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By Edward H. Robie

PROBABLY nowhere in the United States or its possessions is mining development more active at present than in the Philippine Islands. Only a few years ago only one company was of any importance, the Benguet Consolidated. Now, five companies are paying dividends, five others have reached the producing stage, some seven others may produce this year, and a score or so are being actively developed. Gold production in 1933 was valued at about $8,000,000, last year at about $11,000,000, and this year an output valued at about $17,000,000 is envisaged. At the beginning of 1934 about 1750 tons of ore was being milled daily; at the end of the year, the tonnage was approximately 3400. In 1933 there were only thirteen Institute members in the Philippines; a year ago there were 27, and now there are 46. About fifteen thousand amen were employed in the mining industry last year, with mine payrolls amounting to $3,500,000. An immense amount of new machinery has been required. One difficulty has so far hindered gold-mine development to some extent-lack of adequate power. Each company therefore finds it necessary to generate its own power, and for this purpose diesel engines are generally adopted.

Jan 1, 1935

By D. C. Reynolds

Recent experiments with II-VI compounds have shown that they hazle considerable potential for laser applications over a broad region of the optical spectrum. It may be possible to cover the spectrum continuously from 3200A (ZnS) to the far infrared (CdHg:Te) since HgTe is a semimetal. At this writing laser action has been observed in ZnS, Zn0, CdS, CdSe, CdS:Se, CdTe, and some of the CdHg:Te alloys. Of particular interest are those lasers operating in the zlisible and near ultraciolet regzons of the spectrum where detectors of high sensitivity are available. The lasing transitions in II-VI compounds are bound exciton transitions some of which have been identified in auxiliary experiments. High efficiencies and low thresholds for lasing hare been achieved almost exc1usively in plutelet-type crystals. The greater crystalline quality exhibited by the phtelet-type material is shown to result from the crystal growth habit. Phonon scattering- of conduction electrons to the ground-state exciton is discussed ill relution to Lou thresholds and high efficiencies for lasing- observed in the CdS:Se solid solutions. The first successful semiconductor laser operation was achieved in the III-V compounds. It is possible to choose a material in this group that will operate between approximately 0.65 and 8.5 . There are at least two reasons why one would like to have a laser operating at shorter wavelengths. First, it would be easier to experiment with a laser operating in the visible region of the spectrum, and also more desirable to have high-in tensity visible light sources. Second, the most sensitive photomul-tiplier detectors are available in the visible and near ultraviolet regions of the spectrum. It is known that II-VI compounds are direct-band-gap semiconductors and as such offer the potential of operating at any specified wavelength between 3200 (ZnS) and 7772A (CdTe). Light emission from II-VI compounds has been the subject of numerous investigations for many years. These investigations were all primarily concerned with noncoherent emission. It has been only recently that coherent emission from these compounds has been observed. To date, laser operation has been demonstrated in CdS, CdSe, and the solid solutions of CdS:Se, ZnS, ZnO, and CdTe. These compounds cover an appreciable portion of the optical spectrum from the ultraviolet to the near infrared. In considering laser applications, the use of lasers in communication's systems offers many desirable features. In any operation of this type one must consider the losses in transmitting the radiation from the source to the detector. Atmospheric absorption in the visible and near ultraviolet is variable and greater than in certain regions of the infrared. It might be concluded that for long-range communication systems an infrared laser operating in a spectral region that is coincident with a transmission window in the atmosphere would be preferable. However, one cannot overlook the possibility of operating a system in the sensitive region of a highly sensitive photomultiplier detector or other light-amplifying system. LASER CONSIDERATIONS To produce a source of coherent radiation it is necessary to achieve a population inversion. In the case of semiconducting materials it is necessary to raise the electrons from one energy state to a higher-energy state relative to it. In semiconductors, this population inversion can be achieved by three different techniques: 1) Current Injection. This technique uses a p-n junction biased in the forward direction. Large numbers of electrons are injected from the n region into the p region, and recombination occurs close to the junction. An inverted population is obtained in this region and the recombination radiation propagates parallel to the junction. This type of pumping has been used in the GaAs junction-type lasers but has not been successfully employed in the II-VI compounds. 2) Optical Pumping. In this case, one uses photons to obtain a population inversion by exciting electrons to higher-energy states. The pump sources are flash lamps or arc lamps and, occasionally, other laser sources when such sources have the appropriate energy for exciting the electrons. The disadvantage of this type of pumping is that flash lamps put out a rather broad spectrum of radiation, whereas the laser material has a rather narrow region of absorption. This results in an inefficient process. Laser sources provide efficient pump sources but the number of usable wavelengths is limited. 3) Electron Beam Pumping. In this technique, the laser sample cavity is bombarded with electrons having energies in the range from approximately 10 to a few hundred kv. The bombarding radiation excites electrons from valence to conduction band states in the semiconductor, giving rise to an inverted population. This type of pumping has been used successfully in several 11-VI compounds.

