave rise to the same activation energy as that obtained in grain growth. It is reasonable to suppose that the structure of special boundaries does not favor segregation at low concentrations and thus solute, or an inhomogeneity in its distribution, would have no effect. Random boundaries, on the other hand, are affected by solute and the substructure would enhance residual concentrations in the zone-refined lead, leading to a higher activation energy. It is clear, even without a detailed theory, that the apparent activation energies and exact solute dependence in the two experiments must be different as long as the non-uniform solute distribution produced by the substructure is important. Recrystallization experiments should also be susceptible to the same kind of local segregation at subboundaries or disloca tion cell walls; a suggestion similar to this has been made by Leslie et al.&apos; Following the arguments presented here, the effects of a given solute concentration would be like those observed by Aust and Rutter if segregation occurred, and like those of grain growth otherwise. This work was partially supported by the Air Force Office of Scientific Research; Contract AF-49(638)-1029.

Jan 1, 1962

By Charles L. Guettel

The temperature coefficients of electrical resistance of 31 alloys in the nickel-rich corner of the Ni-Cr-Fe system were determined. The results indicate that a range of binary Ni-Cr alloys has lower temperature coefficients than a specific region of Ni-Cr-Fe alloys which has been reported and quoted by others as providing the lowest coefficients in the ternary system. DESIRABLE properties of resistivity and temperature coefficients of resistance have been the basis for the successful commercial application of various Ni-Cr and Ni-Cr-Fe alloys. In particular, low or negligible temperature coefficients of resistance are necessary for wire used in precision wire wound resistors and potentiometers involved in closely controlled electrical and electronic circuitry. Alloys most successfully applied to this purpose basically have not been ternary Ni-Cr-Fe alloys but rather heat-treated Ni-Cr alloys in the region of approximately 73 to 79 pct Ni and 20 pct Cr with significant additions of other elements such as aluminum, silicon, iron, copper, manganese, and cobalt. While the addition elements play a vital role in the nature and control of the temperature-resistance curve of any one of these alloys, the inherent relatively low temperature coefficient of the binary Ni-Cr base composition itself in the approximate region of 80 pct Ni and 20 pct Cr contributes fundamentally to the eventual negligible temperature coefficient obtained with the applied alloys. W. A. Dean 1 has reported mean temperature coefficients (20&apos; to 100oC) of as-cast samples for the Ni-Cr-Fe system, the nickel corner of which is given in Fig. 1. Dean had to use as-cast samples because alloys from a considerable region of the system were unworkable. Dean refers to the work of Hunter and sebast2 who used annealed wire samples to show that, for chromium contents of 10 to 25 pct, the temperature coefficient increases as the iron content is increased at the expense of nickel. Although the data of Hunter and Sebast were limited in the nickel-rich areas to eight samples of 60 to 91 pct Ni with only four samples containing iron, the possibility that no Ni-Cr-Fe alloy has a lower temperature coefficient than certain binary Ni-Cr alloys should have been given serious consideration. However, Dean&apos;s work has been referred to by J. S. Marsh,3 who, quoting Dean, states that for the temperature coefficients "the smallest values-about 0.0001 per oC (100 ppm)—were found for alloys containing about 55 pct Ni and 20 pct Cr" (balance iron). A region such as that reported by Dean would be significant to those trying to develop alloys for the applications described. Therefore, a series of three-pound laboratory open-air induction melts of Ni-Cr and Ni-Cr-Fe alloys were melted, conventionally processed to 0.005 in. diam wire, and continuously strand annealed at 1900° F. The basic Ni-Cr compositions, with balances essentially iron other than usual minor impurities, and the corresponding temperature coefficients of resistance and resistivities are given in Table I. The resistivities are approximate and are not to be considered as a basis for relating them to their position of composition in the ternary system. The wire diameters were determined with a micrometer, and not by weight and density measurements which would be required for accurate resistivity values. However,

Jan 1, 1963