Search Documents

J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919

By E. L. Bruce

THE district of. Patricia, in the province of Ontario, lies northwest of the Albany River and extends northward to Hudson's Bay. Formerly this was the unorganized district of Keewatin, the southern part of which was divided in 1912 between the provinces of Manitoba and Ontario. The interprovincial boundary now runs north from Lake of the Woods for 275 mi. and thence northeast 375 mi. to Hudson's Bay. This district is comparable in size to all the older part of Ontario south of the Canadian Pacific Railway east of Lake Huron-thus it is roughly one-third of the whole of the present provincial area. The central part of this great triangle is one of the least accessible parts of Canada. From it streams flow southward to the English River, southeastward to the Albany, northward to Hudson's Bay and the Hayes River, and westward to Lake Winnipeg. None of the streams is large and canoe travel is not easy. The only industry it has ever had is the trade in furs. Until the development of the airplane on a commercial basis, the only means of travel was by canoe or dog-train. There is not a mile of railway in the whole district. The two areas to be dealt with lie in the southwestern part of Patricia. Red Lake is 50 mi. east of the Manitoba boundary and 75 mi. north of the transcontinental railway from Cochrane to Winnipeg. Woman Lake is 50 mi. farther east and slightly farther north. The late Dr. D. B. Dowling, of the Geological Survey of Canada, visited Red Lake and spent some time there during his exploration survey from Lac Seul to Berens River in 1893. He also visited the Woman Lake basin during the same journey, but his examination of it was much less detailed, the great area covered by him during the one field season making it impossible to make more than a hurried reconnaissance. Some prospecting in the Red Lake district followed Dowling's exploration, but the distance from railway was too great for any systematic work to be done.

Jan 1, 1928

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer's method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By Richard L. Ash

7.3-1. Introduction. All phases of mining competent materials are affected directly by the results achieved from primary blasts. It is imperative that their design suit each particular set of mining conditions. In general, the round design must provide an adequate tonnage of material, properly placed with suitable fragmentation, to ensure that loading, haulage, and subsequent disposal or processing are accomplished at the lowest possible cost. Blasting rounds are designed by the proper application of cratering relationships developed for the single, concentric, confined explosive charge. Blasting for surface mining and most open-cut heavy construction, however, is characterized by the use of rounds, composed of a number of explosive charges with relatively long lengths, which are placed in benches with specific finite dimensions. Therefore, modifications must be made to the classical, single point-charge cratering concepts. It is the purpose of this discussion to outline the basic principles, significant variables, and procedures for their integration in the design of rounds that are applicable to conditions characteristic of surface mining. Because relatively insensitive blasting agents will be used in most instances, particular attention must be given to priming, control of confinement, and selection of charge diameters that ensure complete explosive-reaction execution. 7.3-2. General Considerations. The primary requisites for any blasting round are that it ensure optimum results for existing operating conditions, possess adequate flexibility, and be relatively simple to employ. It is important that the relative arrangement of blastholes within a round be properly balanced to take advantage of the energy released by the explosives and the specific properties of the materials being blasted. There are also environ- mental and operational factors peculiar to each mine that will limit the choice of blasting patterns.

Jan 1, 1968

J. L. CHRISTIE, Chairman T. S. FULLER, Past-chairman W. M. PEIRCE, Vice-chairman W. A. SCHEUCH, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer Executive Committee H. A. BEDWORTH G. O. HIERS D. K. CRAMPTON R. H. LEACH E. H. DIX, JR. R. F. MEHL J. A. GANN J. WALTER SCOTT' JEROME STRAUSS Finance Committee T. S. FULLER, Chairman W. M. CORSE H. S. RAWDON C. H. MATHEWSON SAM TOUR

Jan 1, 1934

By Frank F. Poland

TEE purpose of this paper-is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possible the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. PURPOSE OF DEVELOPMENT It was recognized early in the war effort that nickel would become a critical metal, therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elements (maximum), 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the con- version was successfully made.

Jan 1, 1946

By R. H. Pemberton

The principle of airborne electromagnetic prospecting is well-known. The basic geophysical texts in most cases discuss the main elements involved in electromagnetic prospecting. However, there is certainly little information available to the public concerning the present types of airborne electromagnetic systems being flown today by both contracting companies and some of the mining companies which have their own instruments. This is unfortunate since it is difficult for those people not conducting such operations to understand thoroughly the large variation in the electromagnetic instruments available.

