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By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By R. S. Handy

THE properties of the Patiño Mines and Enterprises Consolidated, Inc., a New York corporation, are near Llallagua in the department of Chayanta in the west central part of Bolivia, South America, about 80 miles southeast of Oruro and 250 miles southeast of La Paz, the largest city in Bolivia and its virtual capital. The properties are accessible by railroad from three points on the west coast-from Mollendo, Peru, across Lake Titicaca, from Arica by way of La Paz, and from Antofagasta, Chile. The latter route, although the longest, is recommended by the companies as affording a more gradual introduction to the high altitudes; the mine being 13,000 ft. above sea level. The company operates its own railroad from its properties at Uncia to Machacamarca on the Chile & Bolivia R. R., a distance of 60 miles. This railroad is well equipped and well operated, and its location among the mountains surrounding Uncia represents excellent engineering skill. In fact all of the railroads, although they are of only a meter gage, are remarkable for the excellence of their construction, the arrangement of their dining and sleeping cars and the precision of their operation. There is only one drawback to rail- road and hotel accommodations and that is the absence of heating facilities, which does not seem to affect the natives but keeps a tenderfoot's teeth chattering continually. The company is a consolidation of the Patiño company, owning properties at Uncia, with the Compafiia Estanfera de Llallagua, a' Chilean corporation owning contiguous properties at Llallagua. Before the consolidation these companies were deadly enemies, and there still remain at the surface plant at Uncia the fortifications and underground defences provided during the warfare between the two factions. Also, in the Azul, or "Blue" tunnel at the junction line between the two properties is a strong steel barricade still bearing marks of the bullets fired during the various armed tilts between the workmen of the two companies. The headquarters for the mining operations and the milling plant have been moved since the consolidation from the original location at Uncia to the Llallagua side of the mountain, where the Chilean company's operations were carried on. The historic old town of Uncia, with its massive stone buildings of Spanish design, is a wreck, while the Llallagua side is being rapidly built up with modern structures.

Jan 1, 1929

By Alden B. Greninger

Many recent contributions in the field of theoretical metallography have been concerned with crystallographic definitions or descriptions of various phenomena. The lattice orientation of the crystal being studied must be known before such definitions can be made. Practically all the metallic crystals used do not have crystal faces—other than the unknown "plane of polish"; hence resort must be had to other means of determining orientations. Some use has been made of etch-figures, slip bands, optical properties, etc., for this purpose; but for accurate results, and because of the fewer restrictions to their use, the various X-ray methods have been the most satisfactory.' The methods that have been used may be divided into two general classes: (1) oscillation methods, and (2) transmission Laue methods.² The disadvantages of these methods are numerous, chief among them being the time required to determine a complete orientation. No method proposed so far is wholly satisfactory for determining the orientation of a small macrograin within a polycrystalline aggregate.

Jan 1, 1935

By Alden B. Greninger

Many recent contributions in the field of theoretical metallography have been concerned with crystallographic definitions or descriptions of various phenomena. The lattice orientation of the crystal being studied must be known before such definitions can be made. Practically all the metallic crystals used do not have crystal faces—other than the unknown "plane of polish"; hence resort must be had to other means of determining orientations. Some use has been made of etch-figures, slip bands, optical properties, etc., for this purpose; but for accurate results, and because of the fewer restrictions to their use, the various X-ray methods have been the most satisfactory.' The methods that have been used may be divided into two general classes: (1) oscillation methods, and (2) transmission Laue methods.² The disadvantages of these methods are numerous, chief among them being the time required to determine a complete orientation. No method proposed so far is wholly satisfactory for determining the orientation of a small macrograin within a polycrystalline aggregate.

