Search Documents

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By H. W. Schull

The Alligator Ridge gold deposits are located in northwest White Pine County at the southwest end of Alligator Ridge. Alligator Ridge is on the west side of Long Valley in the range of hills that separates Long and Newark valleys. The nearest population center is Ely, about 113 km (70 miles) to the southeast. Access to the Alligator Ridge gold mine from Ely is via US Highway 50 and the Long Valley Ruby Marsh Road. The latitude and longitude is approximately 39° 45' north and 116° 30' west. The Alligator Ridge gold deposits occur in the lower 61 m (200 ft) of the Mississippian-Devonian Pilot Shale formation, a laminated calcareous carbonaceous siltstone. The gold deposits contain carbonaceous, oxide, and jasperoid type gold ore. For more details on the geologic features of the deposits, see Schull, Sutherland, and Ilchik (in press). The discovery story of Alligator Ridge began in the spring of 1976 when the areas mapped as jasperoid on the 1:250,000 scale geologic map of White Pine County (Hose and Blake, 1976) were examined and sampled. Seventeen samples, about 23 kg (50 lb), were collected from an area about 0.65 km2 (0.25 sq mile). Of these 17 samples 10 reported atomic absorption values of less than 0. 1 ppm Au and 7 reported values in the 0.1 to 1.0 ppm Au range. In June of 1976 20 lode claims were staked to claim the area of the rock chip sampling. The claims' end and side center lines were used as a grid for soil sampling. Sample stations were 91 m (300 ft) apart and sample lines were 229 m (750 ft) apart. The samples were sieved to - 180 µm (- 80 mesh). Out of 99 soil samples, seven samples reported Au values in the 0.1 to 1.0 ppm range. Of the seven auriferous samples, five were located over the jasperoid outcrops previously sampled; one over unmineralized Pilot Shale a few hundred m (ft) downslope from some Au-bearing jasperoid; and one from a 15 x 15 m (50 x 50 ft) talus outcrop area of hitherto unnoticed mineralized Pilot Shale. Subsequent sampling, mapping and drilling would show that this 15 X 15 m (50 x 50 ft) outcrop area was the top of the Vantage 1 ore body, about 1.27 Mt (1,400,000 st) of over 3 g/0.9 t (0.11 oz/st) Au. Late in the summer of 1976 about 30 more 1.4 to 2.2 kg (3 to 5 lb) rock chip samples were collected in the course of preliminary geologic mapping. This mapping and sampling showed that the gold-bearing jasperoids occurred at the contact between the Pilot Shale and the underlying Devils Gate Limestone. Rock chip samples of 0.1 ppm Au or greater were restricted to the jasperoids and the mineralized outcrop area of Pilot Shale located by the soil sample survey. Rock chip samples from the area of mineralized Pilot Shale were in the 3 to 5 ppm Au range. Activity resumed in the summer of 1977 with a more detailed soil geochemical survey. The jasperoid areas were defined as large geochemical gold anomalies of values greater than 0.1 ppm and locally greater than 0.2 ppm Au. Soil samples from the area of mineralized Pilot Shale outlined a greater than 0.1 ppm gold anomaly 61 x 152 m (200 x 500 ft) in size. Further geologic mapping showed that elsewhere, even where bleached and silicified, the Pilot Shale areas were geochemically very low in gold (less than 0.1 ppm Au). In November, 1977 twelve rotary percussion drill holes were drilled to test the gold-bearing jasperoid areas and the mineralized Pilot Shale area. Drilling of the jasperoid areas showed that the jasperoids gave way at shallow depths [less than 24 m (80 ft)] to unmineralized unaltered Devils Gate Limestone. A five hole cross pattern was drilled to test the area of mineralized Pilot Shale. Four of the five holes re-

Jan 1, 1985

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By J. P. Hammond, C. J. McHargue, S. E. Adair

