Search Documents

By B. G. Klugh

(New York Meeting, February, 1912). IN a paper before the Institute at Wilkes-Barre, Pa., June 1911,1 Mr. James Gayley discussed the application of this process to iron-bearing materials. The same author2 described the results of operations at the plant at Birdsboro, Pa. The purpose of the present paper is to present further discussion of some technical details involved in the operation of this plant, and of the theoretical and practical relations of this product to blast-furnace practice. Since Oct. 1, 1911, the Birdsboro plant has been in operation at the blast-furnace of the E. & G. Brooke Iron Co. The results have been highly satisfactory, although the material treated, being chiefly the flue-dust currently made by the furnace or taken from the accumulated stock-pile, was excessively high, and yet not uniform, in carbon, so that the desirable control or regularity of the amount of fuel in the mixture treated could not be maintained. Nothing could more forcibly demonstrate the flexibility of the process than the fact that, under these conditions, the sinter produced was, in all cases, of excellent quality. The Dwight & Lloyd process, as such, and its present highly-developed mechanical appliances were described by Mr. Gayley in the paper above mentioned. While the repetition of some particulars will be unavoidable in this paper, it will be confined to features bearing upon the metallurgical principles involved. According to the principle of the process, the finely-divided iron-bearing material to be sintered is intimately mixed with

May 1, 1912

By MARSHALL D. DRAPER

THERE are said to be about 150 operating companies in Kotchiu, most of these being small, corresponding in degree to lessees in western mines in the United States. Of the total number there are probably forty large companies having their own smelting plants equipped with one or two furnaces, slag crushing plant and other accessory equipment. A few plants, not more than ten, do custom smelting. There are in all about fifty smelting plants in Kotchiu. With little variation, the equipment and methods are the same. The plant usually consists of two furnaces, one being in operation while the other is being relined 01- re- paired. An adjoining house contains one or more of the large buffalo-drawn Chilean mills for crushing slag. A few houses for the working coolies, with more pretentious ones for the owners, complete the establishment, the whole being surrounded by a compound wall 8 ft. high.

Jan 1, 1931

By F. B. Plummer

PROGRESS during 1940 in oil-production technology has been confined largely to a steady advancement in practices inaugurated in previous years, rather than the introduction of any new startling process or technique. The usual changes, improvements and additions in production equipment have been introduced. An increased attention to, and interest in, research has been noteworthy, resulting in improved efficiency in operation of oil wells. control, utilization of reservoir energies and reduction of production costs.

Jan 1, 1941

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,' wire of some bcc metals,' and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4'5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division, and revised in 1939. Generally in Table 1 the unit for prescntation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each spacc in the tabulation, it is citller (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are detcrminable but not detcrminable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries arc not subject to precise determination. In such rases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1939

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division, and revised in 1939. Generally in Table 1 the unit for prescntation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each spacc in the tabulation, it is citller (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are detcrminable but not detcrminable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries arc not subject to precise determination. In such rases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1939

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

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

Jan 1, 1969

By P. G. Coombs

The kinetics of the cyclic oxidation and reduction processes for palladium powder were examined in the temperature range 848 to 923 K. The changes in oxidation behavior due to cycling are shown to result from the decrease in surface area. Sintering is found to occur only during the reduction process. Oxidation kinetics were found to follow a cubic law with time and yield a relation for the oxidation rate constant of k x = (1.05) 106 exp P74.0). 103 / RT] The kinetics of reduction are demonstrated to be first-order with the rate constant described by the expression: kr = (7.69) 1012 exp [-(208.0) 103 / RT] . In both expressions R is in J.mo1-1.K-1.

Jan 1, 1984

By Stanley J. LeFond

Brazil is one of the most outstanding examples of economic development of our time. Its amazing growth record is substantiated by a GNP which has increased at an average rate of 92% for the period 1968-1970 and estimates for 1971 range from 11.7-12.5%. Hence, this growth, coupled with a more relaxed attitude of the Brazilian government towards foreign participation in business opportunities and the remittance of profits out of the country, has caused many exploration companies to reevaluate the potential of Brazil. Despite recent press notices and publicity, Brazil is still not a mining country in the tradition of Canada or Australia. It is still basically an agriculture and manufacturing country.