Jan 1, 1935

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

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Jan 1, 1938

By M. H. Waxman, M. Gondouin, H. J. Hill

Streaming-potential experiments were conducted within the Muddy- and Dakota-sandstone interval of a Denver basin well. Analysis of the data shows that, for this case, streaming potentials opposite sands were higher than those opposite shales when the mud was fresh. Streaming potentials opposite shales, however, were of sufficient magniiIlde to be important in SP interpretation. They were linearly dependent upon pressure differential, and they increased with mud filtrate resistivity. The magnitude of streaming potentials opposite sands was influenced by the characteristics of the original mud cake formed at the time of drilling. Use of mud samples taken at the time of logging may not always be satisfactory for determining streaming-potential corrections. Both the streaming and electrochemical potentials were found to be affected by the previous history of the borehole system. Following a change in mud characteristics, several days were required for SP stabilization. This was, in part, due to the mud cake acting as an imperfect shale membrane. INTRODUCTION Laboratory investigations by Wyllie,1 Salisch,2 Moore," Sen Gupta and Bannerjee,0 and Hill and Anderson' have shown that streaming potentials developed across mud cakes deposited on permeable filter beds are of sufficient magnitude to be critically important in SP interpretation. Streaming potentials across shales have been reported by Schenck,' Gondouin and Scala; and Hill and Anderson." The magnitude of the shale streaming potentials obtained by Schenck and by Gondouin et a1 led these authors to conclude that in many cases the shale streaming potential would approximately equal the mud-cake streaming potential. Hill and Anderson, however, obtained somewhat lower magnitudes of shale streaming potential. The field experiment described in the present paper was a cooperative project carried out by the respective operations and research departments of Schlumberger Well Surveying Corp., Shell Development Co. and Shell Oil Co. The primary objective of the experiment was to determine in the borehole the streaming-potential behavior of both shales and mud cakes under conditions approaching, as nearly as possible, those normally encountered in logging practice. METHODS AND EQUIPMENT WELL A Muddy- and Dakota-sandstone vie11 in the Denver basin was chosen for the experiment. Both sandstones were water-bearing and, since reservoir pressures in these sandstones are abnormally low (gradient of approximately 0.25 psi/ft), it was expected that studies of streaming potential could be conducted from low-pressure differentials (approximately 200 psi) to about 27000 psi by bailing mud from the hole, filling up and then applying wellhead pressure. The selected well encountered the Muddy sand-

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem'ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam'ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961

By J. D. Forrester

Many have been prone to credit the decline of professional interest in some branches of mineral industry education to the industrialists and other agencies who use our graduates. We hear the cry that industrial salaries are too low, opportunities for advancement do not exist, and the mineral industry specifically and generally is not interested in the engineer's efforts. Perhaps the time now has come when we should "dress-ranks," examine our practices, and publicize and encourage advanced technical training instead of laying all our troubles elsewhere. There can be no doubt but that industry is interested and stands ready and willing to co-operate. This is demonstrated by the numerous grants-in-aid and co-operative industrial projects which have been made available to those relatively few schools which have been encouraging graduate study and research. There is no dearth of research problems in any of the mineral industry fields and the sooner we realize the great opportunities for constructive, technical research in all areas of our profession the sooner we will reap the benefits of our engineering enterprises by closer liaison and broader understanding with industry. An analysis is offered here of the status of graduate work and research in various phases of mineral industry education in the United States. It is

Jan 1, 1949

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not with-stand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these require-ments, but as a result of the extensive research carried on by steel manu-facturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By F. P. Dewey

The subject of this paper does not embrace the consideration of ways and means for the increase of analytical accuracy, or the question what could or should be attained in that direction. I desire simply to call attention to the degree of accuracy exhibited in actual every-day practice. In estimating this, little weight will be given to the evidence afforded by the agreement of duplicate or multiple determinations by the same chemist; for I am convinced that such agreement is a delusion and a snare. Nor will special importance be attached to the agreement of two or even three analyses in special cases, or to the agreement between two methods practiced by the same analyst. I propose to compare the results obtained by several chemists, working upon the same sample and by various methods, in order to exhibit, as I have said, the actual condition of practice. The available material for illustrating this phase of the question is unfortunately scanty; but something has been done; and I hope, by calling attention to some of the work in this line, to stimulate further work in the same direction by inducing others to prepare suitable samples and submit them to various chemists who are competent and willing to make the necessary determinations, and fully describe the methods they employ. I draw most of my illustrations from the Transactions of the Institute, the Proceedings of the Association of Official Agricultural Chemists, and from personal experience. Manganese in Steel.—In May, 1881, Mr. William Kent presented a paper to the Institute entitled " Manganese Deter-