Cold-rolled sheet textures have been determined for binary solid solutions of aluminum, columbium, tantalum, and zirconium in titanium. An alloy containing 3.8 pct Al had a (0002) [10101 texture, whereas alloys with the other elements had rotated (0002) [10101 textures similar to that of iodide titanium. THERE have been relatively few studies of the effect of alloying on deformation textures. A second element may be present in the base metal in solid solution and/or as a second phase. The literature offers no satisfactory explanation for the effects of solid solution alloying on textures noted thus far. For example, there is no satisfactory explanation of the difference in the textures of copper and a brass. The most complete study of the effects of solid solution alloying on deformation textures has been that of Brick, Martin, and Angier.¹ These investigators reported that the copper texture was retained by alloys of copper with up to 30 pct Ni, less than 5 pct Zn, less than 2 pct A1 or Co up to the limit of solubility. Copper containing more than 5 pct Zn, more than 2 pct Al, or the maximum soluble concentration of tin, silicon, or manganese showed the deformation texture of a brass. Bakarian² reported that additions of 0.20 pct Ca to 99.98 pct Mg or 2.0 pct Mn plus 0.15 pct Ca to magnesium resulted in entirely different textures than for the pure magnesium. The texture obtained for high-purity magnesium sheet showed the basal plane to be concentrated parallel to the rolling plane. The texture obtained for the alloy containing 0.20 pct Ca had the basal planes concentrated in elliptical areas whose centers were tilted 15" from the center of the pole figure toward the rolling direction. This split basal orientation was even more pronounced in the alloy containing 2.0 pct Mn and 0.15 pct Ca. Fuller and Edmunds" studied the rolled sheet textures in a zinc alloy containing 1 pct Cu and 0.01 pct Mn. The basal pole figure of this alloy contained a region of strong concentration not found in the pole figure for pure zinc.&apos; In the above cases, results were discussed in terms of possible changes in slip and/or twinning systems and critical shear stresses. However, there were no experimental data to relate these speculations with the observed textures. It has been suggested that the deformation textures of titanium, zirconium, and beryllium could be directly ascribed to their low c/a ratios. The complex deformation mechanisms of titanium" also have been suggested to be characteristic of hexagonal close-packed metals with low c/a ratios. The purpose of this investigation was to study the cold-rolled sheet textures in binary titanium-base a alloys in which the c/a ratios were greater than, less than, and about the same as the c/a for iodide titanium. The annealed textures of these alloys will be reported in a subsequent article. Materials and Methods The chemical analyses of the metals used in this investigation are given in Table I. The alloys were prepared as 15 g buttons on a water-cooled copper block in a vacuum arc-furnace. The furnace was evacuated to pressures of the order of 10.&apos; mm Hg, flushed with 99.98 pct pure argon, and melting was carried out in 0.2 atm pressure argon. Each button was remelted until radiographs and chemical analyses indicated complete solution of the solute elements. All buttons were forged and homogenized 72 hr at 500°C. The buttons to be rolled were ground and etched to sizes and shapes suitable for the rolling

Jan 1, 1954

By M. B. Willey

The Louisiana Continental Shelf is a submarine area extending offshore as much as one hundred miles. The Gulf bottom in this region varies considerably in extent, profile and composition and consists largely of sedimentary deposits, predominantly those of the Mississippi River. It is very young in a geological sense. Up to the present time few major structures have been erected offshore in the Gulf and no comprehensive preliminary tests have been carried out. Results of pile driving tests are of little value as actual bearing capacities far exceed the dynamic resistance to driving as measured by conventional formulas. Soils encountered are, with few exceptions, cohesive and piling consequently develop their supporting power through surface friction. Because of the time required and relatively high costs, no complete load tests have been made. The results of those tests which have been made, and information obtained from pulling piling in one structure, indicate that design loadings could be considerably increased, and it is contended that comprehensive preliminary investigations including an actual load test, combined with borings and examination of materials encountered by competent soil experts, would effect economies in design far in excess of their cost. The Louisiana Continental Shelf—General The Louisiana . . . continental shelf is a submarine area which extends seaward for as great a distance as one hundred miles off the present shoreline. The Gulf bottom in this region is characterized by low slopes and its outer margin is outlined by the fifty fathom (300 ft.) contour. South of the margin of the shelf the slopes steepen abruptly in the continental slope zone and plunge into the deeps of the Gulf of Mexico.l The engineer who is called upon to design a structure on this shelf is concerned only with the uppermost portion to a depth generally not to exceed Ioo to 150 ft. This layer is very young in a geological sense, and it has the characteristics usually associated with infancy. A few of these are lack of strength, lack of uniformity, and high water content. It consists of the sedimentary deposits of the various rivers and streams entering the Gulf. These streams are all heavily burdened in quantities sufficient to fill the areas at their mouths, were it not for the fact that continual subsidence, equal or greater in amount and acting directly opposite, prevail over the sedimentary workings of the streams. This subsidence has been estimated by geologists to be at the rate of at least one foot per century. Influence of Mississippi River The Mississippi River, which has been the predominant factor in the formation of practically all the Louisiana continental shelf, is one of two rivers flowing into the Gulf that have been able to build protruding deltas. The Mississippi has done so because of its enormous size and load. It deposits sediments in amounts sufficient to replace and actually gain on the amount of subsidence.

