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By R. P. Smith

The diffusivity of carbon in iron, cobalt, and alloys of 89.7 and 79.3 wt pct Co has been determined by a decarburization method for the temperature range 850° to 1100°C. The Plots of log D us 1/T for the two Fe-Co alloys are linear through the region of the Curie temperature, showing that, unlike some cases of substitutional diffusion, carbon diffusion in these alloys is not affected by electron spin order. RECENT investigations1-' have shown that for substitutional diffusion in iron the change in diffusivity with temperature does not follow an Arrhenius equation, at temperatures near the Curie temperature. Data on the diffusivity of carbon in a iron5"9 indicate that this anomaly does not exist for interstitial diffusion; however, this has not been definitely established. Since cobalt and Fe-Co alloys, 80 to 100 pct Co, have Curie temperatures in a temperature range convenient for carbon-diffusion measurements they are suitable systems for studying the relation of interstitial diffusion and the Curie temperature. EXPERIMENTAL The carbon diffusivity, D, was determined by a decarburization method. The diffusion cylinders, made from small vacuum melts of electrolytic cobalt and plastiron, were about 0.76 cm diam and 6.3 cm long. A small amount of carbon was added to each melt to keep the oxygen content as low as possible. The cylinders were first treated with a hydrogen-3 pct water vapor mixture at 1100°C to constant weight, then carburized to the desired initial carbon content with a suitable CO-C02 gas mix-

Jan 1, 1964

By W. L. Watts

The existence of petroleum in California has been known for many years. From time immemorial the California Indians used this mineral, in the form of asphaltum, for various purposes. In the early history of the State the Catholic fathers utilized it for roofing their missions and other buildings. It is said that in 1855 or 1856 Andreas Pico distilled petroleum on a small scale for the San Fernando Mission. He obtained his crude oil from Pico canon, near Newhall, in Los Angeles county; and he was probably the first refiner of petroleum in this State. In 1856 a company commenced work at the La Brea ranch, in Los Angeles county, and tried to refine the crude oil. In 1857 an attempt was made to produce illuminating-oil from crude petroleum at Carpenteria, in Santa Barbara county; and there are records of similar attempts in other localities previous to 1860; but none of them were successful. The first scientific report on petroleum in California was made by Prof. B. Silliman, who published his researches in 1865. He spoke favorably of the possibility of obtaining petroleum in remunerative quantities in this State, and gave the results of his experiments in the fractional distillation of California petroleum. The next decade was marked by a considerable oil-excitement in California; and a great many companies mere formed for the purpose of petroleum-mining and for distilling crude oil. In most instances these companies did not meet with success; but it must be remembered that the pioneer oil-miners did not

Jan 1, 1900

G. R. DELAMATER,* Steelton, Pa. (written discussion t)..-Under the heading, "Preparation of Coal," Mr. Campbell discusses the ad-visability of sizing the coal for the jigs. While I fully realize that conditions alter cases, my method at all times is to do everything possible to avoid sizing. It would be unwise for anyone to say that greater ash and sulfur reduction is impossible by sizing. The thing that can be questioned is, will the greater reduction be sufficient to counterbalance the greater cost? The same thing is true of the proper size of crushing for each individual proposition. In past years many washeries have been built and equipped for wash-ing two or more sizes, but I know of few instances where these plants were operated more than a year before sizing was abandoned. Perhaps in some of these cases this was clue to lack of sufficient development of such scheme of operation; yet I have found that most men engaged in this work, including myself, started into the work with a pretty well-fixed idea that sizing would be beneficial. But trials and tests showed that the mixed size washing is necessary for coals requiring crushing to 1 in. or less. Coal is of low value, compared with other minerals segregated by washing or concentration, for which reason simplicity must be the watchword: simplicity in the machine used to attain the separations of impurities from the coal, in the accessory plant equipment, and in its arrangement.