Jan 1, 1968

By R. G. McQueen, E. G. Zukas

THE production of isotropic fine-grained ingot iron would be most useful since physical measurements associated with the elastic properties of iron are influenced by the size and orientation of the individual grains. This can be accomplished at present for small samples by established metallurgical procedures, but for large samples (in excess of 2 in. diam by 1 in. thick) it is virtually impossible to produce reasonably small uniform grains with random orientation. Such pieces can, however, be produced by impulsive loading followed by a suitable recrystallization treatment. The shock loading system employed is diagrammed in Fig. l. Here the 3/8-in. iron plate is accelerated by the plane-wave initiated high explosive charge through a 1 5/8-in. air space. Collision of this plate and the specimen of interest generates a shock wave in excess of 300 kbars which passes through the specimen. For this type of work it is not necessary to use machined parts: for example, the ingot iron pieces are saw cut from the billet so that they can be inserted in short sections of iron pipe. The recovered specimens are less distorted, however, if the air gap between the iron sample and pipe is filled with Woods metal. The dimensional changes resulting from this type of loading technique are minor, usually less than a 10 pct reduction in thickness. Compressive yield

Jan 1, 1962

By J. M. Oblak, W. A. Owczarski

A cellular appearing recrystallization product formed by annealing a cold-worked nickel-base super-alloy at 1800°F has been studied by electron nzicroscopy. Prior to deformation, an equilibrium micro-structure of fcc matrix y and cuboidal ,,', Ni (Al, Ti), precipitates of CuzAu structure had been established by an age at 1825°F. The strain-free recrystallization cells consist of very large rodular y' particles in a y matrix. They precipitate is oriented and coherent both before and after recrystallization. The results showed that y' coarsening accompanies recrystallization at 1800°F. However, it does so as a secondary effect and does not necessarily take place at lower temperatures. The structural similarity of this reaction to cellular precipitation in other systems indicates that lattice strain may also play a significant role during some cellular precipitation reactions. THERE have been numerous microstructural investigations of recrystallization in single-phase materials but two-phase systems have received much less attention. The second phase can either remain inert or be altered along with the matrix during recrystallization. If the second phase is an oxidelm3 or a relatively inert pre~ipitate,~, recrystallization is retarded when the interparticle spacing is less than 1 p. Prior to the onset of recrystallization, these materials show a well-polygonized substructure with the subgrain size limited by the interparticle spacing. Since recrystallization by the motion of preexisting grain boundaries6 is not observed, retardation has been related to particle pinning of the subboundaries. This pinning prevents coalescence' or growth8 of subgrains to a critical size (formation of a high-angle boundary) necessary to initiate recrystallization. In a material such as a nickel-base superalloy both y matrix and y' precipitate are altered by the recrystallization reaction. Haessner et al.' studied the recrystallization of a cold-rolled Ni-Cr-A1 alloy by electron microscopy. The material was initially cold-rolled in the supersaturated condition. upon annealing at 750°C, immediate precipitation of 7'occurred. Presence of this 7' greatly retarded the onset of recrystallization which eventually took