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By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,' Konobejewsky,' Fujiwara," Goss,' and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By A. Gatti

Studies were made on the system iron plus alumina. Various methods of dispersing and various amounts of alumina were used. Powder metallurgy techniques were used to produce the final product. Microstructures and some mechanical properties are presented. Alloys containing up to 16 pct alumina by weight are ductile at all temperatures tested. The ivon-alumina materials have a higher yield stress and improved creep resistance over that of pure iron. SINCE the development of SAP' an A1- Al2O3 powder metallurgy product, great interest has been shown in the development of a SAP-like structure in metals and alloys other than aluminum. The outstanding properties of this class of materials are: 1) Good creep resistance at high temperature. 2) High yield strengths and high hardness at high temperatures. 3) High recrystallization temperature. However, the lack of ductility and formability has thus far limited the applications of SAP-like materials. The following report deals with methods of dispersing A12O3 in Fe, processing of powders into rod, structures produced after processing, and mechanical properties of the iron-alumina material produced. Methods of dispersing the alumina and also the volume fraction of alumina added were varied. MATERIAL Powder Processing— Four methods of obtaining dispersions of alumina in iron were studied. 1) Oxidation-reduction of a Fe + 8 pct Al alloy. .2) Coprecipitation of Fe(OH)3 + Al(OH)3 from aqueous solution. 3) Colloidal mixing of Fe,O3 and Al2O3. 4) Colloidal mixing of Fe powder and A1,O3. Fig. 1 is a processing flowsheet which outlines the processing steps taken to produce a final extruded bar 1/4 in. in diameter and about 30 in. long. The - 100 mesh iron-aluminum alloy was oxidized by placing a thin layer of powder on an alumina plaque. The reduction step was modified to include 1/2 hr at 1000°C since the powders tended to become pyro-phoric unless sintered slightly after low-temperature reduction. Compacting was done in a 1-1/8-in.-diam pressing die. The slugs produced averaged 1 in. in length. The billets were encased in low-carbon steel cans shown schematically in Fig. 2. The blank is included for structure and property comparison purposes. TESTING PROCEDURE All tests were made on as-extruded material.

Jan 1, 1960

By Lewis A. Delano, Harold Rabling

It has been generally recognized that, owing to the extreme friability of galena, fine grinding has a tendency to cause excessive sliming of the mineral, so operators of lead mills have attempted to avoid this condition by commencing concentration at as coarse sizes as any mineral is freed. Jigging has been the basis of the milling process, making a clean coarse concentrate and a large amount of tailing, which was considered sufficiently low-grade to be rejected. However, developments and improvements in concentration processes are everywhere changing the low-grade tailing of yesterday into material worth re-treating today. Investigations of the work of the Hancock jig on the Bonne Terre ore have shown that the best results to be expected will give a tailing assaying 0.75 per cent. lead; the average for all conditions and grades of ore will be between 0.80 and 0.90 per cent. By crushing the jig tailings in ball-mills and retreating by tables and flotation, a tailing of considerably lower grade can be made; the problem then becomes an economic one of increased crushing costs versus higher recovery. In considering the entire elimination of jigging, the increascd smelting charges due to a greater amount of slime galena will be counterbalanced by the lower operating cost, increased recovery, and the many advantages of a simpler flow sheet. In developing these problems in the Bonne Terre mill of the St. Joseph Lead Co., a long series of tests has been carried out covering every stage of crushing and concentration, and a large number of possible flow sheets were considered and tried. Only the final results and a few comparisons will be given here. At the same time, a careful and detailed cost-keeping system has enabled us to compare milling costs with the various Bow sheets, and to calculate the economics of the problem with great accuracy. Concentration Problem The ore occurs as widely scattered deposits of galena disseminated through limestone; it has a specific gravity of 2.8 and the following composition: Pb, 4.00 per cent.; Fe, 3.00 per cent.; Zn, 0.32 per cent.; S, 3.10 per cent.; MnO2, 0.73 per cent.; SiO2, 4.20 per cent.; Al2O3, 3.20 per cent ; CaO, 28.60 per cent.; MgO, 16.85 per cent.; CO2, 36.00 per