Jan 11, 1973

By Kent R. Van Horn, W. P. Sykes

Since Honda and Murakamil in 1918 proposed their constitutional diagram of the carbon-free iron-tungsten system, considerable effort has been expended by several investigators in attempts to define more positively the structural features of the alloys. The existence of an intermediate phase corresponding to the formula Fe3W2 (68.7 per cent W) was proposed from evidence of a purely metallographic nature by one of the present authors2 in 1926. Since that time the identity of this phase has been confirmed by Arnfelt3 and by Takeda,4 both of whom employed X-ray methods as well as the microscope and the chemical analysis of isolated microconstituents. According to Arnfelt, Fe3W2, as crystallized from the iron-rich melts at a temperature above 1450° C., contains by analysis 68.7 per cent W. The lattice of this phase is characterized by trigonal symmetry. Arnfelt, moreover, proposed a second intermediate phase formed at some temperature between 1450" and 1000" C. by a peritectoid reaction involving Fe3W2 and the iron-rich solid solution. A melt containing 25 per cent W was cooled to 1000" C. and heated for 100 hr. The precipitated tungsten-rich constituent was separated and found by analysis to contain 62.6 per cent W. This composition agrees closely with that represented by the formula Fe2W (62.2 per cent W). Diffraction patterns from the concentrated precipitate showed a hexagonal unit cell. Takeda confirmed the data of Arnfelt regarding Fe3W2 but was unable to detect Arnfelt's second intermediate phase. While Takeda failed to describe in detail the treatments employed, he stated that in alloys containing 40 per cent W which were quenched after heating at various temperatures between 1200" and 1450" C. no evidence of the second phase (Fe2W) was observed 'either in the microstructure or in the diffraction patterns of isolated residues. He therefore considered the existence of this low-temperature hexagonal compound as disproved.

Jan 1, 1933

By F. C. Canney

Geochemical prospecting seeks hidden mineral deposits by sampling for variations in the chemical composition of naturally occurring materials. Usually the samples are of soils and other products of weathering and erosion—surface materials extremely susceptible to contamination by human activities. Except when a survey is conducted well away from populated areas, contamination is an ever-present hazard. The program's success is particularly endangered when the contaminants are the elements sought; if these occur erratically throughout an area, spurious anomalies completely unrelated to mineralized areas can be formed. Evenly distributed contamination can be dangerous too, if it raises the background to such a level that true anomalies can no longer be easily detected. Suppose, for example, that in an area where the lead background is 20 parts per million the soil over a lead vein contains 1000 ppm of lead. Here the contrast would be 50 to 1, which is very satisfactory for geochemical surveying. Now if 1000 ppm of lead from some source were added evenly to the soil in this area, the contrast would be reduced to about 2 to 1, and the anomaly would no longer be readily detectable because a threshold of significance twice the value of the background is the minimum generally used for interpreting geochemical data. Of the many possible sources of contamination, probably most important are smelter fumes, which may distribute large quantities of metal contaminants over many square miles of ground. For several reasons, the investigation reported here was begun in the Coeur d'Alene district in northern Idaho: 1) a lead smelter has been operated in this district since 1917 and an electrolytic zinc plant since 1928, and presumably the contamination patterns are strongly developed; 2) to evaluate the usefulness of certain geochemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and other veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; 3) one of the economically important parts of the district lies south of the South Fork of Coeur d'Alene River and within a radius of five miles of the reduction plants near Smelterville (Fig. 1). In this area, and in the entire district, conventional methods of prospecting are hindered by heavy vegetation and thick soil cover, and the possibility of contamination by smelter fumes has discouraged geochemical prospecting. Should data reveal that geochemical prospecting could be done successfully in such an area, a particularly useful tool would be available to mining companies and prospectors searching for concealed orebodies in this economically important part of the district. The field work on which this report is based was done from July 28 to 31, 1955. It should be emphasized that this was reconnaissance study only, and therefore far from exhaustive. Previous Investigations in U. S. : The first geochemical survey known to have been affected by contamination was conducted in 1940—a geobotan-ical reconnaissance made in the Michigan copper district by a private company. Geologists found striking variations in the copper content of oak and maple leaves, but unfortunately the high copper isograds of the study seemed to be related more to the Calumet and Hecla copper smelter fall-out than to mineralized ground.' The leaves of one oak tree near the smelter contained 0.4 pct Cu. Similar contamination was reported by Clarke (Ref. 2, p. 41), who conducted experimental geochemical soil and botanical surveys at Ray, Ariz. He found that the leaves of oak trees growing in unmineralized ground near Superior, Ariz., contained more copper than the leaves of oak trees growing on the capping of the Ray orebody and attributed this fact to contamination from the fumes of the Magma smelter at Superior. According to H. E. Hawkes,3 soils and stream sediments in the Superior area are also severely contaminated. Hawkes' work there has shown a copper content averaging 0.5 pct in the surface horizons of soils within one mile of the smelter stack. Samples taken only a few inches below the anomalous surface samples showed only background copper values. In 1950 L. C. Huff' of the USGS made a geochemical survey in an area near Jerome, Ariz., and found considerable zinc and copper in the soils over unmineralized basalt close to Clarkedale, Ariz., and over limestone close to Jerome. As the amounts were notably greater than could reasonably be expected to be derived from the underlying rocks, Huff suspected airborne contamination from the smelter at Clarkedale. Description of Area: The area sampled in detail (Fig. 1) for the study presented here is one of strong relief. The dominant watercourse is the westward-flowing South Fork of the Coeur d'Alene River. East of Kellogg the South Fork flows in a rather narrow canyon, but its valley floor widens considerably to the west where much of the flood plain is covered by an extensive veneer of mining, milling, and smelting debris. South of the South Fork and between Big Creek and Pine Creek is a mountainous area where