place by the development of randomly oriented, strain-free grains. The original •/ was dissolved at the recrystallization interface and reprecipitated as oriented, coherent par-tiles in the new grain. Recrystallization caused a refinement of .)' particle size. Recently ~hillips'' investigated recrystallization of Ni-12.7 at. pct Al. Reduction by cold rolling presumably elongated the p' precipitate into lamellae that remained coherent with the matrix. After recrystallization at 600" to 750°C, there was no unusual change in y' particle size al- though there was a tendency toward clustering along the prior rolling direction at 750°C. Above 750°C, the recrystallized grains were generally free of precipitate. Studies in the somewhat analogous Cu-3.23 wt pct CO" and Cu-2 wt pct'2 systems demonstrated that the coherent cobalt-rich fcc precipitate in these alloys obstructed softening, initiation, and completion of recrystallization. The precipitates were deformed into lam~llae during rolling and those of diameter less than 250A remained coherent. Recrystallization took place by the growth of new grains into the recovered or poly-gonized material. In the first study," both matrix and precipitate reoriented in the same manner upon passage of the recrystallization interface. There was no change in particle size or morphology. Tanner and ~ervi,~ on the other hand, observed that motion of the recrystallization fronts was strongly hindered by the pinning action of coherent precipitates in the deformed material. Particles in contact with a pinned boundary coarsened and coalesced leaving a denuded zone in the unrecrystallized region. When the number of pinning points was sufficiently reduced by coalescence, the boundary swept past these particles and through the denuded zone. The authors1' considered this as a variation of discontinuous precipitation with both chemical driving force and deformation strain energy contributing to recrystallization. Preliminary observations by the present authors had revealed that recrystallization in Udimet 700, a nickel-base superalloy, occurred in an entirely different manner. Optical metallography showed that the recrystallized product formed as cellular colonies containing coarse y' particles elongated in the direction of cell growth. In this investigation the structural features of this reaction were investigated by transmission electron microscopy. EXPERIMENTAL PROCEDURE As-received I$-in. rounds of Udimet 700* were (wtpct) 18.4 15.2 4.95 4.42 3.43 0.06 0.031 0.14 Bal. solution-annealed for 4 hr at 2150" and then fast air-cooled. An initial y-~' structure was established by a 4-hr age at 1825°F followed by a fast air,cool. Essentially the equilibrium volume fraction of ?' at 1825°F is precipitated within 4 hr. Microstructural examination showed no measurable increase in the amount of precipitate after longer aging times. Deformation consisted of swaging to 52 pct RA with 6 pct reduction per pass at room temperature. To reduce the precipitation potential to a negligible amount, recrystallization anneals were conducted at 1800"~ (982"~). Microstructures were investigated by optical and transmission electron microscopy. To prepare foils for electron microscopy, the material was first sliced into 30-mil slabs parallel to the swaging direction. Discs were dimpled and electrolytically cut from

Jan 1, 1969

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,' and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6's viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG'S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.' Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By J. R. O’Connor