Jan 1, 1922

By Thomas T. Read

EVERYONE engaged in the teaching of mining engineering will, I suppose, agree that the most difficult subject to teach is "Mining Methods." One primary difficulty is that the students taking the course have either had no previous experience in mining, or else they have had; either seeming to be somewhat of a drawback. The students who are unfamiliar with mines find it difficult to visualize underground conditions, as described and illustrated with sketches and maps, while those who have had underground experience seem to 'find it difficult to visualize anything much different from that which they have already seen. This reminds one of the remark about the Presbyterian doctrine of predestination, to the effect that "you are damned ,if you do; and damned if you don't."

Jan 1, 1930

By H. H. Wade, N. F. Schulz

The large quantities of iron-bearing materials, including taconite, semi-taconite," and other low-grade ferruginous materials occurring in Minnesota and elsewhere, constitute an important potential source of iron. Satisfactory grade and recovery of iron ore concentrate cannot ordinarily be obtained from these ferruginous materials by simple methods of beneficiation. Iron is distinctive in that the free metal and two of its oxides [magnetite (Fe,O,) and maghemite (gamma-Fe,O,) ] are strongly ferromagnetic. The successful magnetic separation of natural magnetite from taconite has already been established on a commercial scale. The iron in semi-taconite, how- ever, occurs largely as goethite (Fe,Os.H,O) and hematite (Fe90,) which do not respond to ordinary magnetic separation methods. Magnetic roasting converts these iron oxides to magnetite, which can, after liberation, be magnetically concentrated.

Jan 11, 1960

By W. J. Taylor

It is, perhaps, more important to put on record the particulars of experiments that are derided failures than those that are successful, as those of the latter class are certain to live, while the former may be lost sight of in a short time, and repeated by others. TO this end, I propose to give the particulars of a straight or no-bosh furnace just tried at the Chester (New Jersey) works, which was such a decided failure as to leave no doubt of the plan being wrong, and determining the necessity of a bosh of some kind, as of old. Some experiences during the past year led me to suppose that the bosh or belly of a furnace was unnecessary, and that the contraction of the walls toward the bottom for the stock to wedge in, in its descent, facilitated dirty walls and scaffolding; hence, irregularity and high fuel. I concluded, however, that a very shallow bosh for a skew-back support to the stock would be necessary, and that the proper place for this was in the tuyere-section, beginning just below the tuyeres and ending just above them, where there is nothing in the solid state but fuel, which is consuming, and no slipping or travel of stock takes place. The cubical capacity of a furnace of this design would necessarily be much less than in the old style, unless it was made very much higher. But I assumed that the loss of room for reduction could be overcome by making the size of the ore and stone charged much smaller, so that the gases would act more quickly. The next point was, what should be the size of the shaft, crucible, tuyere-circle, and tunnel-head for a given quantity of air? My first design was 12 feet diameter of shaft for 7000 feet of air, with a 9-foot crucible and 8-foot toyere-circle. This I soon reduced to 8-foot shaft diameter, which I concluded was large enongh for economical work, if regular travel of the stock on the walls could be maintained. I consulted with a number of experienced furnacemen and furnace-engineers, and the plan was well thought of by many of them; and, as I had also some offers of financial aid from them toward the risk of trying the experiment, my firm concluded