Jan 1, 1960

By R. W. Smith, T. J. Smolik

Recent work indicates that fluosilicate ions and or fluosilicate amine complex ions play important roles in fluoride activation of bery and feldspars in cationic flotation systems. In an attempt to further confirm conclusions reached in this earlier work, an infrared and X-ray diffraction study of the action of fluorides in cationic flotation of silicates was undertaken. It should be noted that in recent years considerable use has been made of infrared spectroscopy in studies of surface phenomena,2-4 and these studies have established the excellence of the technique. In the present study infrared spectra were obtained for various products of the reaction of HF and dode-cyclamine hydrochloride with quartz, microcline and beryl. These spectra were compared with one another and spectra of several inorganic and organic substances. In addition to infrared spectra, X-ray diffraction patterns were run on many of the reaction products obtained. A model 137 B Perkin Elmer Infracord double beam spectrophotometer containing sodium chloride optics was used to obtain the spectra. Infrared samples, except for the dodecylamine sample, were prepared by thoroughly mixing the substance to be analyzed with purified KBr in steel vessels on a Wig-L-Bug amalgamator. One-half in. pellets weighing 100 mg were than pressed under vacuum. Details concerning percentage of the substance to be analyzed in the pellets are indicated on the spectra. In all cases except for dodecylamine a KBr pellet was placed in the reference beam of the spectrophotometer to cancel bands due to possible impurities in the KBr. The dodecylamine sample on which an infrared spectrum was obtained was prepared by placing pure dodecylamine between two salt plates. X-ray diffraction patterns were obtained with a Norelco instrument, using a copper target tube, nickel filter and Geiger tube detector. The samples were ground into powders and either placed on glass slides with glue or placed into regular powder sample holders for diffraction studies. Goniometer scanning speed varied from 1°/min to 1/8°/min. EXPERIMENTAL RESULTS AND DISCUSSION Infrared spectra of microcline, beryl and quartz were obtained first and are shown in Fig. 1. These spectra agree reasonably well with previously reported spectra.5,6 The microcline (Fig. 1 a) and beryl (Fig. 1 b) were from good Black Hills crystals. The quartz (Fig. 1 c) was from a large, clear Brazilian crystal. It is not clear whether absorption bands of minerals are due to molecular vibrations, lattice vibrations or both. Fig. 2 shows infrared spectra of dodecylamine (Fig. 2 a) and dodecylamine hydrochloride (Fig. 2 b). The dodecylamine spectrum checks quite closely with that reported in Sadtler.8 Little is known of the spectra of hydrochloride salts of amines,9 and a spectrum of dodecylamine hydrochloride could not be

Jan 1, 1965

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By R. S. Shoemaker, D. L. Harris