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

Jan 1, 1968

By W. E. Quist, R. Taggart, D. H. Polonis, C. J. van der Wekken

An intermediate compound that has been identified as Niab is observed to form as a decomposition product from supersaturaled Ni-Nb solid solutions during aging at temperatures between approximately 300" and 500°C. On the basis of data from electron microscopy and selected-area diffraction, the structure of this compound has been determined as fct with a = b - 3a0 and c = a, wlzere a,, is the lattice parameter of the parent solid solution. The compound consists of close-packed layers with triangular ordering, where the niobiutrl atoms are separated by two nickel atoms ([long- close?-packed directions. A nine layer stacking sequence is required to describe the proposed structure. STUDIES of the Ni-Nb binary system have been limited primarily to phase diagram determinations,'-4 investigations of high-temperature equilibrium phases,5"1 and the determination of the influence of deformation on the structure of the equilibrium compound.8 The nickel-rich portion of the binary system is reported to be of the simple eutectic type in which the maximum solubility of 12.7 at. pct Nb occurs at 1282"c.' The two-phase field below the eutectic temperature is bounded by the a fcc solid solution and an orthorhombic Ni3Nb compound. No metastable phases have been reported in previous investigations. In transformation studies of certain nickel-base commercial alloys that contain niobium, two ordered metastable compounds containing niobium have been shown to precipitate from the solid solution, both of which have been identified as y' and have the composition NisNb or Ni,Nb. One compound has been reported to have the bct DOz2 type Al3Ti structure" and the other the cubic LI2 type Cu3Au structure.9,11 In the present work on Ni-Nb binary alloys a metastable y' compound has not been detected after conventional quenching and aging treatments. An anomalous behavior was noted in electrical resistivity measurements. in alloys containing between 7 to 12 at. pct Nb when aging treatments were performed below 500°C after fast quenching from 1250°C. Transmission electron microscopy has shown that this behavior is caused by the formation of a low-temperature precipitate of unreported structure type and composition. EXPERIMENTAL METHODS Several Ni-Nb alloys, containing up to 11.5 at. pct Nb. were prepared by either levitation melting and casting in copper molds or by induction melting in alumina crucibles; both techniques employed purified helium gas as a protective atmosphere. The purity of the nickel and niobium used to make the alloys was 99.98 wt pct Ni and 99.9 wt pct Nb. The composition and homogeneity of the alloys were checked by weight measurements and by electron microprobe analysis. The induction-melted alloys were homogenized for 100 hr at 1100°C. The resistivity specimens were prepared from rods swaged to 2.5 mm and the electron microscopy specimens were cut from sheet that was rolled to 0.4 mm and thinned using a modified Bollmann technique." The elevated-temperature solution treatments were carried out in a purified helium atmosphere followed by direct quenching into a 10 pct NaCl solution at 23°C. Additional protection against oxidation of the samples during solution treatment was accomplished by using tantalum foil as a "getter" in the furnace. The specimens were aged at various temperatures in salt baths controlled to +2oC. A Leeds and Northrup K5 potentiometer was used to make electrical resistivity measurements on specimens immersed in liquid nitrogen. Electron microscopy and diffraction studies were carried out with JEM-7 and Philips EM-200 microscopes operating at 100 kv. RESULTS AND DISCUSSION Ni-Nb alloys containing between 7 and 11.5 at. pct Nb that have been solution-treated in the range 1220" to 1280°C and quenched to 23°C undergo a precipitation reaction when aged in the temperature range 300" to 500°C. Precipitation was detected by selected-area electron diffraction after aging a specimen for as little as 30 sec at 350°C) whereas the reaction was well-advanced after aging for 150 hr at 475°C. Electrical resistivity measurements were used to monitor the progress of the precipitation reaction. In the present experiments the nucleation process for precipitation required a high solution temperature and a rapid quench into brine. The presence of aluminum, iron? and carbon in amounts totaling less than 1 wt pct was found by electron diffraction to completely suppress the formation of the low-temperature precipitate that has been detected in the binary alloy. Electron diffraction techniques were used to determine the structure of the precipitates that formed during the decomposition of the Ni-Nb supersaturated solid solutions. Figs. l(a) through l(d) show electron diffraction patterns oriented to the [loo], [110], [lll], and [I031 zone axes of the matrix. Areas of reciprocal space between these sections were investigated by slowly varying the orientations of the crystal under study; this procedure revealed no reflections other than those depicted in Fig. 1. The presence of super-lattice reflections at points coincident with the matrix reflections was confirmed by the examination of an almost completely transformed structure. On the basis of the accumulated diffraction data, the reciprocal lat-

Jan 1, 1970

By WILFRED SYKES

IT is with particular pleasure that I welcome the members of the Open-hearth Conference of the I American Institute of Mining and Metallurgical Engineers to this meeting, as I feel this is one of the most useful activities of the Institute in the field of ferrous metallurgy. For the information of our other members I might say the Open-hearth Conference was organized by Mr. Reynders when he was president, and is made up of open-hearth superintendents and metallurgists. All the plants are invited to send representatives, and practically all do, with the exception of the U. S. Steel Corporation. It meets twice a year to discuss various problems in connection with the manufacture of steel, and its minutes are published for the benefit of those attending, the expense being defrayed by the participating companies. This conference, .1 believe, should be a model for activities in the other branches of the work covered by this Institute. It works, not by reading formal papers, which we all know is not a very satisfactory method to bring out the experience of others, but rather by a round-table method of discussion. The spirit of the meetings is such that each member feels perfectly free to state his experience, and he gets as much as he gives. A series of topics for, discussion is brought to the attention of the chairman and after one is exhausted the next point is taken up. In this way there is a real interchange of ideas and experiences which cannot fail l to be of the greatest benefit to those attending. That these meetings are beneficial is evidenced by the "continued growing attendance and lively discussions at these half-yearly meetings.