Jan 1, 1885

By Charles L. Mantell, James E. Hoffmann

Mechanical inclusion, electrophoretic deposition, and adsorption were studied as mechanisms for code-position of aluminas present in copper-plating electrolytes as an insoluble disperse phase. Mechanical inclusion was not a significant factor. That codeposi-tzon of aluminas by an electrophoretic mechanism was unlikely was substantiated by measurements of the potential of the aluminas. The alumina content of the deposits was studied as a function of the pH of the bath. These tests in conjunction with sedimentation studies demonstrated the absence of an isoelectric point for the alutninas over the pH range examined. Thiourea in the electrolyte (a substance known to be adsorbed on a copper cathode during electrodeposition) affected the amount of alumina in the electrodeposit. However, no adsorption of thiourea on aluminas in aqueous dispersions was detected. If it were possible to produce a dispersion-hardened alloy of copper and alumina by electrodeposition, an alloy possessing both strength and high conductivity at elevated temperatures might be anticipated. Investigation of the mechanism of codeposition of aluminas with copper was undertaken with the hope that knowledge of the mechanism would aid in the development of such an alloy. The word "codeposit" here does not necessarily imply an electrolytic phenomenon but rather that the materials codepositing, the various aluminas, are transported to and embedded in the electrodeposited copper by some means. Mechanical inclusion in electrodeposition implies a mechanism of codeposition which is wholly mechanical in nature; the only forces acting on a particle are gravity and contact forces. Such a particle is presumed to be electrically inert and incapable of any electrical interaction with electrodes in an electrolytic plating bath. Processes for matrices containing a codeposited phase by electrodeposition from a bath containing a disperse insoluble phase frequently state that code-position is caused by mechanical inclusion.10,2,12 If settling, i.e., gravity, be the controlling mechanism for codeposition of aluminas, then assumptions may be made that 1) the content of alumina in the electrodeposit should be enhanced by increasing the particle size, 2) the geometry of the system, that is, the disposition of the cathode surfaces relative to the di- rection of the falling particles, should affect the alumina content of the electrodeposit, 3) in geometrically identical systems the chemical composition of the electrolyte employed should exercise no effect on the alumina content of the deposit, that is, the alumina content should be the same in all cathode deposits irrespective of bath composition. A bent cathode19 evaluates the clarity of filter effluent in electroplating baths by comparing the roughness of the deposit on the vertical surface with that on the horizontal surface. Two difficulties are inherent in this technique: 1) the current density on the horizontal portion of the cathode would be substantially greater than that on the vertical surface; 2) should the deposit obtained be rough, projections on the vertical face could act as horizontal planes and vitiate the relationship between the vertical and horizontal surfaces. Bath composition should have no substantial effect on the alumina content of the deposit. Two different electrolytic baths were employed. They possessed variant specific conductances and substantially different pH ranges. The experimental tanks were rectangular Pyrex battery jars 6 in. wide by 3 1/4 in. long by 9 3/4 in. deep. The cathodes were stainless steel 316 sheet of 0.030 in. thickness, cut to 7.5 by 1.75 in. and bent at right angles to form an L-shaped cathode whose horizontal surfaces measured 1.75 by 3.0 in. All edges and vertical surfaces were masked with Scotch Elec-troplaters Tape No. 470. The anodes were electrolytic cathode copper 9 in. high by 2.25 in. wide by 0.5 in. thick. To eliminate inordinately high current densities on the projecting edge of the cathode, the anode was masked 1 in. above and below the projected line of intersection of the cathode with the anode. The exposed area of the anode was equal to that of the cathode, providing both with equal average current densities. The agitator in the cell was of Pyrex glass and positioned so its center line was equidistant from cathode and anode, and a plane passed horizontally through the center of the blade would be located equidistant from the bottom of the cathode and the bottom of the deposition tank. The assembled apparatus is depicted in Fig. 1. Hatched areas on anode and cathode represent the area of the electrodes wrapped with electroplaters tape. MATERIALS The chemicals were copper sulfate—CuSO4 • 5H2O— technical powder (Fisher Scientific Co.). Spectro-graphic analysis showed substantial freedom from antimony, arsenic, and iron. Traces of nickel were present.

