Search Documents

By J. E. Pavlick, W. W. Mullins, H. W. Paxton

The growth of nitrogen-austenite during nitriding of large-gvained ferrite between 650" and 800°C has been studied as a functimz oJ time and nitrogen potential of the atmosphere for a variety of alloying elements dissolved in the ferrite. Whereas no preferential grain boundary penetration by aistenite takes place in zone-refined iron, the addition of aboit I zot pct oj' V, Ti, Cr. Si, or A1 produces significant protrusion of austenite down former 0-0 boundaries. This group of elernents also produces ragged y-0 interfaces in the a grains which advance more slozuly than those in zone-refined iron. 1 zut pct of Ni, Co, Mn, or Mo dissolved in ferrite leads to essentially smooth 7-a interfaces, which advance at rates very sinzilar to those in zone-refined iron. The reasons for this effect are not clear. Two possible limiting hypotheses, not necessarily exclusive, are discussed. One involves p.referentia1 grain bozindary diffusion of nitrogen. the other the production of a zone of ferrite, stpersatcirated with respect to nitrogen, from which austenite precipitates helerogeneozisly on the a-a gyain boundaries. In many phase transformations which occur by nu-cleation and diffusion-controlled growth, information on the parameters which control the rates of nuclea-tion and of growth is frequently not quantititative. The present work describes a continuation of efforts to obtain quantitative data on growth rates in systems where thermodynamic and kinetic factors are known independently, and thus where comparison with models of the growth process is possible. The work has been conducted on iron-base systems for two reasons. Firstly, there are several interesting transformations in this system, many of which are of practical importance. Secondly, the information on phase diagrams, activities, and diffusion coefficients is more complete in this system than in any other. These data are still inadequate to check all the effects of alloying elements, but at worst it is possible to make estimates and thus examine order-of-magni-tude agreement with proposed models. It will be necessary to do this in the present work. The problem studied was the growth of nitrogen-austenite in from the surface of large-grained columnar crystals of alloyed ferrite exposed to an NHs/Hz atmosphere. Earlier work by Grozier et al.' had suggested that growth of austenite may occur preferentially along grain boundaries of alloyed ferrite, whereas zone-refined (ZR) iron shows no such effect, Fig. 1. Growth of nitrogen-austenite into single crystals of zone-refined ferrite is planar provided sufficient nu-cleation sites for austenite are present, and is controlled by volume diffusion of nitrogen through the

Jan 1, 1967

By George H. Found

DURING recent years considerable interest has been focused on the energy-absorption characteristics of metal when it is cyclically stressed in vibration. The most familiar manifestation of this phenomenon, which is called the "damping capacity" or "internal friction" of a material, is involved in the dissipation of mechanical energy of vibration, which otherwise would build up to stress levels where the problems of noise and fatigue are involved. In addition to its engineering importance in structures, the damping behavior of metals, particularly at low stress amplitudes, has also been used as a unique metallurgical research tool with which to provide sensitive means for indicating certain structural changes within metals. Important contributions toward understanding the energy-dissipating mechanisms that are responsible for internal friction in metals have been made in the last few years. The information is not yet sufficiently extensive, however, to provide a useful metallurgical concept describing exactly how the structure affects the internal friction, or to encourage more general use of this technique among metallurgists. Three fundamental mechanisms have been proposed, as a result of recent experimental investigations, to account for the internal friction in nonferrous metals in low-stress amplitude tests. These include damping due to internal thermal currents that are created and flow in metal because of differential vibratory stress effects,1 damping due to localized inelastic stress relaxation at inhomogeneities within the metal,2,3 and damping related to plastic flow of a localized type for which an explanation has been sought in terms of the dislocation theory.4 How each of these mechanisms functions as a result of structural changes in the metal is, in general, not well understood because of insufficient experimental data for which the controlling variables have been segregated and because of uncertainties in regard to the nature of the structural changes themselves. In several investigations the effects of cold-working on the internal friction of polycrystalline brass and aluminum have been described. As reported by Köster and Rosenthal,5 and by Förster and Breitfield,6 there is an initial large increase in the damping when the metal is worked. The initial high value is not stable, but declines rapidly, at first, in a hyperbolic manner. About 100 hr, after straining, a stable value is reached of magnitude proportional to the amount of strain.7 In Fig. I is shown the relationship found by Zener and his collaborators between the internal friction due to cold-working of alpha brass and the amount of cold-working.8 Several investigators have made internal-friction measurements on worked poly-