Jan 1, 1949

E. T. Dumble, Houston, Texas (communication to the Secretary) : During the field-season of 1890 I had occasion to examine some of the salines of eastern Texas. As the result of my stridy of them I came to the conclusion that, together with the oil of Hardin county (since extended to Beaumont by the work of Capt. Lucas) and the rock-salt and gypsum-deposits of the coast country, extending southward to the Rio Grande, these were simply a continuation of similar deposits in Louisiana described by Hilgard, Hopkins, and others; and I recommended the sinking of wells wberever they were found.

Jan 1, 1902

By Charles A. Stetefeldt

This treatise is the sequel of a paper on "Russell&apos;s Improved Process for the Lixiviation of Silver-ores," etc., read at the Chicago meeting, in May, 1884, and published in the Transactions, vol. xiii., page 47. The facts it presents are principally compiled from Mr. Russell&apos;s notes on his practical experience gained in various places where the Russell process has been introduced. For a complete understanding of this paper a perusal of my former one is desirable, as can be seen from the frequent references here made to it. All silver-ores that do not carry a large percentage of lead or copper can be treated by Russell&apos;s process with success and economy. I do not mean to create the impression that from ores containing considerable quantities of lead and copper a high percentage of the silver cannot be extracted by this process. Such ores, however, will, in many localities, be reduced to better advantage by smelting. In case lead-bearing silver-ores are suitable for concentration, it may be profitable to concentrate the ore by Krom&apos;s dry system, obtaining a smelting-product high in lead, and to lixiviate the tailings and the dust. This plan has been adopted in a mill recently erected in Cortez District, Nevada. The dry system of concentration deserves the preference because it delivers the tailings and the dust in a condition ready for chloridizing-roasting. In wet concentration the drying of the tail ings would be expensive, and there would be a considerable loss of silver in slimes. Oxidized ores, containing silver chloride and lead minerals, may be lixiviated after crushing, and the tailings may be concentrated for lead. In this case wet concentration would be most suitable. This has been done at the Old Telegraph Mine, Utah. I would give, however, the preference to dry concentration in all cases which, of course, requires that concentration should precede lixiviation. The Russell process is also adapted to the treatment of tailings resulting from ores which have been worked either by the old