Jan 1, 1967

By Ralph Hultgren

FEW phase diagrams of alloys composed of two transition metals have been adequately studied, probably because of the high melting points involved. Transition metals are the elements that have inner shells incompletely filled with electrons. They comprise groups IIIa to VIIIa of the periodic table, including more than half of all metals. We have chosen to study two systems whose comparatively low melting points allowed the alloys to be melted in a molybdenum resistance furnace. The nickel-palladium system proved to consist of a simple series of solid solutions, but iron-palladium manifested several remarkable features. The main characteristics of the latter diagram were decisively established, but lack of time prevented precise determination of phase boundaries. The gamma to alpha transformation in this system is unusual and warrants further study. Grigorjew1 determined the liquidus and solidus of the iron-palladium system by thermal methods. He found a minimum melting point, but no eutectic. He also found that palladium lowered the gamma to alpha and raised the gamma to delta transformation temperatures of iron, with a complete series of solid solutions existing between gamma iron and palladium. His measurements also indicated a compound or super-lattice near the composition FePd3. Jellinghaus2 found that annealing at 500° C. greatly increased the magnetic coercive force of an alloy of composition FePd. X-ray dif-fraction photographs showed that a tetragonal ordered phase had formed during the anneal.

Jan 1, 1939

By H. I. Aaronson, C. Laird

Cold rolling by 50 pct a A1-4 pct Cu alloy containing many 0' plates has been found to accelerate markedly the transformation of 8' to 0 upon further aging. Although the basic mechanism of this transformation remains unchanged by plastic deformation, the nuclea-tion kinetics of 8 become appreciably more rapid and also less dependent upon temperature. Particularly at lower aging temperatures, rounded idiomorphs replace several faceted rnorphologfes. The rates of growth of 9 idiomorphs in deformed specimens aged at 300°C are appreciably more rapid than simple volume diffusion control allows. This observation is shown to be explained by an excess vacancy, rather than by a dislocation Piping mechanism of growth. ThE rather complex phenomenology of the 8' —8 transformation in Al-Cu alloys has been recently elucidated in considerable detail by means of transmission electron microscopy.'-4 This technique was also employed in the present investigation in order to examine the effects of plastic deformation upon the transformation of 8' to 8. The mechanism of the transformation in undeformed Al-Cu alloys has been established as the following sequence of events.1"4 The first step is the nucleation of 9 at (Y:8' boundaries. Nucleation of a 0 crystal takes place, however, at only a very small proportion of the 8' plates present. Each 0 crystal simultaneously consumes the host 8' plate and the a! in the immediate vicinity, with growth into a being the rate-controlling process. The remaining 8' plates are then dissolved as they fall under the concentration shadow of the growing 8 crystals. The evidence on the effects of plastic deformation upon these processes is intriguing, but much less detailed. The careful X-ray studies of Graf and Guinier have shown that the aging times required to form detectable amounts of 8' and 8 are reduced by prior cold working. Thomas and Nutting confirmed these results by replication electron microscopy. Nile-shwar,* on the other hand, reported that creep deformation decreases the rate of formation of 0. While this difference may have been caused by the use of concurrent rather than successive deformation and ag- ing, the X-ray technique which he used was able to monitor only the 0 phase. It is thus possible that the times needed to form 8' were increased moreg than the kinetics of 8' — 8 transformation were accelerated. At 90 pct deformation by cold rolling, Graf and Guinier found that the usual 0' —0 8 sequence is reversed: 0 forms first. von Heimendahl 10 confirmed this result with transmission electron microscopy. Pollard and Nutting, 11 and more recently Driver and Barrand, 9 having used the same technique, report that 9 also forms first during creep deformation. In the present study, the maximum amount of deformation was limited to 50 pct reduction by cold rolling in order to insure that 8 formed principally by the decomposition of . I) EXPERIMENTAL PROCEDURES This investigation was conducted on an Al- 3.93 pct Cu alloy, prepared as previously described. 4 Morphological and crystallographic effects of plastic deformation were studied in specimens annealed 6 hr at 548°C, quenched, and then aged for either 3 or 8 hr at 250°C to form large numbers of 0' plates. After cold rolling to a 50 pct reduction in thickness, the

Jan 1, 1969

By Richard McCaffery

CONTENTS PAGE 1. Research on Blast-furnace Slags (A Progress Report). By Richard S. McCaffery 5 2. Determination of Viscosity of Iron Blast-furnace Slags. By Richard S. McCaffery, Clarence H. Lorig, Ira N. Goff, Joseph F. Oesterle and Oscar O. Fritsche 27 3. Effect of Magnesia on Slag Viscosity. By Richard S. McCaffery, Joseph F. Oesterle and Oscar O. Fritsche 55

