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By T. S. Lundy, J. I. Federer

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystalline thoria.

Jan 1, 1962

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By Tracy Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical proper-ties such as color, hardness, corrosion resist-ance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,1 E. M. Wise,5 and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that meas-ured 3 by 1/4 by 3/4 in. The method of determining the melting points, color deter-minations and acid test have been discussed in previous papers by the author.2,3 It is necessary to use small test bars (Fig. r). The tensile bars were annealed at 1300°F. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point.

Jan 1, 1940

By Henry M. Howe

This paper gives the results of an investigation of the beha vior of the argentiferous cobalt-nickel arsenides of Temiskam-ing, Ontario, in roasting, made in the metallurgical laboratories of the School of Mines of Columbia University in the City of New York. The ore was kindly given by the owners of the La Rose and Trethewey properties at Cobalt, Ontario, and Mr E. J. Hall, Tutor in Assaying in Columbia University, has helped us much. I. Object of the Investigation. The object of the investigation was to learn: 1. The temperature at which the arsenic is most rapidly expelled ; 2. The thoroughness with which it is expelled by prolonged roasting at this temperature; 3. The effect of adding charcoal (a) near the end of the roast and (b) at. the beginning of the roast. II. Nature of the ORe. The important ores mined in the Temiskaming deposits are: native silver—with small amounts of dyscrasite (Ag,Sb), ar-gentite (Ag,S), pyrargyrite (Ag,SbS,)—smaltite (CoAs,), chlo-anthite (NiAs,) and niccolite (NiAs). Mispickel (FeAsS) and cobaltite (CoAsS) also occur in smaller quantities. The average composition of the ore shipped from this district for the first six months of 1905 was: silver, from 4.1 to 4.8 per cent.; cobalt, from 6.9 to 8.2 per cent.; nickel, from 3 to 4.7 per cent.; and arsenic, from 30.9 to 34.6 per cent. The ore which we treated consists chiefly of smaltite. In our 1aboratory-work

Jan 1, 1908

By Bezalel C. Haimson

Anna, Ohio, at the junction of Cincinnati, Findlay and Kankakee arches, has been the site of repeated and sometimes damaging earthquakes. As part of a seismicity investigation near-surface (0.15-1 m depth) overcoring strain measurements were conducted in four limestone and dolomite quarries surrounding Anna, the results of which suggest a complicated regional stress pattern, with changes in the maximum horizontal stress direction from N45ºE to N15ºW. Since such abrupt stress fluctuations are rather atypical in the Midwest and since the reliability of near-surface tests in defining regional stress had not been established, we decided to remeasure the stresses at the same locations but at greater depths (0-200 m) using the hydrofracturing method. Owing to the weak horizontal bedding planes of the Silurian shaly limestones and shaly dolomites and the relatively shallow depths, many of the tests yielded horizontal fractures, providing information only on the vertical principal stress (-0.029 MPa/m depth). However, sufficient tests in each of three testholes resulted in vertical hydrofractures to enable the calculation of all three principal stresses. Within 50-170 m depth the horizontal stresses in all three quarries appear to belong to a uniform regional Stress field defined by the following relations: [']Hmin = 5.1 + 0.014 D; [0] Hmax = 10.1 + 0.014 D, where D is depth in meters. The direction of [O]Hmax within 50-170 m depth is uniform at N70°E (±15º). The hydro- fracturing results obtained at Anna, Ohio are in agreement with the prevailing stress regime in the midcontinent both with respect to magnitudes and directions. The results suggest a possible thrust mechanism for a proposed NW-SE fault along which most of the earthquake epicenters have been located, and a left lateral strike-slip at greater depths. The focal mechanism solution of a recent major earthquake near Sharpsburg, Kentucky, some 200 km south of Anna, also indicates strike-