Jan 1, 1887

By M. Yoshinuga, S. Watanabe

Some iron ores, sinters and pellets occasionally show abnormal behavior during reduction which makes them undesirable as blast furnace burden. These may be divided into the following three types: (1) decrepitation of iron ore, (2) swelling of iron ore and pellet, (3) size degradation of sinter. In this paper reduction experiments and microscopic examinations were made to clarify the mechanisms and causes of these abnormal phenomena. Decrepitation occurs mainly when compact hematite ores containing small amounts of limonite are heated to about 500°C. Abnormal swelling of ores and pellets is caused by the rapid growth of fibrous metallic iron from the surface of wustite grains during rapid reduction and is fundamentally related to their original microstructure. Size degradation of sinter occurs through the development of cracks in the reduction stage from hematite to magnetite. About 80% of the iron ore used in Japan&apos;s blast furnaces comes from abroad, and the iron and steel industry must import this raw material from distant overseas places at high freight rates. The blast furnace operators, therefore, have made strong efforts to cut costs under these restrictive raw materials conditions by increasing productivity and simultaneously decreasing coke consumption. If, however, a high proportion of the ore burden consists of unsuitable materials furnace irregularities often result, establishing the need for detailed investigations of the basic natures of the ore constituents and their reactions during the reduction process. Recent investigations &apos;-&apos; of various ore burdens suggest that some iron ores, sinters and pellets are occasionally abnormal in appearance and behavior during reduction studies and may prove to be undesirable for use in the blast furnace. In the present study reduction experiments and microscopic observations were made to clarify the causes and the mechanisms of the abnormal behavior observed in some constituents of the burden and their effect on blast furnace performance. REDUCING APPARATUS The four kinds of reducing apparatus used in this investigation were the following: 1. The JIS* (Modified Gakushin&apos;) apparatus shown in Fig. la is most commonly used in Japan to evaluate the reducibility of ores under static conditions. It consists of a stainless steel tube of 60 mm inside diam suspended from a balance. 2. Linder&apos;s Reduction Test apparatus (Fig. lc) has a reducing barrel 130 mm diam and 200 mm long which rotates at 30 rpm. Some modifications were made in test procedures. 3. Gakushin Standard Test apparatus for determining the reducibility of granular ores (Fig. Id) consists of a horizontal silica tube 32 mm diam, 370 mm long and a movable electric furnace which enables rapid heating and cooling of the specimens. 4. The test apparatus for reduction under load (Fig. lb) gives a comprehensive evaluation of the behavior of ores under conditions simulating the static loading and the chemical reduction conditions encountered in. a blast furnace stack. A stainless steel tube of 50 mm diam and a carbon rod of 35 mm diam were used as the sample container and the support for the weight, respectively. In each investigation care was taken to select the most suitable method and apparatus to distinguish the abnormal nature of the ore in question. SIZE DEGRADATION OF SINTER DURING REDUCTION Sinter makes up the major portion of the blast furnace burden and its behavior during reduction should bear a close relationship to the iron productivity. Recently, some of the sinter was found to show serious size degradation during reduction at a relatively low temperature range. Because this phenomenon was thought to be a possible source of furnace irregularities, tests were made to clarify the phenom-

Jan 1, 1969

By B. M. Larsen

A discussion based on three commercial furnace tests and electrical analogue calculations is presented. It shows that while regenerator efficiency is mainly dependent on loading or relative amount of heat exchange surface plus the heat transfer coefficients as effected by flow velocity, the actual air preheat temperature can be high or low, largely independent of regenerator efficiency, mainly due to the diluting or unbalancing effects of cold air leakage into various parts of the furnace system. THERE are many signs of a renewal of interest in the heat regeneration aspect of the open hearth process, among them being the recent paper by Marsh,&apos; the introduction of auxiliary checkers in the stacks of the Isley furnace design, and a number of recent installations of two-pass checkers in new and old furnaces. However, there are also signs of yielding to the usual temptation of oversimplifying a problem. Faced with the job of obtaining better draft on a furnace, for example, a good designer always recognizes that focusing attention on some one factor, such as height of the stack or capacity of the exhaust fan, does not make his problem any easier; rather he must look at the whole system, including such items as valve resistances, bends in the flues, and flow resistance in the waste heat boiler; then he must make his design in relation to the available draft so as to avoid any serious bottleneck in the system. Yet this example is really much simpler than the problem of air preheating, and again, the latter problem is not really made easier by concentrating on air temperature in uptakes and on the more obvious methods for making this air as hot as possible. Also to be considered are such things as the total amount of air needed theoretically for complete combustion at any selected fuel rate, together with that needed for oxygen absorbed into the bath and for burning the combustible gases given out from the bath, plus some excess air. Furthermore, how does this total air requirement relate to the regenerator efficiency at various loadings? How much of the total air equivalent in stack gases will come from preheated air passed through the whole length of the incoming regenerator and how much from air leakage into various zones of the whole furnace system? Does the effect of leakage air differ depending on whether it leaks into the ingoing regenerator, the furnace above floor level, the outgoing regenerator, or the stack zone? Over a number of years we have in this Laboratory experimented with methods for measuring hot gas temperatures; we have measured, approximately, the efficiency of a few regenerators on commercial furnaces and we have developed an electrical analogue&apos; for calculations of regenerator efficiency. The whole problem is too complex to cover in one paper even with a more complete background of data than we possess, but we can attempt here to clarify certain aspects in a general way, hoping to assist specific plant studies on individual furnaces. Some of our earlier experience has been incorporated into chaps. 4, 19, 20, and 21 in the book "Basic Open Hearth Steelmaking,"" and on the assumption that this text is available to most readers, this discussion has been shortened by references to that book. The most recent design of a flowing-gas thermocouple which we are now using for measurement