Jan 1, 1945

By E. W. Davis

On the eastern end of the Mesabi Range, in Northern Minnesota, is a large formation of siliceous rock which contains bands and fine grains of magnetite. The magnetite comprises about 35 per cent. of the rock, the remainder being chiefly quartzite and iron silicates. The rock has a specific gravity of 3.4, a hardness of 7, and is extremely tough. This large deposit was located early in the history of the Minnesota iron-ore industry but has not been utilized because of its low percentage of iron as compared with the other Mesabi ores, and because of the difficulty and expense of any milling treatment that would concentrate the iron. An investigation, begun about 3 years ago, shows that the magnetit,e is finely disseminated throughout the entire formation and that there are bands or lenses of higher- and of lower-grade material, in which the magnetite and silicate are intimately mixed. As a result, the scheme of milling adopted must include a fine-crushing plant. As it is necessary to crush to 200 mesh in order to produce the desired grade of product, the fine crushing is one of the largest items of expense and for this reason has been given detailed study. It is the purpose of this paper to present some of the results of the work on fine crushing, as to both theory and practice. Previous to fine crushing the part of the rock that contains little or no magnetite can be discarded by magnetic concentrators after each reduction in size in the dry-crushing plant. This-makes it possible to fine-crush a minimum of rock and also establishes the feed to the ball-mill as below % in. The fine-crushing problem, then, consists simply in crushing the rock from 1/4 in. to 200 mesh at the minimum expense. Equipment of the Testing Plant In order to determine, among other things, the operating conditions of the ball-mill when working on this rock, a test mill of about 300 T. daily capacity was erected at Duluth, Minn. The fine-crushing plant contains a Hardinge 8-ft. by 22-in. (2.4-m. by 55.8-cm.) conical mill, a 6- by 27-ft. (1.8 by 8.2-m.) Dorr duplex bowl-type classifier, a 41/2-ft. (1.37-m.) standard Akins classifier, and the auxiliary machinery necessary to handle the products. Each machine is driven by an individual motor, each of which is provided with meters for measuring the power required. Over 150 tests have been made in the ball-mill, varying in

Jan 1, 1920

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By J. W. Spretnak, G. W. Cunningham

Grain growth across the bond region in Pressure bonded copper was found to be mainly dependent upon the presence or absence of microvoids, but it was also found that prior history, bonding pressure, bonding time, and bonding temperature are important variables. An increase in pressure, time, or temperature tends to promote grain growth in the interfacial region. Polygonization is observed after pressure bonding except for specimens previously annealed at temperatures on the order of 1800°F or higher. The dislocation density in bonded specimens was found to be greater in the bond region. THE bonding of metals by the application of gas pressure at elevated temperatures is a relatively new process, having been developed over the past 10 years. The technique, as described by Paprocki, Hodge, and Boyer,l is unique in that assemblies of many parts and complex shapes can be bonded with a negligible amount of deformation. The process thus differs metallurgically from pressure welding, cold welding, and recrystallization welding in that deformation occurs only in a microscopic region whereas, in general, the welding requires severe deformation and may extend the contact surface by a factor of 3 to 10 during the welding. From a practical standpoint, pressure welding is not amenable for bonding large surfaces. During the time in which Paprocki and coworkers were deve1oping the process, West2 established aproc-ess,for bonding aluminum to uranium, and Barnes and Maze? developed a gas-pressure-bonding technique for nickel and copper. Recently, Fugardi and Zambro4 have used equipment similar to that developed by Paprocki and coworkers to establish parameters for bonding stainless steel, aluminum, and zirconium. Most of the investigations on pressure bonding have been empirical in nature and, although methods have been developed for bonding such metals as molybdenum, columbium, titanium, zirconium, and stainless steel, the information concerning the mechanism of bonding is limited. Several workers5"7 have studied the pressure bonding of dissimilar metals in order to gain information on diffusion and formation of inter-metallic phases under application of pressure. Clapson and Robbins8 have shown by a series of annealing studies that voids in the interfacial boundary of roll-bonded copper can prevent movement of the boundary until the voids are spaced far enough apart to prevent pinning. They also indicated that recrystallization and grain growth can eliminate the voids. In this paper it is shown that voids are the major detriment to grain growth across pressure-bonded interfaces, but it is also shown that prior history, bonding pressure, bonding time, and bonding temperature are