Jan 1, 1930

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1' of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By Walter Bradley

MINING by hydraulic process of the important gold-bearing gravels of the Sacramento Valley in the basins of the Yuba, Bear and American rivers began in 1853, and continued at an ever-increasing rate for 30 years. In its most active days it reached an annual production of $15,000,000, and averaged $10,000,000 per year over the 30 years. During that period no provisions were made to prevent the debris from being dis-charged into the water courses, and ultimately large quantities of silt, sand and gravel were washed down to the lower valleys; filling channels, causing overflow of agricultural lands and difficulty in maintaining navigable depths in the Sacramento River. Agitation and suits filed because of these damages finally resulted in the injunction decision of Judge L. B. Sawyer,1 in the U.S. Circuit Court, Jan. 23, 1884, which closed down practically all hydraulic mining operations not having means to restrain their debris. In 1893 (approved March 1, 1893), Congress passed the act introduced by Representative Anthony Caminetti, of California, creating the California Debris Com-mission, composed of three officers assigned from the Engineer Corps of the U.S. Army, and since that time it has been legal and possible within the drainage systems of Sacramento and San Joaquin rivers to conduct hydraulic mining of gold-bearing gravels behind dams built under this commission's permit and supervision. In the watersheds of the Trinity and Klamath rivers, which flow directly to the Pacific Ocean and do not affect navigation or agriculture, operating permits from the California Debris Commission are not required. There is a measure of restriction there, however,. through what is known as the Trinity and Klamath River Fish and Game Dis-trict. Chap. 215, Stat. 1931, in order to secure relatively clear water for the fishing season, provides that between July 15 and October 15 each year there must not be discharged into these rivers debris that will cause a turbidity greater than a content of 50 parts per million in the

Jan 1, 1936

By Stanley J. Gasior, Albert J. Forney, Joseph H. Field

Most bituminous coal mined near Eastern industrial areas requiring high-Btu pipeline gas is caking and therefore unsuitable for fixed-bed pres- sure gasification by present techniques. If the caking property of such coal can be destroyed, the resulting fuel can be gasified in a fixed bed at pressure with steam and oxygen as a preliminary step in making a high-Btu gas. To find a practical way to convert strongly caking coals of granular or small lump size to noncaking fuel was the object of this study. In previous work, strongly caking coals of 1/8- to 1½ -in. size were converted to a noncaking coal char by treatment in a static bed in about 3 hours1 and coal of 18-100 Tyler mesh in a fluidized bed in about 5 min.2 An inert gas such as steam, nitrogen, carbon dioxide or a mixture of all three with a small amount of oxygen was used in both studies. In our work a strongly caking bituminous coal from the Pittsburgh seam of 4-8 Tyler mesh size was converted to a noncaking form in free-fall in about 2 sec by dropping it through a countercurrent flow of steam containing 4% to 7% oxygen at 1150º-1200°F and 300 psig. This method should also be applicable to smaller-sized material.

