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By Ernest Burchard

A RECONAISSANCE of the chrome and manganese'1ore deposits of Culm was made in the spring of 191s by Albert Burch representative of the U. S. Bureau of Mines and the writer representing the U. S. Geological Survey. The object of the study was to obtain authentic information for use of the: United States Government as to the location, character, size, and availability of the Cuban deposits of the ores of these important steel-alloy metals. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the Island. Mr. George A. Wright, of Baracoa, Cuba, a mining engineer especially familiar with the chromite deposits of Oriente Province, was a member of the party from Feb. 25 to Mar. 20. It was possible to visit most of, the chrome-ore deposits that seemed to be of promise, but there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Furthermore, no attempt was made to examine the extensive chromiferous iron-ore deposits of the Mayari, Moa, and Cubitas districts, as these deposits cannot be regarded as sources of chromium except indirectly. At the close of the field work the essential data concerning the quantity and quality of ore probably available for shipment during 1918 and 1919, in the event of the continuation of the European war, and of the tonnage of ore in reserve, were furnished to such Government bureaus as were interested, including the Shipping Board and the War Industries Board, and as soon as chemical analyses of the chrome ores could .be obtained, a press bulletin on the subject was published by the Geological Survey. In the present paper the engineering data, and tonnage estimates contained in the unpublished notes of Mr. Burch have been freely used, and their helpfulness is hereby gratefully acknowledged. Many thanks are due Senor Montoulieu and Mr. Wright for their valuable work in the field; to the officials of the Spanish American Iron Co. and of the various other companies; and to individuals holding chromite claims, for courteously facilitating the work of the party. In the study of material for the present paper, chemical analyses have been made by R. C. Wells and petrographic determinations and descriptions were furnished by Miss E. F. Bliss, both of the U. S. Geological Survey.

Jan 9, 1919

Sixteen executives, technicians and operative personnel from the French mining industry, now touring mining operations in the U.S., will wind up their visit to this country at the AIME Annual Meeting. Traveling under ECA auspices, they will be in Denver on Feb. 5, Salt Lake City, Feb. 8 to 13, Bonne Terre on Feb. 16. Four of the group are engaged in bauxite mining, nine in lead and zinc, two in pyrites mining. All are interested in American mining equipment and methods, and hope to contact manufacturers' representatives in the various areas they visit. A $600,000 manganese pilot plant is expected to be put into operation by Sept. 1, by the Bureau of Mines at Boulder City, Nev. S. R. Zimmerly, chief of the Bureau's metallurgical div. for the region, recently completed the mill design and flow sheet; and the Bureau is awaiting steel priorities before building. Ore from the Artillery Peak area, 60 miles south-west of Kingman, Ariz., will be used in the mill. Construction will be handled by Rex Lloyd of Boulder City.

Jan 2, 1951

By S. K. Nicol, A. R. Swanson, J. C. Day

Addition of oil to a suspension of hydrophobic coal particles can influence its dewatering characteristics. An agglomeration process occurs in which coal particles are held together by negative capillary pressure at particle/oil/water contacts. Consequently, the units round which flow can occur are enlarged and this improves dewatering parameters such as drainage rate, solids recovery, and equilibrium moisture content. This paper discusses processes which attempt to use this principle, in terms of metallurgical and economic efficiency. The discussion is augmented by results of recent experiments on the effect of oil addition to centrifuges and vacuum filters.