PST investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation. The X-ray diffraction analysis of chemical compounds of crystalline form has proved of inestimable value for structure studies and rapid qualitative analytical purposes in a number of fields.' In some cases X-ray diffraction analysis has been found suitable for quantitative determinations. H. P. Klug2 found that quantitative procedures for quartz powders when mixed with calcium fluoride were reproducible within ±1.0 pct. Talvenheimo and White3 reported quantitative analyses of clay minerals to be accurate within 10 pct and also detected 1 pct of bentonite in 99 pct illite. In other investigations,'" powders of quartz and mica have been analyzed quantitatively with accuracies from 1 to 5 pct. A powder of tungsten carbide was analyzed similarly by Redmond7 and Rooksby8 reported the determination of small amounts (0.11 pct) of calcium oxide in magnesium oxide. In the most generally practiced use of X-ray diffraction, traces of the diffracted beam are recorded as lines on a film much as lines of elements are recorded on an optical spectrograph film. As with the spectrograph, the darkness of the lines denotes the amount of the constituent in the sample. If the film is replaced by a Geiger tube assembly and a graphic recorder or a scaling unit, the intensity of the diffracted beam can be registered as a peak on a chart or energy impulses per unit of time on the scaler. Several methods of quantitative measurement have been investigated and reported in literature. Klug2 used manual operation of the goniometer and a counting technique to determine the difference in counting rates at the diffracted angle and for the background. In another case3 the area under the recorded diffracted peak was the basis for the determination. In other instances the height of the recorded diffraction peak above background, measured while the goniometer was moving, has been the basis for the measurement. The sizes of particles most suitable for diffraction techniques are reported in the literature as follows: for tungsten carbide a maximum of 40 microns7 and for quartz a maximum of 5 microns.' Very fine sizes of crystals are known to cause a broadening of the diffused beams; hence some workers have set a lower limit of 0.1 micron for quantitative results. Guinier10 has indicated that broadening of the diffracted X-ray beam is not appreciable for crystallites larger than 0.02 to 0.03

Jan 1, 1956

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

Jan 1, 1880

By Samuel H. Dolbear

NOT WITHSTANDING the extremely low ebb of business activity, the nonmetallic industries have fared somewhat better than some other branches of mining. The average price level in nonmetallics, although far from satisfactory, has resisted any cataclysmic fall such as has been suffered by copper and other metals. Stocks, also, though too abundant, represent no corresponding overhang of the market, which should result, in some branches, in a more rapid recovery. Research work has continued in some industries with interesting developments.

Jan 1, 1933

By Johnson Crawford, Alan H. Hoagland

Zinc mining at Jefferson City began in 1854 with small scale production of oxidized ore from open pits. Significant production began in 1913 with the development of the Mascot Mine by the American Zinc Company. In 1965, four flotation mills were treating crude ore at the rate of about 12,000 tons per day and the Mascot-Jefferson City district currently is the largest zinc producing area in the United States. The producing mines, Mascot, Young, North Friends Station, New Market Zinc, Grasselli, Davis-Bible, Coy, and the Jefferson City, are 15 to 28 miles northeast of Knoxville in the Valley and Ridge physiographic province, an area of gentle relief lying between the more rugged Great Smoky Mountains and the Cumberland escarpment. The ore is strata bound, occurring essentially within a stratigraphic range of 200 feet in the Lower Kingsport and Upper Longview formations of Lower Ordovician age. In the lower strata of the mineralized section, the ore generally is found in coarsely crystalline elastic dolomite breccia containing silica and chert debris within a sequence of aphanitic limestones. The upper strata of the mineralized section are fine-grained primary dolomites that, in the ore zones, have been fragmented in mosaic patterns by solution collapse with the interfragmental space filled by white gangue dolomite and sphalerite. The mineralogy is unusually simple, sphalerite being the only important sulfide. Pyrite is very sparse. Dolomite gangue is abundant, silica was deposited in quite small amounts, calcite is minor, and fluorite and barite are very rare. The principal ore controlling structures are rubble breccia zones that were formed during the post-Lower Ordovician-pre-Middle Ordovician erosion interval by supergene solution as a phase of the development of a regional karst system of underground drainage that extended to' depths of at least 800 feet. The major Appalachian orogenic structures are post-ore and have been superimposed on the ore bodies. There is substantial evidence to support the current thinking of the writers that the ore deposits were formed at a depth not exc1~eding 800 feet.

Jan 1, 1968