Jan 1, 1897

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By Arthur Notman

SacRamento Hill is a mass of granite porphyry intruded along a fault between Paleozoic sediments and pre-Cambrian schists in the Bisbee district, Cochise County, Arizona. The intrusion invaded both walls of the fault to a large extent, and the accompanying extensive mineralization of the Paleozoic limestones is the locus of the great high-grade copper orebodies of the Bisbee mines. Prior to 1909, although the presence of ore in the masa of the hill itself had long been suspected, systematic exploration had not been attempted. A few shallow pits on the surface here and there had disclosed some chal-cocite with associated carbonates as stringers in a mass of strongly brccciated, silicified, and iron-stained porphyry. The workings in the surrounding limestones had penetrated the porphyry in a dozen or SO places for some distance from the contact but had disclosed no ore. However, the rock had been largely altered to quartz and sericite and very thoroughly impregnated with pyrite and traces of the copper sulphides. A close geological study of the conditions, both surface and underground, strengthened these suspicions, and plans for prospecting the hill were made in 1909. Reference to the accompanying illustrations, Figs. 1 and 2, will give an idea of the general appearance of the surface. The mineralization is more intense in two main zones, one at the west end and the other at the east end of the hill. The outcrop of the hill is elliptical and approximately 3,000 ft. long by 1,400 ft. wide. The Sacramento shaft, which is the main hoisting shaft of the mine and situated at the east end of the hill, as shown by the accompanying map (Fig. 3), offered a convenient base for prospecting that end of the hill, while the workings from the Holbrook shaft offered a similar opportunity at the west end. The choice of level for the first work was determined by analogy with the most favorable depth for enrichment below surface obscrved in the other disseminated deposits of the Southwest.

Jan 1, 1916

By Frank Firmstone

In April, 1873, No. 2 furnace at the Glendon Iron Works being out of blast, it was decided to alter it from an open to a closed top. The three side flues, through which a part of the gas was formerly taken off, were 15 feet below the top, and as, for various reasons, it was not convenient to cut new flues through the brickwork at the top, as is commonly done with closed-top furnaces, a modification of Coingt's charger was employed. This apparatus, as figured by De Vathaire,* consists of a cup or hopper, like that used with the cup and cone, and a central pipe for taking off the gas, which descends some distance into the furnace, and has a projection around it forming a seat for a ring of a triangular cross-section, which closes the opening between the cup and the central gas-pipe. The charge is put into the cup, and by lowering the ring, is thrown into the furnace, a part going outside of the ring toward the walls, and a part through the inside toward the gas-pipe. In this form the apparatus was not applicable, for: 1st. With a gas-pipe three feet in diameter, in a top eight feet in diameter, the openings left by lowering the ring would not be large enough to let lump coal pass through. 2d. For the charger to shut tight, the ring must bear equally against the projection made for it on the gas-pipe, and against the edge of the cup. This would not be difficult to effect when the apparatus is first put up, but a comparatively small change in the relative position of the parts, such as is almost certain to occur from expansion, would cause the ring to touch the pipe or the cup, whichever happened to be the lower, first, and leave a leak between it (the ring) and the other. In the plan adopted (Figs. 5 and 6, Plate I), the central opening in the ring is closed by the bottom of the gas-pipe, whereby more room is left for the passage of the stock when the charger is open, than if the pipe descended into the furnace; and the pipe, instead of being rigidly supported, rests on the ring, when the charger is closed, and follows it for two or three inches as it opens, until stopped by the counter-balance lever C. When the ring is raised to close the furnace top, it comes in contact first with the bottom edge of the gas-pipe, then both are raised together, until stopped by the ring touching the edge of the cup. In this way a good joint is made at both places.