Jan 1, 1980

COUNCIL OF SECTION DELEGATES Nicholas A D'Arcy, Jr, Chairman (Southern California Section) Charles Chapman, Vice-Chairman (Florida Section) Ben H Parker, Secretary (Colorado Section) Frontier Refining Co Boston Bldg Denver 2, Colorado

Jan 1, 1956

By J. D. Ridge

The geologic setting and mineral relationships of seven European massive sulfide deposits that more or less conform to the bedding of the largely noncal-careous sedimentary rocks and/or bedded volcanics in which they are found are considered here. These orebodies consist largely of massive beds or lenses of sulfides usually surrounded by halos of disseminated sulfides and distorted by tectonic activity. The formations containing these deposits have been metamorphosed in varying degrees at times subsequent to their lithification. The ore-forming process is thought to be essentially volcanic, with the ore constituents being brought to the shallow-water site of deposition through tectonic fissures from magma chambers at depth as gases or relatively concentrated hydrother-mal solutions. Certain European ore deposits of base metal sulfide have previously been considered to be of hydro-thermal or magmatic origin, but today a number of European mining geologists consider them to be syngenetically produced. In an effort to provide American geologists with some idea of the reasons behind this change in thought, the geological settings of seven of these deposits have been studied. These are: Ldkken, Meggen, Rammelsberg, Ergani-Maden, Outokumpu, Boliden and Roros. These deposits lie in bedded rocks that have undergone metamorphism from causes not universally agreed upon; most of the formations were originally shales, and may have been intercalated with limey and occasionally quartzitic beds, volcanic tuff, agglomerate, extrusive lavas and usually basic intrusives. Deposits of the conformable type, however, are not confined to these rock types but may be in calcareous and associated igneous rocks or almost entirely in volcanics. These deposits may be closely associated in space with igneous rocks that, again, are usually basic types. Although the ages of the enclosing rocks range from mid-Precambrian (Boliden and Outokumpu) to Eocene (Ergani-Maden), the bulk of them are Paleozoic, with two (Meggen, and eammelsberg) being upper middle Devonian and two (LØkken and RØros) being Cambro-Ordovician. Geographically, two are in West Germany, four in Scandanavia and one in Turkey. Of the seven deposits, six are mined for copper, with three of these also producing zinc, and two lead; one is mined for zinc and minor lead. In the discussions of the seven conformable deposits that follow, I have attempted to present as uniform a treatment as their varying characters will permit. For each deposit, I have considered the stratigraphy of the area, its major structural characteristics, the form of the orebodies, their mineral content, and the origin of the ore. In the last of these subdivisions, I have presented only the viewpoint of those who believe the ores to have been formed by syngenetic processes, processes that went on at the same time as those which produced the beds that enclose the ores but that are not, in the deposits in question, thought to have been sedimentary in the strict sense of the term. The materials of which these orebodies are composed, it is suggested, did actually collect by falling through sea water to the floor of that portion of the sea in which they accumulated. The ore constituents, however, are believed by a considerable number of European geologists to have been added to the sea water from intratelluric sources, probably igneous magma chambers, as exhalations — hydrothermal solutions or volcanic gases. The effect of the encounter with sea water on these ejected gases or water-rich vapors was to precipitate their potentially solid constituents with great rapidity; they were deposited so quickly, in fact, that the amounj of normally accumulated mechanical or chemical sediment deposited over the same period of time was essentially negligible. The ores formed in this manner, however, are generally interbedded with normal sediments or with lava flows, or with any combination of these two types of rock-forming materials. Such departures as these deposits may have from their original mineral content and attitude are thought to be directly related to the degree of dynamic or static metamorphism that they may have undergone after their accumulation. I have not attempted here to present alternate hypotheses to that of so-called exhalative sedimentation although, of course, such exist and, in my

Jan 1, 1963

By R. G. Bowman

DISCUSSIONS of processes for the manufacture of white lead generally open with the statement that white lead is the oldest chemical pigment known to man. This fact is of more than historical interest; in the light of the present extensive use of white lead, ii indicates that the .compound possesses characteristics that make it unique among white pigments, and superior to all ;in its particular field. A greater variety of processes have been proposed for manufacturing white lead than for any other one chemical compound. Only a few of these processes have come into commercial use, however, and a large part of the present production here and abroad is made by the process used in ancient times. The outstanding disadvantages of the old process are that it is slow and laborious, affords no control of the product, and yields at best an impure material lacking in uniformity. Improved processes, sometimes classed all together as "quick processes," have had as their main object the shortening of the time required. Most of them accomplish this and some have yielded a superior product as well, but only two or three are now in use commercially. For centuries the manufacture and mixing of paints has been treated as an art, and the practice has been much influenced by tradition and precedent. There is a reluctance to abandon old materials for this purpose, and as few new uses for white lead have been developed, the adoption of the quick processes has been slow. The electrolytic production of white lead is not-new, a large number of processes and forms of apparatus have been proposed and patented within the past 25 years, all directed toward the, production of white lead, wholly or in part, by electrolysis. One or two of these processes were tried commercially but proved unsuccessful.