Jan 3, 1965

By G. F. Dillion, A. F. Armington

THE present method for the ultrapurification of boron involves the formation, distillation, and decomposition of boron tribromide.' However, the boron tribromide prepared contains several impurities in the ppm range, even after distillation. Some of these impurities, notably carbon, can be reduced after decomposition by zone refining. In this study, a comparison of the purity of boron tribromide at various formation temperatures is presented. The apparatus employed consisted of a bromine flask connected to a 22 mm ID horizontal quartz reaction tube packed with amorphous boron powder, which was in turn connected to a receiving flask cooled with an ice bath. Argon was used as a carrier gas. The approximate rate of passage of bromine to the reaction tube was 25 g per hr. The reaction was first investigated at several temperatures in order to determine the lowest temperature necessary to produce a colorless product which was assumed to be an indication of complete reaction of the bromine. The lowest temperature found in this study was 420oC. The amount of impurities found in the boron tribromide at various formation temperatures is shown in Table I. The data presented are emission spectroscopic results of boric oxide produced by the hydrolysis of 2 to 3 g of boron tribromide in 10 ml of distilled water. After hydrolysis, the samples were dried several hours on a hot plate. Assuming equilibrium conditions in the reactor, one can make approximate thermodynamic calculations estimatling the completeness of reaction of bromine with boron and its impurities at various temperatures. Data for these calculations were taken from Rossini,3 and must be taken as approximations since the T?S factor was not included in the calculations. The results of such calculations indicate that, with the exception of carbon bromina-tion, all impurities would react almost to completeness (> 99 pet) at all temperatures between 400" and 900oC. In the case of carbon, which cannot be accurately analyzed spectroscopically, it is estimated that only about one sixth as much carbon tetrabromide would be formed at 400" than at 900°C. Since some marked reductions in impurity content were observed at the lower reaction temperature which would not be predicted by thermo-

Jan 1, 1962

By Roger E. Barthelemy

PRIMITIVE mining and metallurgy has today almost disappeared. Probably the only remaining tribal tin mining and smelting is practiced by the Laotian natives in one of the less known tin areas of the world. This district lies almost a thousand miles from the sea along the Mekong River, one of the longest rivers in the world, that marks the border between Siam and Laos, one of the five states forming French Indo-China. Less than twenty years ago it took more than two weeks' travel on elephant-back to reach the spot and today it still takes many days of travel, using all kinds of transportation from automobiles to native

Jan 1, 1938

CONTENTS DAVIS, CARL R., WILLEY, J. L., and EWING, S. E. T.-Recent Developments in the Fine Grinding and Treatment of Witwatersrand Ores. Discussed by Charles E. Locke, H. W. Hardinge, H. N. Spicer, G. M. Brown, Justice F. Grugan, R. C. Canby 1 WEINIG, A. J., and BOWEN, MAX W.-Determination of Dissolved Oxygen in Cyanide Solutions. Discussed by A. L. Blomfield, M. F. Dycus, A. W. Bull.... 4 LEPSOE, ROBERT.-Precipitation Efficiency of Zinc Dust in Cyanide Process. Discussed by G. M. Brown, Charles E. Locke 5 Recent Developments in the Fine Grinding and Treatment of Witwatersrand Ores Discussion of the paper of CARL R. DAVIS, J. L. WILLEY, S. E. T. EWING, presented at the New York Meeting, February, 1925, and issued as Paper No. 1386-B, with MINING AND METALLURGY, December, 1924. CHARLES E. LOCKE, Cambridge, Mass.-In this country, we have come to think that we should use smaller size of feed in our ball-mills. I will admit that a ball-mill is not comparable to a tube-mill, as conditions may not be the same, but there we have an unusual demonstration of the advantage of a coarser feed. Further investigation along this line is going to lead to some valuable results. The authors have overcome the difficulty of this coarse feed by taking out what I would call the difficult lumps, It is not clear from the paper whether many of these difficult lumps' may not be 'reduced portions of their grinding media. H. W. HARDINGE, New York, N. Y.-The idea is not exactly new because in 1911 they used the miner to reduce the finer material. We proceeded three or four years using many tons, about 15 tons. or nearly the same proportion of ore to grinding medium. Another thing to be taken into account is the hardness of the ore being ground. In South Africa, the transportation costs must be, taken into account. They are also making progress in the method of using tube-mills and ball-mills instead of stamps. Experiments are to be conducted with 10-ft. diameter mills there, with the object of increasing the mass action and agitation which, as has been demonstrated under different circumstances, increases the overall efficiency.