Jan 12, 1919

By J. K. Gustafson

Since prehistoric times, gold has been sought for its beauty and its unusual physical and chemical properties. Early in the dawn of civilization it became the ultimate unit of value, and for at least 6000 years it has been used to barter for other commodities. It has been prospected for, treasured and made into works of art and personal adornment. From time to time, it has even been the object of conquest. Because of its predominant role as a basis for money in recent centuries, economists have come to think of gold solely in these terms. Gold, however, has physical and chemical properties that make it one of the most useful metals in the modern world. It is the most ductile metal known. An ounce of it can be drawn into a continuous wire over 35 miles long. It is also so malleable that an ounce of it can be beaten into films 0.00001 in. thick covering 68 sq ft of surface. It has a density of 19.3 and is so heavy that 1 cu ft of it weighs more than half a ton. Gold is nonmagnetic and has a high electric conductivity that is only slightly less than that of silver and copper. Gold is so inert to all the chemicals found in nature that gold coins and jewelry buried beneath the soil or at the bottom of the sea for thousands of years appear to be as bright and perfect as when they were first immersed. Finally, gold has an extremely high reflectivity of both light and infrared rays.

Jan 1, 1971

WHEN Magma Copper Company in 1952 set about finding $100,000,000 to finance the project of developing and equipping the property of its lusty progeny, the San Manuel Copper Corporation, A. J. McNab, president and guiding genius for both companies (and incidentally a mining engineer by profession), determined that he would avoid the mistake frequently made in such circumstances, of underestimating the cost, and thereby running short of funds before the job was completed. The fear that this might happen was one of the reasons why insurance companies, one potent source of "big" money, were reluctant to finance the enterprise. How, they asked themselves, would Magma, a relatively small company, get additional money in such a contingency? Insurance officials' thumbs were turned down. Conditions Imposed by R.F.C. The upshot was the negotiation by Mr. McNab for San Manuel of a contract with the Reconstruction Finance Corporation, dated July 10, 1952, whereby needed monies in amount up to $94,000,000 would be advanced as a loan, bearing 5 per cent interest. Arrangements were made for the separate financing of the new $10,000,000 town, needed for the project, through the Del E. Webb Construction Company of Phoenix, Arizona, and M.O.W. Homes, Incorporated, of Los Angeles. Thus the $94,000,000 drawing account was believed ample to provide for building the railroad, the mine plant, the concentrator, and the smelter, as well as for the underground development of the mine needed to start production. As a matter of fact, only

Jan 1, 1957

By William A. Hustrulid

INTRODUCTION Prior to the mid-1970's, the U.S. Radioactive Waste Disposal Program was focused on salt deposits as the geologic medium of choice, almost to the exclusion of other rock types. These efforts are illustrated by the Project Salt Vault experiment in a salt mine at Lyons, Kansas, in 1965-1967 followed by attempts to locate a repository site in central Kansas. Preliminary evaluation of other geologic media led, in 1978, to the GAIN (Geotechnical Assessment and Instrumentation Needs for Nuclear Waste Isolation in Crystalline and Argillaceous Rocks) Symposium held at the University of California (Berkeley), for the purpose of preparing a state-of-the-art document together with research needs for some of the other possible rock types. Because possible sites had not been selected, nor would they be for some time, the primary emphasis was for research and development focused on generic rocks and generic sites. A basic ground rule at that time was that the host rock formation should provide the primary containment for the waste. Also, the U.S. Nuclear Regulatory Commission (NRC) was just drafting the proposed rules regarding site suitability so that this input was not available. The collection of baseline data, conduction of some critical experiments both in the laboratory and field, and the performance of scoping studies were deemed needed. Such work was indeed undertaken; and to date, a great deal of information has been compiled and much has been learned regarding the characteristics of rock masses, rock behavior