Jan 9, 1925

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.' All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.'' This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1' to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

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 M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By A. W. McReynolds

One characteristic of plastic deformation which distinguishes it from elastic strain is the essential inhomo-geneity of plastic strains. Elastic strain varies continuously through a material, and average relative displacements of initially adjacent atoms are only small fractions of their initial spacing, (strains of the order of 0.01 or less). On the other hand, plastic flow corresponds to the appearance of discontinuities in strain of the lattice, such as dislocations or slip bands, where local strain, on an atomic scale, is several orders of magnitude higher. These discontinuities are visible on a microscopic scale as the familiar slip lines (Fig 1). In spite of this obvious microscopic inhomogeneity, however, macroscopic measurements almost invariably show a smooth curve of stress vs. strain (Fig 2b) even if measurements of linear strains be made to an accuracy of one part in 107. This macroscopic homogeneity of strain indicates that the discontinuities in strain on slip planes occur in increments too small or too slow to be recorded individually, and further that they occur sufficiently independent of one another so that the small increments add at random to a smooth stress-strain curve. The present paper describes observations of plastic strain in aluminum of commercial purity and in high purity Al-Cu alloys, where there exists a strong coupling between slip in various regions of the specimen such that once initiated it spreads rapidly through a large volume. The total effect is that of relatively large, rapid, and regularly spaced steps of strain followed by periods of only elastic strain. Fig 2a illustrates the type of "stair-step" stress-strain curve which results. The properties of this cooperative slip phenomenon will be described further in the section on results: in par- ticular it will be shown that each step corresponds to the propagation of a wave of plastic deformation through the specimen. Some interpretations of the mechanism by which it occurs will be made in the following section. Although the type of plastic wave phenomena to be described has not previously been reported, there are numerous cases of related effects in the plastic yielding of metals: YIELD POINT PHENOMENA The most familiar of such effects is the "yield point" observed in low carbon steels, brass, duralurninum, and the like. It consists in the sudden termination of the elastic portion of the stress-strain curve by a large plastic strain. Since the usual tensile machine is such that yielding of the specimen relieves the load, the resulting curve is as shown in Fig 3. As the strain continues, deformation occurs at a lower stress for some time, then follows a rising curve, but with no further sudden yielding. This effect has been observed in brass by Sachs and Shojil and later by many others. Edwards, Phillips and Jones2 made extensive studies of the effect in steel, and of the role of various alloying elements. Although there seems to be fairly clear evidence that the yield point is caused by a hardening of the material by precipitation of impurities, no satisfactory explanation for the sudden yielding has been given. Winlock and Leiter3 have shown that the strain. level of the upper yield point depends strongly on the rate of loading, the yield point increasing by almost a fac- tor of two as the strain rate goes from 0.002 in. per in. per min. to 4.4 in. per in. per min. This effect would seem to imply an incubation period before yielding is initiated at a certain stress. On the other hand, by going to very slow loading rates, Edwards, Phillips and Jones2 showed that the yield point does not become lower and eventually disappear as might be expected, but, on the contrary, begins to rise at loading rates below about 25 Ib per in. per min. becoming much higher than at rapid loading rates. STRAIN AGING If, instead of continuing straining of a specimen after occurrence of a yield point, the load is removed and the specimen aged, resumption of the test results in occurrence of another yield point as shown by the dotted curve of Fig 3. The new yield stress is generally higher than the previous maximum applied stress. This hardening of the material by straining and subsequent aging is undoubtedly related to quench age-hardening resulting from the aging of a specimen quenched from high temperature. Since neither effect is observed in pure metals, it is generally accepted that quench-aging in all cases is the result of hardening by precipitation of a supersaturated alloying element, and that strain-aging is probably a similar precipitation, accelerated by disruptions of the lattice by previous strain. Pfeil4 has shown that strain-aging does not occur in iron from which all of the carbon has been removed, but that only a very small carbon content, around 0.003 pct, is necessary to cause strain-aging. In accord with this observation is recent work by Dijkstra5 in this laboratory showing that the solubility limit of carbon in iron is extremely low, less than 0.001 pct at 400°C. Edwards, Phillips and Jones2 have shown that the strain-aging effect is also removed by the addition of small quantities of elements such as Mo, Mn, Ti, and the like, which readily form carbides. Their results demonstrate the