Jan 1, 1931

By W. A. Vine

When a hole is made in a stressed solid, such as rock pierced by mine openings, equilibrium of the solid is destroyed. To restablish that equilibrium the stress condition in the rock surrounding the opening becomes rearranged. This rearrangement may or may not develop local stresses in the vicinity of the opening which exceed the elastic strength of the rock. Since stability of the opening depends, therefore, on the strength of the naturally occurring rock surrounding the opening, this rock is an engineering material of construction, and all rock affected by the associated opening or system of openings may be considered a structure. The term invert is chosen to describe the formation of the structure built from the inside, as it were, and a consequence of mining rather than an entity built for a purpose. By definition, an invert structure is formed when openings are made underground and is com- posed of that material on the solid side of a rock-air interface wherein the stress condition is affected by the associated opening or system of openings. The shape of an invert structure is never clearly defined; the skin of the structure may be mapped, and even described, but the boundary of the structure within the solid rock mass must be arbitrarily set.

Nov 1, 1955

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960

CARL HENRICH (communication to the Secretary*).-I have read with much interest the discussions of my paper by Messrs. A. S. Dwight, E. P. Mathewson, Win. B. Boggs, Jos. W. Richards, and W. C. Smith. Mr. Dwight's acknowledgment that he always-in lead smelting¬obtained better results by figuring A1203 as an acid in his slags, I may take as a confirmation of my views, notwithstanding his later conversion by, the late T. S. Austin to the latter's empirical view and way of neglecting the consideration of A1203 altogether in the composition of slags-letting the slags "dissolve" in Al203. I have a strong suspicion that Mr. Austin, in a large custom smelting plant at El Paso, has been able to keep the alumina percentage of his slags sufficiently low, not to give him much trouble, although I have also a suspicion that his furnace foreman may have had a somewhat differing opinion of the practical working of the "dissolving" theory,, whenever its applicability was tested to its limits. That Austin should have conceived the notion that the Ca of CaF2 would enter into a slag as CaO, seems hardly in accord with the recognized ability of that late metallurgist. It is a well-recognized fact that even small amounts of CaF2 will reduce the viscosity of a slag; but I did not think anyone ever had an idea that CaF2, in some mysterious way, parted with its F and coupled itself with 0 to satisfy a craving for CaO on the part of 802-least of all in a lead furnace. The "dissolving" theory for CaF2 was doubtless appropriate, and an improvement on figuring the Ca of CaF2 as CaO to satisfy the demand of Si02 for RO bases. However, I cannot understand the rationality of extending this "dissolving" theory to A1203 and to ZnO. It would be interesting to have more specific data from Mr. Mathewson in regard to the actual composition-analyses-of the slags made, when he had these unusually high alumina slags in Colorado. We "old" smelters all know that within certain limits, usually found out by rather tough experience, we could safely "disregard" A1203. In fact, I believe, we never really analyzed for alumina, except in slag analyses, when we

Jan 6, 1917

By E. Peters

As in other fields of Extractive Metallurgy, Hydrometallurgy is preoccupied with separation processes and with oxidation-reduction processes. The physical chemistry of each type of process can be described in terms of thermodynamic equilibria and in terms of reaction kinetics. Reaction kinetics are much more important at the low temperatures limiting hydrometallurgical processes than in com- parable pyrometallurgical operations and the number of cases in which the kinetics can be described by simple liquid-phase mass-transfer models are sharply limited. It is convenient to subdivide the applicable rate phenomena into processes in which (a) interface reactions control the rate,(b) mass transfer processes control the rate, (c) solid state process affect the rate, (d) thermodynamically predicted phase changes or molecular reactions fail to take place, (d) metastable substances or supersaturated phases persist, and (elchomogeneous reactions in solution affect the chemistry and the kinetics. Examples are drawn from the unit steps of leaching, cementation, hydrogen reduction, and electrowinning.