Jan 1, 1982

By B. D. Cullity, O. P. Puri

The magnetostrictia of nickel after increasing amounts of plastic elongation was measured at field strengths up to 1500 oe. In addition, the residual stress was measured by means of X-ray line shifts. The observed decrease in magnetostriction following plastic strain is shown to be associated with residual compressive stress. If a metal bar, whose longitudinal axis is taken as the x direction, is plastically elongated in the x direction and then unloaded, X-ray diffraction measurements will indicate the presence of a residual compressive macrostress 0%. However, stress measurement by means of mechanical relaxation does not reveal any macrostress. In a previous paper1 the fictitious macrostress indicated by X-rays was ascribed to a particular distribution of micro-stress, namely, one in which the bulk of the material was stressed more or less uniformly in compression and a very small portion in tension. It was shown that this distribution would account for Neurath's measurements2 of magnetic losses in silicon steel, because of the effect of residual stress on magnetostriction. The present paper is concerned directly with magnetostriction, in nickel, and with the effect on magnetostriction of the residual stress created by plastic elongation. The residual stress was determined by measurements of X-ray line shifts. MATERIAL AND METHODS Commercially pure "A" nickel was investigated. Its nominal composition, in weight percent, is 99.4 Ni + Co, 0.2 Mn, 0.15 Fe, 0.1 Cu, 0.1 C, 0.05 Si, and 0.005 S. Magnetostriction was measured by means of SR-4 electrical-resistance strain gages mounted on specimens 1/4 in. sq and 8 in. long. Magnetic fields up to about 1500 ce were provided by a multilayer, non-cooled solenoid. A considerable amount of heat was developed at the higher field strengths, and, to avoid errors due to changes in the specimen temperature, the following procedure was adopted. Each measurement of the magnetostriction X at a particular field strength H was preceded by demagnetization and an adjustment of the strain indicator to zero; the field H was then quickly switched on and the strain read immediately. Curves of ? vs H were flat for field strengths above about 750 oe for all specimens, and this constant value of X was accordingly taken as the saturation magnetostriction ?s The X-ray measurements of residual stress were made with a Norelco diffractometer on specimens cut from flat bars 1 1/4 in. wide, 1/8 in. thick, and 12 in. long. These measurements were confined to lattice planes parallel to the surface of the specimen. Two reflections were studied: the 311 CrKß line at 28 = 157 deg, and the 420 CuKal line at 28 = 155 deg. The line centers were determined by fitting a parabola to the peak of the line, as suggested by Ogilvie3 and as modified by Koistinen and Marburger.4 The CuKa doublet from the plastically elongated specimens was first resolved by the Rachinger method5. All X-ray measurements were made by counting at fixed angular positions. RESULTS The results of the magnetostriction measurements are shown in Fig. 1 and Table 1. The magnitude of

Jan 1, 1963

By J. W. Faust, H. F. John

Generalized conditions for rod or ribbon growth by the twin plane re-entrant edge mechanism are given. It was shown that this mechanism can result in growth of twinned platelets from dilute metal solutions. The platelrts 01 the fee metals are faceted by (111) planes and contain two or more twin planes. Microsegregation traces were revealed in silver grown from a thallium solution. VOGEL has already set down conditions for dendritic growth;1 however, this was the normal single-crystal dendritic growth experienced during solidification. In this work it is desired to set down the crystallographic conditions that will lead to rod or ribbon growth with smooth facets. These are as follows. a) The growth must be crystallographically limited (i.e., faceted growth). b) In order to have directed growth, some mechanism must allow easier nucleation than two-dimensional nucleation. That mechanism is afforded by the re-entrant edges at twin planes.213 Thus there must be twin planes present in the rods or ribbons. c) The growth direction must lie in the twin plane. If not, the twin plane will grow to the face or side of the ribbon and the site of easy nucleation will be lost. d) The growth direction must be parallel to at least one plane of the faceting planes, and no set of the faceting planes can be perpendicular to the growth direction. A corollary to these conditions involves the number of twin planes necessary to maintain the indestructible re-entrant edge. The number depends on the crystal structure of the material. An analysis of the data available shows that a material whose faceting planes form an open figure requires at least one twin plane while materials whose faceting planes form a closed figure require at least two twin planes in order to form the indestructible re-entrant edges for extended growth. The conditions and an assessment of the possibility of rod or ribbon growth are given in Table I for several crystal systems. As can be seen the fee, diamond and zinc blende, or-thorhombic, rhombohedral, and one form of the hexagonal lattice systems can yield this type of growth, but not the bcc metals nor the hexagonal