Jan 1, 1950

By Armando M. Lago

Secular and cyclical patterns of postwar sources and uses of funds of the mineral sector are analyzed. A simultaneous equation behavior model of sources and uses of funds is developed for both mining firms and integrated producers, and these models were put through the task of predicting the financial and expenditure be-havior of mineral corporations in response to mergers and changes in investment tax credits and depletion allowances. Finally, the quantitative analysis methodology is applied to the analysis of optimum capital structure of mining corporations. The postwar changes that have occurred in the expenditure and financial behavior of mineral corporations are reviewed, particularly the relative importance of factors that affect the industry's supply and demand for funds. This quantitative statistical investigation of factors affecting sources and uses of funds of mineral corporations is achieved through the formulation of a simultaneous equation model of sources and uses of funds. After a description of the study sample, the postwar cyclical and secular financial behavior of mineral corporations is analyzed in detail. An econometric model of mineral corporate financial behavior is formulated. This model is then estimated and reviewed. Policy issues regarding depletion allowances, investment tax credits, and industrial organization of the mineral sector are discussed. Finally, the optimum financial structure of mining firms is discussed and the effect of corporate financial structure on the mining corporations' average cost of capital is analyzed.

Jan 1, 1971

By W. A. Backofen, A. T. English

The kinetics of re crystallization were determined metallographically for a 3-1/4 pcl Si-Fe rapidly compressed at temperatures of 710° to 911°C, and held for various times at the working temperature. As in re crystallization following cold wwk, the time for re crystallization was reduced by increased temperature and strain. Nucleation occurred chiefly at grain edges, although other pre-existing interfaces, notably inclusions, also served as nucleation sites. The importance of intragranular nucleation to grain refinement in hot working is pointed out, together with some possible techniques by which nucleation might be induced within the grains. The observed isothermal growth rates are quite accurately described by the equation G = 4 x 10-'/t (cm per sec), independent of temperature and strain at all but the shortest times. Changes in G during recrystalliza-tion can exceed two orders of magnitude. It is argued that release of stored energy associated with lattice defects cannot adequately explain the time dependence. A suggested alternative involves processes of solute segregation and desegregation in the unrecrystallized matrix and at the moving boundary, respectively. EFFORTS to improve hot-working practice are hampered by an incomplete understanding of the fundamental metallurgy involved. Research directed at establishing the required basic foundation falls into two categories, the first concerned with measurement of mechanical properties under the conditions of high temperature and strain rate which characterize such processing, the second focused on structure and its relation to the deformation conditions. Rossard,' Rossard and Blain,2 and Hardwick and Tegart have conducted many high-speed, high-temperature torsion tests on various metals. One of their objectives was interpretation of stress-strain curves in terms of the structures of specimens rapidly quenched following interruption of twisting. They showed that appreciable hardening occurred in the early part of the test, and that this hardening reflected the concurrent development of an increasingly dense substructure within the grains. The detailed nature of this substructure was observed to depend on the ease of polygonization which, at least in fcc metals, varies with the stacking-fault energy.= By holding specimens after interruption but before quenching, the nucleation and growth of new grains could also be studied. Some success has been realized in relating the microstructure of hot-rolled steel to its temperature:strain rate:strain history with such testing.' The same general observations have been made by others investigating rolling4f5 and drop-hammer forging.~-~ Incident to these experiments, some efforts were made to determine the kinetics of re-crystallization as well as the velocity of the migrating boundaries. The results have been largely qualitative, owing to difficulties of interpreting hardness measurements5 and microstructures. The work described here was undertaken to obtain more quantitative information from tests on a material having suitable metallographic properties, and, in this way, to provide further insight into the fundamentals of this practically most important kind of deformation processing. I) MATERIALS AND EXPERIMENTAL TECHNIQUES Materials. Electrolytic etching of a Si-Fe alloy reveals dislocations and substructure in unrecrystallized grains.8'9 This unique characteristic makes possible a precise determination of the extent of recrystallization. For that reason, it was the material selected for all experiments in the present work. The two particular alloys that were used are identified in Table I. A major difference between "A" and "B" is the number of inclusions, as noted in the table. Most of the experiments were made with material "A". It was received as hot-rolled plate 1 in. thick, sawed to 2-in. widths, hot-forged at 1200°C to 5/8-in. rounds, and finally annealed in a mechanical vacuum at 1000°C for 24 hr. The result was substructure-free grains of mean diameter 0.05 cm.*