Jan 1, 1962

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strainaging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 720°C. The time of treatment is relatively short (about 3 hr. to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say almost 30 per cent by volume. At this temperature, the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a very low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,000 lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantially constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1943

By Herbert H. Kellogg

RECENTLY the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authors1-5,18 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, lauryl amine hydrochloride, as a collector for the flotation of galena-sphalerite ores. The results show that lauryl amine hydrochloride (LAmHCI), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. CONTACT-ANGLE TESTS The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-covered glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the dean surface to air or any other source of contamination.

Jan 1, 1945

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By J. T. Michalak, H. W. Paxton

The recovery of the initial flow stress of poly-crystalline iron is characterized by a) a logarithmic time dependence; b) an increasing activation energy with increasing recovery; c) an increased ?,ate and fraction of recovery with decreased temperature of deformation; and d) an increased rate with increased deformation. Isochro)ml studies of the recovery of single crystals revealed more sluggish recovery. The original flou3 stress of single crystals could be regained by recovery anneals at 800"or 900°C. ThE great majority of the theoretical treatments and experimental studies of strain-hardening have been concerned with the close-packed lattices.' Very little effort has been expended on the bcc structure so that the theory of work-hardening of this lattice is essentially nonexistent. The limited amount of experimental data resulting from the direct studies on silicon-iron,2 low-carbon steel,3 and purified irons4"7 does not as yet permit a detailed analysis of the strain-hardening. Studies concerned with the effects of annealing following deformation have been few in number," have been somewhat limited in extent, and have had the disadvantage of using irons containing a substantial impurity content. The present research was undertaken to augment the limited knowledge we have of the characteristics of a bcc metal as regards strain-hardening and recovery from the strain-hardened state. The recovery of the flow stress has been employed since it was felt that the stress associated with the hardened state gives at least a fair qualitative description of the state of the imperfections causing the hardening. The study was concerned primarily with the recovery of flow stress following strain-hardening of polycrys-talline, zone-melted iron as a function of the amount of deformation, the temperature of deformation, and the time and temperature of the recovery anneal. A limited investigation of the recovery of the initial flow stress of single crystals of this same material as a function of the recovery temperature was also conducted in conjunction with the Lambot X-ray technique." MATERIAL The zone-melted iron used in this investigation was obtained through the courtesy of the American Iron and Steel Institute and Battelle Memorial Institute. The analysis, as given by the supplier indicated a maximum impurity content of 0.02 wt pct excluding those impurities listed in Table I. (The actual impurity content is very probably less than this since detection limits were considered as the amount of a particular impurity level.) Also listed in Table I are the interstitial impurity contents of the iron at various stages of experimental work indicating that these im-