Jan 1, 1984

By G. B. Clark

Dynamic rock mechanic as it pertains to blasting has involved several areas of active research effort. Among the important problems which have been the subject of research are wave mechanics in rocks, mechanisms of rock breakage, cratering, applications of similitude, energy partitioning of explosives, coupling, and other related factors. In some of these areas many problems have received fairly complete answers, while in others, investigations have raised new questions while attempting to answer existing ones. The slabbing mechanism explains many of the phenomena observed in blasting, but is hot the complete answer to observed breakage and fragmentation phenomena. There is currently a gap between coupling experimental results and theory. Applications of similitude to open pit blasting have been made unnecessarily complicated. Basic scaling laws for large true and apparent craters have not been derived for either chemical or nuclear explosives. There are few useful data and little developed theory on the partitioning of energy of explosives in all types of blasting. No suitable mathematical model has been developed which will describe the stress waves in rock which are responsible for rock breakage: Significant progress has been and is being made in these areas of research, however. ELASTIC AND NONELASTIC WAVES Complete solutions for spherical wave equations in viscoelastic media are not available in the literature. Equations for certain viscoelastic models do show limited promise, however, of being applicable to rock masses, particularly for pulse type phenomena. Seismic investigations, blasting operations, the design of protective underground structures, and the evaluation of other explosive effects in solids would be greatly bene-

Jan 1, 1967

By John A. Oberteuffer, Ionel Wechsler

High gradient magnetic separation, first introduced in 1968 as a means for the removal of very fine magnetic contaminants from clay, is no longer a new technology. Applications to a number of solid-solid and solid-fluid separation problems are now being exploited. Recent pilot tests and full-scale industrial installations of high gradient magnetic separators and filters have established their commercial viability and have demonstrated their superiority both in efficiency and cost effectiveness to conventional prior-art methods for water treatment and mineral processing. In high gradient magnetic separators, the magnetic trapping force for fine, even weakly magnetic particles is greatly increased over those available in previous magnetic separators. These very strong trapping forces are created on the edges of fine filamentary ferro- magnetic materials in the presence of a strong background magnetic field. In the basic cyclic high gradient magnetic separator, particles are trapped in the filamentary matrix until it is loaded, at which point the magnetic field is turned off, and the filter is back- flushed. Applications of cyclic high gradient magnetic filtration for water treatment include filtration of waste and process waters in steel mills. Treatment of hot rolling mill scale pit effluent and cold rolling mill emulsion has been successfully tested, and 2-meter diameter SALA-HGMF® magnetic filters have been installed at Japanese steel companies for the treatment of recirculating scrubber waters in a de-gas- sing system. A second major application in water treatment is for the polishing of recirculating waters in power and steam generating systems. High gradient magnetic filters can operate under conditions of

Jan 1, 1980

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbogenerator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring. Hardening in this case was obtained by cold working, such as hammering, rolling or some means for stretching the steel while at a temperature near 500" C. One means for stretching2 is to rotate the forged or rolled ring in a centrifugal machine so as to develop within it stress higher than

Jan 1, 1931

By Hewitt Wilson

IN 1903, T. M. and E. H. Alvord, of Marblemount, Wash., built a soapstone-grinding mill in the Skagit River Valley and are reported to have produced "ground talc" during 1904 and 1905, shipping to the paper mills in Wisconsin. Between 1916 and 1920, the Western Talc Co. built and operated a talc-grinding mill north of Mondovi, on the banks of the Spokane River, in eastern Washington, and sold powdered talc to the Inland Empire Paper Co. of Spokane. ? The most active develop-ment in recent years has been by two companies in the Skagit Valley-the Skagit Talc Company, Inc., which has been sawing soapstone block for the soda-recovery furnaces of the pulp and paper companies, and the Asbestos-Talc Products of Washington, Inc., at Burlington, which has been mining and dry-grinding a soft serpentine for the structural filler and insulation trade. Many prospects have been opened in the northern part of the state on both sides of the Cascade Mountains, and these activities undoubtedly are the forerunner of an industry that promises to attain considerable magnitude in the North Pacific States. At the present time, talc is imported from California for use as paper filler, and soapstone block from Virginia for use in the soda-recovery furnaces. A small market has been created locally for tailor and foundry:, pencils, stove grills, and block soapstone for art objects. The results of the present study, as yet incomplete, indicate that the use as a refractory and as a ceramic filler and flux can be expanded.