Jan 1, 1964

By F. E. Bash

Constantan is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported and the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts against pure iron at 1500" F. (816" C.) with the cold-junction temperature at 0" F., or a proportional e.m.f. at temperatures near 1500" F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure iron. The couple was then insulated and the fire end was tied to the

Jan 1, 1921

E. K. Landis, Philadelphia, Pa. (communication to the Secretary) : Mr. Firmstone's paper is of great interest; but he has unfortunately otnitted to state the most important point, viz., the percentage of sulphur in the two materials he compares; and this omission vitiates the conclusions which he draws. Comparing by grade, instead of silicon-contents (as in his Table III.), the iron made using limestone with that made using dolomite, we find for gray-forge the average of four analyses under limestone to be, Si, 0.644; S, 0.089 ; while one analysis under dolomite gives Si, 0.508 ; S, 0.070. For No. 2 iron, the limestone flux gives, as an average of 19 analyses, Si, 1.107; S, 0.051; while the average of 4 analyses made with dolomite flux gives Si, 0.630; S, 0.056. It will be observed, that no No. 1 pig is given under limestone, while 14 analyses appear under dolomite, averaging Si, 0.950 ; S, 0.028. As nothing is said about changed conditions, it is Fair to presume that the ore and fuel, as well as the blast-temperature (which is stated to have been uniform at about 750' F.) remained practically the same; and since the sulphur in the two fluxes is not given, it is impossible to know whether the lower sulphur for equal silicon-contents is due to the use of dolomite or to other conditions. The use of dolomite would produce a more fusible cinder, and the furnace would be hotter than when using limestone; therefore, we might expect to see a grayer iron. The amount of So. 1 iron made with dolomite seems to confirm this supposition; and, under these conditions, we might expect more of the sulphur to be volatilized, and to pass off in the gases. The easier fusibility of the cinder would also permit more rapid driving; and this should reduce the amount of silicon and sulphur in the iron, as the amount of reduced metalloids in the pig is directly proportional to the length of time it remains in the reducing-zone.