Jan 6, 1925

By SAM YOUR

PROCESSING, technology and application of non- ferrous metals-copper, lead, zinc, aluminum, nickel, precious metals, foundry metallurgy, less common metals, secondary metals-are the special field of the Institute of Metals Division. New developments in this field during 1930 are more or less briefly out- lined in this review prepared by the papers and publications committee of the Institute of Metals Division as follows:

Jan 1, 1931

By Charles R. Keyes

I. INTRODUCTION. FOR a period of several years, and in a large number of cases, the Metallurgical Laboratories of the New Mexico School of Mines were employed in umpire work. During this time many important local problems were solved. Against the results of careful chemical analyses of ores, assay-returns were often checked. In many cases the assay-methods of mine and custom-smelter were compared, and both often found faulty for the ore concerned. A wide range of ores was covered. Many of the chemical analyses and assays were made by Dr. F. C. Lincoln, Professor of Metallurgy, now of the Montana State School of Mines. A varied series of instructive assays was prepared by Prof. R. B. Brinsmade, now of the West Virginia State University. Single assays and given series of tests were undertaken by H. T. Goodjohn, now chief chemist to the Cia. Metalurgica de Torreon, Coahuila, Mexico; by H. J. Hubbard, now superintendent of the Butters Divisadero Mines, Jocoro,. San Salvador, C. A.; by E. D. Morton, now superintendent of the Arizona & Nevada Copper Mining Co., at Lunning, Nev. ; and by A. W. Edelen, now superintendent of the Angangueo Unit of the American Smelting & Refining Co., in Michoacan, Mexico. A critical comparison of assay-methods that were found to be followed in the case of certain gouge-ores mined in the Mimbres range in New Mexico, and about which there had been much controversy, was made by D. F. Riddell, then Acting Professor of Assaying, and now superintendent of the Providentia Mines Co. of Parral, in Chihuahua, Mexico. To him is due the credit of much that is contained in the following notes, which be has generously permitted -to be used in advance of the publication of the complete results.

Jul 1, 1911

By R. M. Schuller, J. J. Suloway, W. F. Childers, R. A. Griffin, S. J. Russell

Seven solid wastes from coal conversion processes were characterized chemically and mineralogically. The wastes included three Lurgi gasification ashes, two liquefaction residues (SRC and H-coal), a fly ash, and a water-quenched slag. Leachates generated from the solid wastes at various pH levels over the range 2.5 to 11.0 were analyzed for over 40 constituents. Results of the leachate analyses demonstrate the wide variation in constituent solubility for the solid wastes. To help assess the environmental impact of the disposal of these wastes, the leachates were also employed in soil attenuation studies and acute 96-hr static bioassays using young fathead minnows.

Jan 1, 1981

By R. W. Smith, R. W. Lai

Very recently there has been a quickening of research effort in the field of silicate mineral flotation, particularly as regards the flotation of beryl.' These studies have already contributed much to the understanding of both anionic and cat-ionic flotation of silicates. Of particular interest concerning anionic flotation has been the work done on heavy metal activation of silicates by M. C. Fuerstenau and co-workers.4,7 In addition. in the paper by Fuerstenau, Rice, Somasundaran and Fuerstenau7 attention was paid to low pH anionic flotation of beryl in the absence of activators. This subject was also covered in the papers by Avotins,3

Jan 1, 1967

NEW MEMBERS. The following list comprises the names of those persons who became members during the month of October, 1913: Members. BARNES, KENNETT F., Secty Granby Min. & Smelting Co., St. Louis, Mo. BILLINGSLEY, PAUL, Geol 526 Hennessy Bldg., Butte, Mont. BLANCHORD, RALPH C., Geol 3 Lombard St., London, England. BOYLE, ALBERT C., Jr., Prof. of Min. and Met., University of Wyoming, Laramie, Wyo. BRADFORD, JULIUS S., Min. Engr Chiksan Mining Co., Chiksan, Korea: CLEMES, ALFRED W., Min. Engr P. 0. Box 6,88, Moronic, Ariz. COPELAND, DURWARD, Met Cia. Estamifera de Llallagua, Bolivia, So. America. CRAWFORD, JOHN, JR., Mgr Noble Elec. Steel Co., Heroult, Shasta Co., Cal.

Jan 11, 1913