Jan 1, 1961

By A. C. Fieldner

THE older coal chemist had a much simpler conception of coal than we have today. To him coal was a mineral composed essentially of carbon, hydrogen, oxygen, nitrogen, sulfur, ash, and water, in various proportions. His studies on the constitution of coal were directed along the conventional lines of proximate and ultimate chemical analyses and making deductions from these data without any real appreciation of the fact that coal is a conglomerate of various chemical compounds, including many of the most complex structures known to organic chemistry. The view of the modern coal chemist is well expressed by Franz Fischer, I who says that while proximate and ultimate analyses are important both from the scientific and technical point of view, they tell the chemist no more concerning the number and kinds of chemical compounds that constitute coal than the reader would learn of the contents of a book if told that the printed contents consisted of 15 per cent. of the letter "e," 5 per cent. of the letter "n," 1 per cent. of the letter "g," 4 per cent. of the letter "b," etc. As the reader must have the grouping of letters into words and words into sentences, so the chemist must have the grouping of atoms into molecules and the proportion of each molecular compound in the coal aggregate before he acquires an adequate knowledge of the constitution of coal. Modern investigators2 are laying the foundation of a new chemistry of coal based on the biochemistry of plants and the chemical changes involved in processes of fermentation and decay. As

Jan 5, 1925

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By V. J. Decarlo, J. J. Gilman

POLISHING pure zinc differs somewhat from polishing less reactive metals. The problem is not that of finding a suitable reagent, but rather of producing the polish in such a way that the surface remains polished after it is removed from the polishing bath. In other words., the anodic film that is vital to the polishing mechanism' must be tightly adherent and nonporous. It is usually desirable that it be thin. Polishing solutions consist of proper proportions of an acid and a strong oxidizing agent. In electro-polishing, the external circuit acts as the oxidizing agent. The proportions are critical because the essential surface film must be maintained at approximately constant thickness during the polishing process. In the case of zinc, chiefly two oxidizing agents, chromic and nitric acids, have been used. The simplest polishing reagent is concentrated nitric acid. However, it has certain disadvantages. It tends to pit: an excessive amount of heat is evolved during polishing; and the oxide film that it produces is not very stable, so that the polished sur-

Jan 1, 1957

By R. P. Rothwell

About thirty miles north of the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario, there is found a belt of gold-bearing quartz veins, which present geological mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded hills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaceous or talcoid slates forming the walfs of and horses in the veins. This

Jan 1, 1881

By K. J. McGrew, J. W. Murphy

Introduction Maximization of profit consistent with environmental protection is the principal goal of new applications development for any conventional or in situ mining technique. Efficient evaluation of all the parameters that contribute to mining costs and production hinges on proper design and evaluation of testing programs and data. The program discussed uses several field and laboratory procedures to estimate ore deposit characteristics and optimize lixiviant compositions. Ore characteristics and lixiviant compositions are then used in a long path leaching test (stream tube test). Stream tube test data are analyzed by mathematical models with computer assistance to predict such wellfield rate parameters as target metal production, lixiviant consumption, and restoration. When these predicted rates are combined with market values for target metals, capital expenditures, prices of lixiviant chemicals, and other economic variables (labor costs, power rates, and licensing fees), an assessment of the relative feasibility of various proposed mining plans is possible. The flowsheet in Fig. 1 illustrates this process. [ ] Field and Laboratory Procedures In general terms, the procedures followed in the evaluation of an in situ leaching application aim at accomplishing: •rapid leaching and maximum recovery of the target metal in a marketable form, •low consumption of lixiviant chemicals, •unquestionably satisfactory restoration of the mined aquifer, and •minimization of capital and operating costs for the above through development of an optimum mine plan. Keeping these goals in mind, the following minimum test program is generally recommended. Geology •Estimate of ore reserves and their variability. •Average disequilibrium value for uranium deposits. •Ore thickness, depth to ore, water level, degree of confinement, and consolidation. •Characterization of quality and quantity of other ore deposit constituents (e.g. sulfide minerals, ion exchange parameters). Hydrology •Single well pump and injectivity test. •Downhole vertical permeability test to compare flow rates of barren and mineralized formations. •Groundwater quality as it may affect licensing, hydro metallurgy, and restoration. Hydrometallurgy • Flask or autoclave tests for optimization of lixiviant parameters and determination of specific reaction rate constants. • Flask or autoclave tests for assessing amenability of lixiviant solutions with ore, consumption of lixiviant, stability of metal in solution contacting ore, and environmentally important species mobilized. • A long-path leach test for modeling the behavior of the lixiviant solution flowing through a long mineralized streamline (stream tube testing). •Metal recovery tests from lixiviant solutions (ion exchange, electrowinning, etc.). •Lixiviant regeneration tests. •Environmental restoration tests.

Jan 1, 1985

By John H. Hall

The Frémont test for measuring the energy consumed in breaking a notched bar of steel is not so well known in this country as it deserves to be. The test specimen used in this test is about # by 6 by about 16 in., notched with a hack saw on the lower side to cause the piece to break at a fixed point. A weight of 10 kg. falling 4 m., and provided with a knife or chisel which strikes the specimen, breaks the test piece by impact. The residual force in the falling weight after it has broken the specimen is recorded by a suitable device, and the difference between the total energy and the residual energy of the weight (in kilogrammeters) is the force consumed in breaking the specimen. An experience of several years with the Frémont testing machine has shown its great value in readily detecting brittleness not revealed by tensile testing or slow bending testing. In this paper it is proposed to discuss (1) the supersensitiveness of the test as applied to cast steel and (2) its value in revealing the effect of heat treatment under certain conditions. In testing coupons cut from castings heat treated by quenching and annealing, attention was drawn to the wide variations in the value of the Frémont test of specimens cut from different parts of the coupon. The latter was of the form and dimensions shown in Fig. 1, and Fremont test pieces were cut from two parts of this coupon, marked A and B in that figure. The results of the tests are shown below, tests A and B in each instance being from the same coupon: A. B. A. B. Coupon. Kilogram- Kilogram- Coupon. Kilogram- Kilogram- meters. meters. meters. meters. 1,........ 12.0 12.5 9,........ 27.5 32.5 2,........ 11.0 32.5 10,........17.5 31.0 3,........ 11.5 30.0 11,........ 14.5 31.0 4,........ 20.0 33.0 12,........ 15.0 27.5 5,........ 17.5 33.0 13,........ 19.0 30.0 6,........ 17.5 20.0 14,........ 17.5 25.5 7,........ 17.5 13.0 15,........15.0 30.0 8,........ 10.0 30.0