Jan 1, 1955

By Dunbar D. Scott

The development in the perfection of mine-surveying instruments has been by no means rapid, as it has depended somewhat on the details of construction borrowed from astronomical and geodetic theodolites, largely on the restrictions laid down by mining companies and the prejudices of mine managers themselves, but more than all on the methods used in conducting surveys and the importance attached thereto. Mine-surveying, in some form or other, has been practiced from the very earliest times; but it has never kept pace with the other branches of surveying, or even with the art of mining itself, and cannot be recognized as an exact science until shortly before the beginning of this century. The works of Hero of Alexandria, who lived in the second century B.C., are still extant, and contain descriptions of a rectangular sighting-instrument, which he invented and called a diopter. His improvement upon this simple construction, which possibly he devised for use in the Greek mines for rough leveling-purposes and for laying out any angle, must be considered, says Hübner," as the origin of the highly perfected theodolite of to-day. Whether this instrument came into general use during the first centuries of the Christian era, is not recorded; in fact, no writer undertakes to tell how mine-surveying was conducted until 1556, in which year Agricola expounds the principles of mining and metallurgy in his De Re Metallica, devoting the entire fifth chapter to the practice of mine-surveying (see Fig. 1). In mediæval times those who possessed any knowledge of engineering skill made strenuous effort to keep their art a secret, partly on account of the miners&apos; proverbial conservatism and partly for their own personal aggrandizement, and were, in

Jan 1, 1899

C. Edward Stafford, Chester, Pa.:—Doring all my business life, I have been engaged in the manufacture of Bessemer and open-hearth steels, but, during my long connection with the Shoenberger Steel Co. of Pittsburg, I had some experience in the manufacture of high-grade puddled iron for horseshoes, and in making, by Dr. Otto Wuth&apos;s process, extremely pure, low-phosphorus puddled blooms (analyzing from 0.005 to 0.01 per cent. of phosphorus and sulphur), which were melted with low-phosphorus pig-iron in acid open-hearth furnaces, to make extra locomotive fire-box steel. I have also seen the Danks puddlers in operation at different times and places, notably where they were most successful, at the Otis Steel Works, Cleveland, Ohio; then under the management of our friend, Mr. S. T. Wellman. These Danks blooms were made solely for open-hearth melting-stock, to which they were well adapted. (The unavoidable presence of bits of ore-fix imbedded in the mass of the metal always prevents the profitable manufacture of merchant iron from Danks&apos; blooms.) With the experience just described, I was to some degree in position to value fairly the means, methods and results of Mr. Roe&apos;s mechanical puddling from the metallurgical or technical and economic points of view, when given an opportunity by Mr. Roe to see his puddling-furnace or machine in operation in Pottstown, Pa. Briefly, the furnace, with water-cooled bottom, is rectangular in plan, about 20 by 8 ft. in the clear, suspended by trunnions at the middle of the long sides, at a height of 17 or 18 ft. above the general level. The oscillation (65" each way from the vertical) is accomplished by geared segments (attached to the downward-projecting side or trunnion-plates) with which engage pinions driven by a reversing engine. The whole section