Jan 1, 1962

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By E. F. Raffo

THE design of the Chuquicamata concentrator offered an unusual combination of problems, all of which had, in one way or another, a definite effect upon the final arrangement of all the equipment and necessary facilities. First of all, a remotely located project of this magnitude required careful selection of equipment with an adequate supply of replacement parts and in some cases necessitated stand-by spare equipment ready for immediate use. Fortunately, in the course of determining the proper flowsheet, in itself a prime factor in the concentrator design, it was possible to conduct numerous grinding and flotation tests at the Anaconda and Andes concentrators. As a result of these tests made under actual operating conditions, most of the major equipment best suited for treating the Chuquicamata ore efficiently was decided upon while preliminary design layouts were still being made. The design has been based primarily on the treatment of sulphide ore crushed to about 3/4 or 1 in. However, until the new sulphide crushing plant is completed it will be necessary to handle ore crushed to 3/8 in. in the existing oxide crushing plants and to some extent a mixed ore which has had its oxide copper content removed by leaching. This mixed ore, known as leached residue, will contain a certain amount of sulphuric acid from the leaching process which necessarily requires special protective measures. Several factors influenced the final location of the Concentrator. The only established fact known during preliminary design layout was the elevation of the dumping floor over the fine ore bin. This was predetermined by the desired level railroad grade across part of the existing tailing and leached residue dumps from the oxide plant to the bin. Next it was necessary that a site be chosen that would not require an excessively long haul from either the present oxide plant or the mine and in addition provide a fairly constant natural ground slope sufficiently wide to accommodate the length of the ultimate concentrator. The site as finally chosen to meet the foregoing restrictions provided a natural ground slope of 6 to 7 pct. This was excellent, especially in a region subject to earthquakes, as it assured that foundations of heavy equipment and footings for building and crane columns would rest on cut or undisturbed ground. However, this shallow slope, although having some definite advantages in the overall consideration of plant layout, resulted in the need for extensive studies in the general arrangement of equipment. Wasteful and excessive vertical drops had to be eliminated in the

Jan 1, 1952

By Harold Markus, Arthur H. Grobe, Gerhard Derge

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study. has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from 1/2 to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.? After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been damped. The pH of the electrolyte was controlled? by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.10. Potentials were measured against a saturated calomel electrode connected. to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By H. M. Otte

Certain choices for the shear elements of the inhomogeneous distortion in the phenomenological theory of martensite formation are examined for their agreement with crystallographic and X-ray data of iron alloys. The assumption that the shear elements must represent slip or twinning systems characteristic of bcc metals is found to covey all observations, even when a small uniform dilatation is taken into consideration. In bct martensite, (011) becomes a possible twinning or faulting plane, in addition to {112), and qualitatively similar X-ray line broadening is to be expected from both. The basic concept inherent in the current theoriesl-4 of the formation of martensite is that the interface between the parent (austenitic) and product (martensitic) phase is an invariant strain plane (i.e., one that is undistorted and unrotated). Experimental evidence that the interface is of such a nature is available in certain transformations2'5'6 but for the transformation in iron alloys direct observation has not proved enlightening. Internal strains resulting from the formation of the small martensite platelets within the parent austenite matrix7 make it difficult to produce the desired evidence. Indirect evidence, however, such as the continuity of scratches in passing from untrans-formed to a transformed region, strongly indicates that the habit plane in iron alloys is an invariant strain interface. The scatter in habit planes in a given specimen8 would suggest that internal stresses have a slight but definite influence. On the other hand, composition changes which affect the lattice parameter can alter the habit plane appreciably, and by an amount greater than the scatter.' The success of the theories depends on the choice made for the "inhomogeneous distortion" or "complementary shear'' in the analysis and also on the choice for the parameter 6 representing a small uniform dilatation. In the approach developed by Wechsler, Lieberman, and Read'," it is implicitly assumed that 6 is unity. In the case of iron alloys, all observations cannot be explained without varying either the inhomogeneous distortion or 6 . Bowles and Mackenzie3 considered only the effect of varying d. They found it difficult to reconcile the wide scatter of habit planes with the theory and were forced to the conclusion that it may also be necessary to consider variations or different choices of the inhomogeneous distortion. Wechsler and Read" considered a limited number of possible choices for the inhomogeneous distortion, but no variation in 6, though this could easily have been introduced if so desired. It is the purpose of the

Jan 1, 1961

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942