Jan 1, 1965

By D. E. Trout, W. R. Hibbard

Previous investigations have shown that the cold rolling textures1n2 and the drawn wire textures3 of copper change their secondary components after the addition of about 1 pct aluminum and 5 pct zinc, but do not change after the addition of as much as 30 pct nickel. However, few data are available on compression textures. Barrett4 reports from unpublished work with E. L. Layland that compression rolled copper develops a texture which is predominately (110) in the compression plane with a secondary spread to (113) and weaker spread to (100) as shown in Fig 1. However, 70-30 alpha brass similarly treated develops a texture again predominately (110) in the compression plane and with a weak secondary spread to {113} but with moderate (111) secondary intensities illustrated in Fig 2. Experimental Procedure Specimens of the compositions shown in Table 1 remaining from a previous investigation3 were annealed to a grain size of 0.090 mm average diam and machined to cylinders 0.20 in. diam and 0.20 in. high. Cylinders were compressed 90 pct reduction in height between lubricated steel blocks in a tensile machine. Glancing X ray photo-grams using copper K-alpha radiation were taken at an angle of 0 degrees to the compression surface. (111), (002) and (220) rings were analyzed to define the textures shown in Table 1. The results are in agreement with Barrett4 as to types of textures and are essentially in agreement with previous work1,2,3 as to the effects of composition. In the wire study3 it was reported that the 4.99 pct zinc alloy had a brass-type texture, while the data in Table 1 indicate a copper-type texture for compression. The wire specimen of the 4.99 pct zinc alloy was re-examined by X rays and it was established that the [loo] component still exists in the wire axis. Therefore, Table 2 of Ref. 3 is in error and should indicate a double [ill], [loo] copper-type texture for this alloy. This correction results in complete consistency with regard to compositional effects, namely that copper and its alloys containing up to approximately 1 pet aluminum, 5 pct zinc and at least 30 pct nickels develop a copper-type texture and more concentrated copper-aluminum and copper-zinc solid solution alloys will form a brass-type texture. Summary Compression textures developed in copper and its alpha solid solution alloys of aluminum, nickel and zinc are essentially the same types as those re- ported by Barrett4 with compositional effects occurring at approximately the same percent additions as previously reported for rolled sheet182 and drawn wire.3 The Scovill Manufacturing Co., Waterbury, Conn., furnished the copper and brass alloys, performed certain chemical analyses and supplied laboratory facilities where needed. References 1. Brick, Martin and Angier: Tram. A.S.M. (1943) 31, 675. 2. Dahl and Pawlek: Zlsch. Melall. (1936) 28, 266. 3. Hibbard and Yen: Trans. AIME 175, 126. Melals Tech.. Feb. 1948, TP 2334. 4. Barrett: Structure of Metals, mc- Graw-Hill (19421, 386.

Jan 1, 1950

By John Dasher, M. C. Chang

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to beneficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly -24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant.

Jan 3, 1959

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By W. L. DeMoulin

A rather detailed description of the entire plant and leaching process was given in a paper recently presented to the Institute,I so this paper will cover briefly only the crushing practice of the New Cornelia Copper Co. for the year 1918. The ore, which is mined by steam shovels and loaded in side-dump cars, passes through two crushing plants. These crushing plants were constructed to crush the ore required by a leaching plant of 5000 tons daily capacity, during a crushing period of 16 hours. The primary plant reduces to less than 3 in. (76 mm.) and the secondary plant, to 1/4 in. (6.35 mm.), which is sufficiently fine for satisfactory percolation of solution through the ore in the leaching tanks, and to give-good extraction. The ore is then conveyed to the leaching tanks by a system of 28-in. (71-cm.) belt conveyors. On the way to the leaching tanks, it passes through an automatic sampling plant, where a 1-per cent. sample is taken. From the primary crushing plant, the ore is conveyed by two 36-in. (91-cm.) belt conveyors to a 10,000-ton steel storage bin, with a reinforced-concrete flat bottom. The ore discharges from the bottom of this' bin onto four 20-in. belt conveyors, which deliver it to the four units of crushers in the secondary crushing plant. There is no storage bin between the mine and the primary crushing plant. The ore breaks very coarse, is very hard, and contains a great many boulders, some as large as 4 1/2 by 4 1/2 by 10 ft. (1.3 by 1.3 by 3 m.). Jams form in the bowl of the coarse crusher in the primary crushing plant, as a consequence, and are freed by means of an immense steel hook operated from a 40-ton electric traveling crane. Primary Crushing Plant The primary plant consists of one No. 24 Gates, style K, gyratory crusher, followed by four Gates No. 8, style K, gyratory crushers. All