Jan 1, 1906

By C. M. Schwartz, J. R. Bridge, D. A. Vaughan

THERMAL expansion coefficients of a uranium were originally reported&apos; on the basis of X-ray diffraction measurement of lattice constants at 25°, 300°, and 650°C. These data have been reproduced by Katz and Rabinowitch.&apos; CuK radiation had been used in this work, with consequent crowding of the patterns. Considerable overlap of the back-reflection lines was observed as the temperature was raised. Subsequent reexamination of the data led to the conclusion that errors had resulted from failure to obtain unequivocal indexing of the high angle reflections at elevated temperatures. The measurements have been repeated, using FeK radiation, which provided sufficient dispersion to assure proper indexing of the reflections, at each temperature level. The unit cell dimensions were re-determined at ten temperatures, from 25" to 650°C. Schuch and Laquer easured the macroscopic contraction from room temperature down to —253°C, and reported a negative value from —210" to —253°C; they suggested the possibility of the occurrence of a phase change. In the present work, the lattice constants of uranium have been measured down to —253°C, to test this hypothesis. Filings were prepared from a single piece of pure uranium bar stock. They were carefully cleaned with a magnet and pickled in nitric acid to remove traces of iron from the file. They were then annealed at 600°C in a sealed evacuated silica tube. The annealed filings were pickled in strong nitric acid to remove any oxide layer, washed in water and alcohol, quickly dried, and sealed in evacuated thin-walled silica capillary tubes. If properly sealed, the sample could be heated to the a-ß transforination temperature without significant buildup of the diffraction pattern of oxide. The high temperature X-ray diffraction camera was modified from the design of Hume-Rothery and Reynolds.&apos; The thermocouple used to record the specimen temperature was calibrated from lattice-constant measurements of a standard silver specimen, using the Hume-Rothery and Reynolds values for silver over the temperature range from 25" to 700°C. Temperatures were reproducible to 210°C. Temperatures to —210°C were attained by passing precooled gas over the sample. The gas from the cooling train was directed over the sample capillary tube and thermocouple by means of a chimney of 1-mil polystyrene. The 36-gage Cu-constantan thermocouple had been calibrated by

Jan 1, 1957

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of&apos; the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak&apos;s theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days &apos;steel&apos; was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Norman D. Fitzgerald

The growth of domestic requirements for motor fuel has been phenomenal, rising year after year in a fashion almost unique among commodities, resisting depressions and forging rapidly ahead in times of prosperity. Consumption advanced from 226 millions of barrels in 1925 to 522 millions of barrels in 1938; or 130 per cent. The economic influences generating and sustaining this demand are of vital concern to the petroleum industry. The general factors affecting utilization of motor fuel are well known but it is the purpose of this paper to employ the recently developed technique of economic dynamics to describe them mathematically. Such problems in economic analysis are complicated by the freedom of all the variables to fluctuate, their mutual interdependence, changing incidence upon one another, and the nonquantitative character of some of them. Economic quantities and relationships, unlike those of the physical world, are continuously changing and this dynamic characteristic is both a distinguishing and confusing feature in economic research. The complexities of the problems require application of the analytical devices of mathematical statistics to uncover the probable relationships between factors. The procedure employed is to formulate a logical relationship linking the dependent to the independent variables, and then simultaneously, rather than sequentially, determine their separate effects by multiple correlation. This transformation of common knowledge to quantitative terms makes it possible to measure the probable effects of changing conditions upon requirements, assisting in the sound interpretation of economic policies. The utility of the results of such dynamic analysis is in sharp contrast to the sterility of the trends and other simple empiricisms of descriptive statistics. It is not intended in this study to throw light on the reasons why any motor fuel at all is consumed; but to discover relationships explaining why more was consumed at one time than at another. Specifically the problem is confined to the measurement of the influences of statistically

Jan 1, 1940

By G. St. J. Perrott

One of the important hazards in coal mining is the danger of ignition of explosive mixtures of methane and air or coal dust and air, or both, by the explosives used in blasting the coal. It has long been recognized that certain explosives are more dangerous than others in this respect. &apos; In America and abroad, government testing stations have been established for officially passing on the suitability of explosives for use in coal mines. In this country the Federal government is given no power to enforce the use of the approved explosives but merely publishes from time to time, through the Bureau of Mines, those explosives which have passed the tests necessary to place them on the list for use in coal mines. In spite of this lack of police power, the increase in the use of permissible .explosives since the promulgation of the fist list in 1909 has been rapid. In 1912, only 8 per cent. of the explosives used in coal mines were permissible; in 1925, this figure had increased to 25 per cent. While the past record of permissible explosives has been most gratifying, it is very desirable that we pave the way for further improvement in explosives and blasting methods by learning more about the mechanism of ignition of gas and coal dust by explosives. To this end a considerable amount of investigative work already has been carried out and a large amount yet remains to be done. It is the purpose of this paper to discuss briefly the effect of the characteristics of explosives and method of loading in the borehole on the liability of a blown-out shot to ignite explosive mixtures of gas or dust. For an account of the methods by which an explosive is tested for permissibility for use in coal mines, the reader is referred to Schedule 17-A of the U. S. Bureau of Mines. Safety Factor in Using Explosives The factors that affect the liability of an explosive to ignite gas or dust are already known in a qualitative way but quantitative data are

Jan 1, 1927

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938