Jan 1, 1936

By R. N. Zitter

PRESENT work was done in connection with a program for obtaining a low energy gap semiconductor suitable for photodetection. The inter-metallic compound InSb, which is now being in-

Jan 1, 1959

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1'4'5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,' basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,'' modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.' These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.' All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study' of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.' While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker's work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By Stanley D. Michaelson

The selection of the proper size of grinding mill for a given installation has long been a subject of discussion by mill manufacturers, consulting engineers, and their clients. It would be presumptuous for the author to propose a simple cure-all. Instead this paper describes a method that has been used over a period of years to determine mill size with a reasonable degree of accuracy. Furthermore, this method claims no theoretical background, for ball milling, as practiced today, is still an art. The selection of the proper size and type of mill must, therefore, be made on an empirical basis. A ball mill, in order to grind, must deliver power through its grinding media to the material to be ground. Assuming that a mill is properly supplied with grinding media, ore pulp, and power, the amount of grinding done is closely proportional to the power expended. With this as a basic premise we can, for the moment, forget about type of mill (i.e., overflow, low-level mill, or other design) and base our calculation of mill size on the total power required to grind a ton of a particular ore from a given size of feed to a given size of product. When this is determined the type and size of mill, its speed, and the weight of the load of grinding media can be selected to absorb this amount of power. Development of Technique Some years ago, W. L. Maxson, F. Cadena, and F. C. Bond, working in the Minerals Research Laboratory of Allis-Chalmers Co., Milwaukee, developed and described a laboratory technique for comparing grindability (or relative ease of grinding) of various ores at different mesh sizes of grind.&apos; Additional papers2 have described the work done since that time, and the most recent paper3 summarizes results for hundreds of tests on many ores and materials. The essentials of the testing method are: a 12 by 12-in. laboratory mill operating at a constant speed of rotation, using a constant volume of ore, and a constant ball load having a relatively constant grinding surface. Tests are run at 250 per cent circulating load with the feed, circulating load and products screened on calibrated Tyler standard screens. Certain ores from operating mills, representing various mineralogical types, were selected for reference and designated "standard ores." In most cases, detailed studies of the grinding circuits were made when samples of mill feed were taken for grindability tests. Each analysis formed a basis for comparison of the grindability in the laboratory with actual power requirements for a particular grinding circuit. In addition, a critical study was made to evaluate the differences in the various grinding circuits so that two or more field installations having different layouts (single-stage grinding, two-stage grinding, or others), and using mills of various diameters operating at various speeds with differing circulating loads, etc., could be compared. Large-scale tests by mill operators complemented by laboratory investiga-