Jan 1, 1914

By C. R. Kuzell

INTRODUCTION KNOWLEDGE of the thermal capacity of gases is of great importance in making metallurgical calculations. The metallurgist is, frequently called upon to investigate and determine furnace efficiencies in which the heat carried into or out of the furnace by gases is a large item in the heat balance. Not only do such problems present themselves in the determination of furnace efficiency, but also in the study of the application of heat is accessory apparatus, such as stoves, regenerators, waste-heat boilers, driers,.etc. The thermal effect of the use of excess air in the combustion of fuel, the theoretical temperatures of combustion, the quantity of heat in hot blast at various temperatures, the effect of hot blast on furnace temperatures, are a few more examples of frequently occurring calorific problems involving gases. So many are the applications of the data on the heat capacity of gases that the subject merits careful study. The heat in a gas maybe due to its heat of combustion, if it is a combustible gas, and to its temperature. The latter is called its sensible heat and is the heat absorbed or evolved by a gas as its temperature is raised or lowered. The heat of combustion of gases is well established and is commonly known. The values can be found in almost any mcdern treatise on metallurgy. The sensible heat of gases has not been so well established because it is in most cases a function of the temperature, and the values of specific heats of gases over a wide range of temperatures have only recently been determined. It is the purpose of this paper to deal with the sensible heat of gases.

Jan 8, 1914

By Zay Jeffries

This paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.l The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the At transformations. 4. The grain-size refining of steel and iron is brought about by the combined effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation products do cst inherit their grain size from the austenite on cooling through the transformation range nor does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. In this instance small austenite grains may form very large ferrite grains on cooling through Arg.

Jan 1, 1918

By Alfred W. Gauger, George A. Burrell

The senior author of this paper, while in Colorado on other official business, made a trip to the Cripple Creek gold-mining district to get more data than are at present available regarding the composition of the gas that issues from the rock into the mines of the district. This was done at the suggestion of George S. Rice, Chief Mining Engineer of the Bureau of Mines. There are -many questions of interest and importance in connection with the ventilation of the mines in the Cripple Creek district, such as the menace to life and mining of a suffocating gas entering the mines from the rock, the danger due to powder smoke (from blasting operations), and danger of continued inhalation of rock dust by the miners. This report confines itself to the first problem, the gas from the rock, and principally to one phase of this question, the composition of the gas and its effects on men and lights. A more thorough study of this and other ventilation problems is planned. That the rock gas is a real menace is shown by the fact that miners (variously estimated from 25 to 50 by different persons interviewed) have been killed by it in the 25 years that mining has been vigorously carried on at Cripple Creek. Many men have had narrow escapes from death, some of them having been incapacitated for days. In addition, much loss of time results because at certain periods of the year or on certain days it is impossible to enter some workings. At a few mines, fans force air into the workings, thus supplementing the natural ventilation and much improving conditions, but the improvement is not entirely adequate at all times. Origin of the Gas Lindgren and Ransome1 think that the gas found in the rocks of the Cripple Creek mining district represents the last exhalations of the ex-

Jan 1, 1917

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By A. U. Seybolt

The pressure-temperature relations required to maintain the existence of Si3N4 in silicon-iron of 0.44-11.7 pet Si have been partially explored. The critical data obtained have allowed the calculation of some thermodynamic quantities, and have shown evidence of an order-disorder two-phase field extending at 800°C from about l pet to 5.5 pet Si. THE presence of silicon nitride in electrical sheet, nominally about 3 1/4 pet silicon, balance iron, has been described by several authors&apos;" but there has been some discrepancy among them regarding the identity of the nitride. Also, little has been reported on the quantitative thermodynamic prop- erties. In the work to be reported here, the nitride has been found to be more stable than described by Corney and Turkdogan." Several silicon nitrides have been described in the past, including SiN, Si3N4 and Si2N4 (see, for example, Abegg6 and Pascal7). However, the literature on nitrides other than Si,N, is all very old. No recent investigators using the more powerful tools available today have reported the presence of any nitride other than S3,N4. W. B. Hicke and L. R. Brantley8 in 1930 determined the dissociation pressure of Si3N4 which they made by reacting nitrogen

Jan 1, 1959

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e. g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1, 5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface [must] first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976