Jan 1, 1920

By H. L. Talbot, R. S. Young, A. Golledge

The differentiation of oxidized forms of lead from lead sulphide in complex products by chemical analysis is of considerable importance to certain mining and metallurgical companies. A method for the separation of "oxide" lead, (non-sulphide), from sulphide lead, based on the solubility of the former and virtual insolubility of the latter in concentrated ammonium acetate solution, has been employed for many years in the industry.1,2 Unfortunately this solvent, while satisfactory for lead sulphate and carbonate, is without action on lead phosphates or vanadates, with the result that at .Rhodesia Broken Hill Development Co. where these latter minerals are present, they have counted as sulphides when using this procedure. For the control of operations in the new concentrator it became necessary to have a closer check on sulphide lead than could be obtained by the only current method of differentiating this constituent from oxidized lead. For some time this problem has engaged our attention, and after a large number of solvents had been tried, the following procedure was evolved. Like all methods depending on selective solution in a com- plex material, it will not give 100 pct separation into oxide and sulphide portions. Because of the ease of oxidation of galena this is almost an impossibility. Our procedure will, however, give a recovery of 99-100 pct of the oxidized lead, contaminated with very small quantities of lead sulphide, and a corresponding recovery of 97-98 pct of the sulphide lead. The procedure is simple and reproducible, and gives results quite .satisfactory for routine control purposes. Experimental For this work standard samples of the following pure lead minerals were obtained from Broken Hill, Northern Rhodesia. These were hand-picked specimens, and were carefully ground to —200 mesh. Since it was realized that a fair-sized sample would be necessary for this work to thoroughly test the large number of procedures we had in mind, a compromise had to be effected between a few grams of very pure minerals and a large sample of lower grade material. For this work the presence of gangue was not deleterious, so long as the oxide lead minerals did not contain lead sulphide, and vice versa. Table I shows the lead minerals used, and their total lead content, both theoretical and actual. Apart from the pyro-morphite the minerals are seen by analysis to be quite pure. Many solutions were tried in an effort to dissolve the oxidized lead minerals and

Jan 1, 1949

By J. Parker

As a practicing mining engineer, I face many rock mechanics' problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert's suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast's results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground. are often at least as large as the vertical stresses. Visual observation of the deformation of roof and pillars (including failure due to horizontal compres- sion) also demonstrates that the horizontal stresses are often most important: Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic.

Jan 1, 1967

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By Robert Schorr

A Discussion of the Paper by Robert Schorr, read at the Atlantic City meeting, February, 1904. (Washington Meeting, May, 1905.) E. T. DUMBLE, Houston, Texas (communication to the Secretary*) :-In addition to the list of publications mentioned by Mr. Schorr and those by Prof. Hofman, I call attention to the following references : Studi sulle Lignite, by Capacci. Turin (1890). (An excellent work.) Report of Brown Coal Industry in Germany. J. Cosmo Newberry. Department of Mines, Victoria (1892). Second Report of the Royal Commission. on Coal Supply. Vol. II. London (1904). Peat Fuel: Its Manufacture and Use. Report of the Bureau of Mines of Ontario, 1903. Mr. Schorr says : " Brown coal and peat are briquetted as a rule without binder," but this statement is entirely true only so far as raw peat is concerned, and it is but partly true of brown coal. With regard to raw peat, briquetting without bond is carried on successfully both in Europe and America, and the development of the industry in Canada is fully described in the Bureau of Mines report for 1903, mentioned above. While there is still room for improvement in the efficiency of some of the arrangements for drying the peat previous to briquetting, a very satisfactory fuel is made at a price which enables it to compete with coal. During the late strike in the anthracite regions of Pennsylvania, the manufacture of peat: briquettes received a considerable impetus, and possibly the attention directed to it on this account may result in a. considerable increase in the output. In Canada. the peat when it is first excavated from the ground

Mar 1, 1905

By A. G. McGregor

In the Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 1/2 in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining CO.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally 1/4in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft, from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 1/4-in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar —water, sodium silicate, and finely ground silica—was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By Thomas A. Edison

We have not yet begun. to realize the possibilities of automatic machinery, in part because we have not developed the designing brains, and in part because we have not sufficiently simplified industry to make possible the economical use of such machinery. The principle of the Jacquard loom, has scarcely been utilized except in weaving silk and in the player piano. It is the principle of bringing into action the various parts of a machine in accordance with a pattern traced on a steel card by perforations or as on the paper roll of a player piano. This principle gives us a control which can be applied to any kind of machine. It is a' great reserve principle for the future. But even now, with the machinery that we have at command, anyone can cut the number of employees in two, at the same time doubling his output, by installing semi-automatic or automatic machinery. And no one knows how far this process can go on. Cutting down the number of men is not just putting some poor fellows out of a job. It is increasing the number of good jobs by increasing the production per capita to a point where really satisfactory wages can be paid out of it, and this in turn- increases the amount of work required to be done and creates new jobs. Thus, cheapening in- creases the demand.

Jan 1, 1929