Jan 1, 1947

By Stanley D. Michaelson

The selection of the proper size of grinding mill for a given installation has long been a subject of discussion by mill manufacturers, consulting engineers, and their clients. It would be presumptuous for the author to propose a simple cure-all. Instead this paper describes a method that has been used over a period of years to determine mill size with a reasonable degree of accuracy. Furthermore, this method claims no theoretical background, for ball milling, as practiced today, is still an art. The selection of the proper size and type of mill must, therefore, be made on an empirical basis. A ball mill, in order to grind, must deliver power through its grinding media to the material to be ground. Assuming that a mill is properly supplied with grinding media, ore pulp, and power, the amount of grinding done is closely proportional to the power expended. With this as a basic premise we can, for the moment, forget about type of mill (i.e., overflow, low-level mill, or other design) and base our calculation of mill size on the total power required to grind a ton of a particular ore from a given size of feed to a given size of product. When this is determined the type and size of mill, its speed, and the weight of the load of grinding media can be selected to absorb this amount of power. Development of Technique Some years ago, W. L. Maxson, F. Cadena, and F. C. Bond, working in the Minerals Research Laboratory of Allis-Chalmers Co., Milwaukee, developed and described a laboratory technique for comparing grindability (or relative ease of grinding) of various ores at different mesh sizes of grind.&apos; Additional papers2 have described the work done since that time, and the most recent paper3 summarizes results for hundreds of tests on many ores and materials. The essentials of the testing method are: a 12 by 12-in. laboratory mill operating at a constant speed of rotation, using a constant volume of ore, and a constant ball load having a relatively constant grinding surface. Tests are run at 250 per cent circulating load with the feed, circulating load and products screened on calibrated Tyler standard screens. Certain ores from operating mills, representing various mineralogical types, were selected for reference and designated "standard ores." In most cases, detailed studies of the grinding circuits were made when samples of mill feed were taken for grindability tests. Each analysis formed a basis for comparison of the grindability in the laboratory with actual power requirements for a particular grinding circuit. In addition, a critical study was made to evaluate the differences in the various grinding circuits so that two or more field installations having different layouts (single-stage grinding, two-stage grinding, or others), and using mills of various diameters operating at various speeds with differing circulating loads, etc., could be compared. Large-scale tests by mill operators complemented by laboratory investiga-

Jan 1, 1947

By Orville R. Lyons

THE continuous vacuum filter, whether it be a vertical or horizontal disk, inside or outside drum, when properly applied is a very effective device for dewatering fine solids. Because of the number of variables that affect its performance, however, it is not possible to obtain consistently maximum moisture reduction in an operating plant. This paper presents a method for determining the average cake moisture and the variations in cake moisture to be anticipated when dewatering fine solids by continuous vacuum filters under normal operating conditions. Previous investigators1,2 have found that certain factors influence filter performance, drum or disk diameter, speed of rotation, percentage of immersion, and the percentage of solids in the feed influence capacity. Blinding of the filter cloth reduces effective vacuum, produces a wetter cake, and may decrease capacity. Reduced vacuum or improper adjustment between vacuum and blowing portions of the cycle will produce a wetter cake and also may decrease capacity. Widely fluctuating feed tonnages will adversely affect cake moisture and capacity. Flocculation, when properly applied, increases capacity and reduces cake moisture. Without flocculation, the slimes are the first particles sucked to the filter medium, which becomes partially blinded in consequence. With flocculation, the flocs act as coarse particles and the filter medium is not blinded. Overflocculated pulps, although filtering well, may yield wet cakes. Average Particle Size and Cake Moisture A method for predetermining the surface moisture content of coal filter cakes was published in 1949; but this method could not be applied to coals deficient in —200 mesh material or to fine mineral concentrates. Test data obtained for geared-weight types of vibrating screens4 and for centrifuges5 used to de-water coal provided definite correlations between the average particle size of a dewatered cake and the surface moisture content of the cake. It was thought that this same method of correlation should be applicable to filters, whether dewatering fine coal or fine mineral concentrates. To develop a correlation or correlations between average size of cake and cake moisture, the author collected data for filtration operations from as many sources as possible. In a considerable number of instances the information was provided by plant preparation engineers,"-" a few of the tests were on a laboratory scale: and the remainder of the data was obtained from published articles.10-17 Table I contains size-consist and miscellaneous data for coal filter cakes, and Table II contains the same data for mineral concentrate filter cakes. Fig. 1 shows the relationships existing between the average particle size of the cake and cake moisture (surface moisture for coal and total moisture for minerals) when dewatering fine solids by a variety of makes and types of filters. Average particle size is calculated by averaging the linear openings of the various pairs of screens used in the screening test, weighted in accordance with the percentages of material in the various fractions.

Jan 1, 1952