Jan 1, 1973

By P. H. Brace, N. A. Ziegler

THE study of the relations between gases and metals is one of perennial interest to all who are connected with the production of high-grade metallurgical products. The data reported here are the outcome of work of which the object is to determine the effects of dissolved gases upon the properties of metals and to gain a more detailed knowledge of the reactions between gases and molten metals, particularly iron, under definitely controlled conditions. We have attempted to reduce our margin of error by dealing with relatively large quantities of metal, from 4 to 13 lb. (2 to 6 kg.), and keeping the ratio of refractories to metal as small as practicable. The ingots produced are large enough to provide adequate material for making determinations of magnetic and other physical properties. In choosing the bell-jar type of furnace we were influenced by the results of considerable experimentation along the same general line which indicated that, for the scale on which we were to work, it was important to have the furnace structure independent of the vacuum enclosure. The use of a bell-jar surrounding the entire furnace accomplishes this and also gives great freedom of observation during operation and ready accessibility for the replacements which are necessary after each run. Our choice of analytical method was made in the light of the results secured by H. M. Ryder, who used a method similar in principle for the analysis of very small quantities of gas extracted from strips of metal heated electrically in high vacuum. We have presented some selected preliminary experimental data as being illustrative of the quantity and nature of the gases which occur in iron of different origins, but do not urge any hypothesis at this time. THE FURNACE Our furnace may be described as "a high-frequency induction furnace of the bell-jar type." It is similar in a general way to that described by Cain and Peterson' though we have introduced certain refinements of

Jan 1, 1928

?AARONSON, ALFRED E, .Vice-Pres, Mid-Co Petroleum Co , Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr - Box 927, Porterville, Cal '76 ||ABADILLA, QuiRiCo A, Student, Colorado School of Mines, Golden, Colo. '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co , 1405 Minnesota Ave, Bessemer, Ala. '04 ABBOTT, Louis BENJAMIN, Chief Engr, Consolidation Coal Co-, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met. Engr, Peerless Motor Car Co, Cleveland, Ohio. '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 633 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Mgr., Pittsburgh Dist, Valley Mould & Iron Corpn, 28th St & R R Ave, Pittsburgh, Pa '19 ABEL, W D, Min. Engr. 3897 Sacramento St , San Francisco, Cal. '19 ABELL, 0 J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY, G E Willow Springs, Mo '20 ABEY, HIROSHI, Min & Met Engr, Arakawa Mine, Mitsubishi Co, Senpoku-gun, Akitaken, Japan '17