Jan 1, 1895

By T. R. Cass

THE renewed interest in titanium, resulting from its increasing application as a structural material, has stimulated basic deformation studies on this metal. In the course of our work, we have developed a dislocation etchant and applied it to a perfection study of melt-grown single crystals as well as to a preliminary investigation of plastic deformation in titanium. The etchant, Keller's etch (21 cu cm HF, 64 cu cm HC1, 106 cu cm HNO3, and 160 cu cm H20), reveals the emergence of both grown-in and fresh dislocations on pure titanium and a-phase Ti-Al single crystals. Pits are produced only on surfaces within a few degrees of the basal plane; the more exactly parallel to a basal plane the surface is, the more distinct are the pits. The observed pit density, however, does not appear to depend on the surface orientation; the pits simul- taneously become less distinct as the misorientation from a basal plane increases. Etch times are short, a few seconds, for pure titanium; longer times are necessary for alloy crystals.

Jan 1, 1968

By Henry Rawdon

THE RELATION between the course, or path, of the fracture of metals and alloys, produced in service or as a result of certain laboratory tests, and the crystalline units of which such materials are composed is of utmost importance. The fracture of normal material is, in general, intracrystalline, i.e., it consists of a break across the grains rather than of a separation between them. An intercrystalline fracture indicates either that the metal is of very inferior quality or that the break occurred under very unusual conditions, e.g., at a very high temperature. The usual mechanical tests, when applied to metals of the type that breaks with an intercrystalline fracture, merely measure the coherence of adjacent grains for one another and reveal little as to the real properties of the metal itself. Even such a soft plastic substance as lead, under suitable conditions, may be rendered so weak and brittle that the metal can be easily crumbled into powder by the fingers although the constituent grains have lost none of the intrinsic properties of lead. Various erroneous explanations of this behavior of lead have appeared in the scientific literature, the change being described usually as an allotropic one. The importance, in an industrial sense, of a proper explanation of this type of the corrosion of lead justifies the description of the type of metal deterioration that follows.

Jan 2, 1920

By J. P. Murphy, T. E. Leontis

DURING the last few years, the trend in the aircraft and automotive industries has been toward higher and higher operating engine temperatures. This has created considerable interest in the effect of temperature on the properties of alloys. In the magnesium field, it has been recognized for many years that the addition of cerium imparts high strength and good resistance to creep at elevated temperatures. Beck,1 in his treatise on-magnesium, has summarized the work of German investigators. This includes the unpublished data of Menking, showing the increase in strength and hardness of extruded alloys containing 2 to 20 per cent Ce at temperatures from 200 to 300°C. (68° to 572°F.) and the results of Vosskühler, who demonstrated the improved resistance to creep of alloys containing 6 per cent Ce plus 2 per cent Mn and 0.5 per cent Ce plus 2 per cent Mn at 150°C. (302°F.). Wellinger and Keil2 have also reported the creep properties of a forged magnesium-cerium-manganese alloy at 200° and 250°C. (392° and 482°F.). Haughton and Prytherch have determined the tensile properties of various forged magnesium alloys containing cerium, cerium plus manganese, cerium plus calcium, cerium plus nickel, cerium plus nickel plus manganese, and cerium plus cobalt plus manganese at temperatures up to 290°C. (554°F.). Magnesium-cerium alloys have been used in some commercial applications. It is reported that an alloy containing 3 per cent Ce plus 0.5 per cent Mn plus 0.5 per cent Ca is being used on a forged impeller in Great Britain. Two forged parts made from an alloy with a nominal composition of 5 per cent Ce and 2 percent Mn have been found on the German .BMW-801D aircraft engine. These two forgings consist of a supercharger impeller and a rear cam-follower guide. In this country, several types of pistons have been made experimentally in both .the cast and the forged conditions from an alloy containing 6 per cent Ce plus 2 per, cent Mn and in the cast condition from an alloy of magnesium plus 10 per cent Ce. The cast pistons have been tested in various types of internal-combustion engines, with promising results. This paper presents the results of an extensive investigation on the properties of various cerium-containing magnesium alloys in both the cast and the forged conditions. Data are presented to show the beneficial effects of increasing amounts of cerium on the mechanical properties of magnesium at elevated temperatures. The effects of heat-treatment on the properties of these alloys and the attendant changes in the microstructure are discussed. The

Jan 1, 1946