Jan 1, 1923

By F. V. Lenel, G. S. Ansell, J. A. Dromsky

The growth of aluminum oxide particles in a nickel matrix was studied eve?. the temperature vange of 2140° to 2470°F. The instability of the dispersed alumina was shown to be independent of the crystal structure of the alumina. The activation energy for the growth of the dispersed alumina was found to be 84.7 1 2.0 kcal. The particle radius increased as a function of time. These results indicate that the growth is not diffusion controlled. It is believed that the rate controlling mechanism is the dissolution of the aluminum and oxygen atoms into the nickel lattice. THE strength properties of alloys which consist of a finely dispersed second phase in a metallic matrix depend upon the spacing between the second phase particles. It is therefore desirable to achieve very fine dispersions in these alloys. Furthermore, to retain the properties these very fine dispersions must be stable during fabrication and service of the alloys. The best known of the dispersion strengthened materials, the SAP type alloys, which consist of a dispersion of aluminurn oxide in aluminum, have exceptionally good stability up to the melting point of aluminum. There is evidence, however, that other dispersion strengthened alloys, even those consisting of refractory oxides in a metal matrix, may be less stable. This investigation is concerned with the stability of Ni-Al2O3 alloys in the temperature range in which these alloys are usually fabricated. The mechanical properties of Ni-Al2O3 alloys at elevated temperatures have been previously investigated by Crelnens and rant,' and Gregory and Goetzel.2 The behavior of these alloys in stress rupture tests appears to indicate that at temperatures below 1800°F they are highly stable. There is some doubt, however, as to their stability at the higher temperatures used during the conventional fabrication. Cremens and Grant, in preparing their test alloys, cousolidated, by powder metallurgical techniques, nickel powders as fine as 0.13 µ diam and alumina powders as fine as 0.018 µ. Metallo- graphic examination of the alloys following fabrication revealed that none had interparticle spacings of less than 2 µ. Considering the size of the original component powder particles, it is likely that the dispersions coarsened during fabrication. Gregory and Goetzel, in their studies of extruded alloys of 80 pct Ni—-20 pct Cr matrixes with nonmetallic dispersion, observed a definite coarsening of the alumina dispersions in alloys sintered at 2280°F as cantrasted to those sintered at 2000oF. Similar observations on the spheroidization and growth of thoria particles finely dispersed in a nickel matrix were made by D. K. Worn and S. F. Marton.3 As a result of such coarsening, much of the effort expended in the preparation of very fine powder mixtures would be lost. The mechanical properties of the alloys which had experienced coarsening would be expected to be poorer than if the original dispersions had been retained. EXPERIMENTAL PROCEDURE Ni-Al2O3 alloys were produced from powder prepared by a coprecipitation technique. Aluminum hydroxide and nickel hydroxide were coprecipitated from chloride solutions of the metals. The mixed hydroxides were calcined to form metal oxides and the nickel oxide in the mixture was selectively reduced to nickel by treating it in hydrogen. Specimens were compacted from the resultant powder which consisted of a fine, uniform mixture of aluminum oxide and nickel particles. The compacts were sintered by resistance hot pressing4, a densification technique which requires exposure times of the order of only a second or less at elevated temperatures. A conventional sintering process was not used, since the temperature required for densification would have to be in the region in which the stability of the dispersion was to be studied. A series of hot pressed specimens were treated in hydrogen at temperatures from 2140o to 2470°F (1171o to 1355oC, for times up to 120 hr. Changes in the microstructures were studied by electron microscopy using the two-stage preshadowed carbon replica method.5 In performing a lineal analysis on a series of micrographs from each specimen it was found more convenient to determine the mean free path between alumina particles rather than particle radii as the parameter of growth. Although these quantities are directly proportional for only spherical particles, the alumina particles in these alloys

Jan 1, 1962

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By L. O. Howard

The practice of using acid-lined converters at the plant of the Old Dominion, Copper Mining & Smelting Co. was discontinued early in January, 1913, and replaced by basic-lined converters. The new equipment consists of one electrically operated 12-ft. upright converter stand and two basic-lined shells for same. These shells are provided with twenty-four 1 1/4-in. tuyeres. The mouths are 5 ft. in diameter. Owing to the fact that there is no bedding system or other large storage capacity between the mine and the smelter, the furnaces must handle as fast as produced ore and concentrates, which may vary considerably from day to day, both in tonnage and copper content. Consequently the converter is often crowded to its utmost capacity by the frequent fluctuations in the daily matte supply. From the foregoing, it will be seen that in no way can the 'converter be favored by running light charges or by transferring to it from other stands in operation. Neither can it regularly be allowed to cool between blows, and only occasionally can it be run at as low a temperature as might be wished. No copper precipitate or other foreign material high in copper is available to help out the tonnage. Repairs and alterations or the removal of defective tuyeres must wait until such time as a slight falling off in.the matte supply allows the converting operations to ease up. These variable conditions all combine to interfere with the systematic operating of the converter. The first 12-ft. shell was blown in on Jan. 6, 1913, and ran until June 27, 1913, when it was removed to patch the brick. A record of operations covering this period follows: Shell No. 1. First Campaign, Jan. 6,to June 27, 1913 Commenced blowing............................Jan. 6, 1913. Taken off stand for patching.....................June 27, 1913. Total blowing time..........................2,689 hr. 40 min. Total number of, blows made.............................. 664 Average time of blow............................ 4 hr. 3 min. Tons matte charged.................................. 18,157 Average copper content of matte................ 43.9 per cent. Average time blowing one ton. copper................ 22.5 min. Total copper made............................... 7,250 tons

Jan 1, 1915