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By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.' Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.' Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,' has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

By H. H. Uhlig

IN our study of the mechanism of and the prevention of corrosion in stainless steels, it was considered of fundamental importance to obtain knowledge of the surface structure of such alloys. If corrosion resistance is due to a self-healing oxide layer, which like a paint film protects the underlying metal, it would be obviously relevant were the effort made to make the film less permeable and more adherent; for example, the surface might be expected to respond to an anodizing process, which is found successful in increasing the film thickness and corrosion resistance of aluminum. However, if passivity and corrosion resistance of stainless steels are due to another cause, the attack of the problem would follow another path. One of the most effective techniques for studying passivity and corrosion tendency is the measurement of the electrochemical potential. Not only can one determine by potential measurements whether a metal is active or passive, but also one can determine the degree of passivity and rate of transformation of passivity with time. Chemical media that build up or destroy passivity when in contact with the steel can also be classified by potential measurements. Something can be learned, too, of the effect of alloy additions such as molybdenum to 18-8, known to decrease corrosion of the alloy in chloride solutions. A study of alloys in previous investigations has sometimes included data on the electrochemical potentials. Tammann and Sotter1 measured the electrochemical potentials of alloys of iron-molybdenum and iron-chromium and reported the critical concentration of molybdenum or chromium at which passivity initiates. Strauss2 made similar measure-ments for the iron-chromium system. The electrochemical potential' has also been used to indicate carbide precipitated 18-8. In 18-8, heat-treated to precipitate carbide, active metal exists at the region of the grain boundaries, contrasted with passive metal within the grains, the active metal accounting for a resultant active potential. Several

Jan 1, 1939

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y ' and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? ' phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?' and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

By Newell G. Alford

At its meeting in the fall of 1937, the Executive Committee of the Coal Division considered the growing scarcity of young engineers entering coal mining with serious intentions. This scarcity was the cause of considerable alarm and a committee consisting of C. T. Hayden, E. A. Holbrook, C. E. Lawall and L. E. Young, with the writer as chairman, was appointed to gather factual data on the current trend. A questionnaire1 was designed and mailed to the heads of the 60 mineral technology schools listed by Prof. W. B. Plank in his article in September 1937.2 Replies were received from 46 institutions, not all from heads of coal-mining courses but all from men that at one time or another have had experience with some kind of coal-mining curricula and know current student impressions. Our committee is indebted to all of these gentlemen for their cooperation. Our committee hoped by this means to quickly reach the root of the trouble and make a set of comprehensive recommendations to the Coal Division for relieving the industry immediately from the growing dearth of youth who yearn for coal-mining careers, but the condition is more serious than at first diagnosed. We must now refer the question back to the Coal Division, with the recommendation that the Division get the industry's permission for still another major operation on its frame of mind. In addition to 10-year statistics on the first pay received by graduates in coal mining and other technical work, we requested enrollment data for 20 years from all schools with either mining engineering or mineral technology curricula. Nine leading questions were also plied, as shown in the Appendix. Every one of the answers was significant and interesting. Fortunately, we encountered positive frankness that was extremely helpful.

Jan 1, 1938

By Newell G. Alford

At its meeting in the fall of 1937, the Executive Committee of the Coal Division considered the growing scarcity of young engineers entering coal mining with serious intentions. This scarcity was the cause of considerable alarm and a committee consisting of C. T. Hayden, E. A. Holbrook, C. E. Lawall and L. E. Young, with the writer as chairman, was appointed to gather factual data on the current trend. A questionnaire1 was designed and mailed to the heads of the 60 mineral technology schools listed by Prof. W. B. Plank in his article in September 1937.2 Replies were received from 46 institutions, not all from heads of coal-mining courses but all from men that at one time or another have had experience with some kind of coal-mining curricula and know current student impressions. Our committee is indebted to all of these gentlemen for their cooperation. Our committee hoped by this means to quickly reach the root of the trouble and make a set of comprehensive recommendations to the Coal Division for relieving the industry immediately from the growing dearth of youth who yearn for coal-mining careers, but the condition is more serious than at first diagnosed. We must now refer the question back to the Coal Division, with the recommendation that the Division get the industry's permission for still another major operation on its frame of mind. In addition to 10-year statistics on the first pay received by graduates in coal mining and other technical work, we requested enrollment data for 20 years from all schools with either mining engineering or mineral technology curricula. Nine leading questions were also plied, as shown in the Appendix. Every one of the answers was significant and interesting. Fortunately, we encountered positive frankness that was extremely helpful.

Jan 1, 1938

By A. R. Kinkel

Robert T. Walker and Woodville J. Walker (Walker Engineering Corp., Salt Lake City)—Mr. Kinkel's article embodies, in condensed form, the results of the first detailed and complete geological survey that has ever been made of the long neglected but potentially very important West Shasta Copper-Zinc district, in Shasta County, California. In view of the difficulties of the terrain and the complexity of the geological structure, this represents a notable achievement, and it is with regret, therefore, that the writers find it necessary to differ from Mr. Kinkel's conclusions on two important points. The first has to do with the interpretation of two members of the stratigraphic column of formations in the district; for purposes of comparison, the description of these two members according to Mr. Kinkel is shown parallel to the description of these members according to the writers, see Fig. 14, Mr. Kinkel's nomenclature being used. The first member, which Mr. Kinkel terms the upper unit of the Balaklala rhyolite, consists of a single, massive, homogenous body of very silicious igneous rock, consisting almost wholly of quartz and albite, and averaging about 80 pct silica. Most geologists of the U. S. Geological Survey who have previously inspected the district have called it an alaskite. It is not a pile of several members, but is a single unit, without internal subdivisions. It has the form of a recumbent lens, approximately flat on the bottom and arched on top, several miles in diameter, and attaining a maximum thickness of 1000 to 1200 ft. It varies in texture from porphyritic to holocrystalline, and contains unusually large quartz phenocrysts up to 4 mm diam. Mr. Kinkel considers this formation to be a thick lava flow that is older than the overlying Kennett shale, while the writers interpret it as being intrusive, constituting a domed sill or laccolith that is younger than the Kennett shale. Their reasons are as follows: 1) This formation shows none of the features which within the writers' experience invariably accompany very silicious lava flows. Nowhere is it vesicular; nowhere does it contain any glass or its devitrified equivalent; nowhere does it contain flow breccia; and nowhere has it a ragged top, in spite of the fact that there is no evidence of surface erosion, which might have removed such a top.

Jan 1, 1957

By Y. C. Liu, W. R. Hibbard

An analysis of the relationship between the deformation and recrystallization textures in face-centered-cubic metals is presented. The analysis assumes that orientations of the secondary as well as the primary textures are related to the deformation texture. The effect of alloying elements on the recrystallization texture of copper-base alloys is also discussed. ROTATIONAL relationships based on prior orientations have been used to derive both the primary and secondary recrystallization textures."" This similarity suggests that, if the secondary texture arises from grains formed during primary recrystallization, as proposed by Dunn: and if primary recrystallization derives its lineage from the deformation structure, then the orientations obtained in secondary recrystallization .as well as those obtained in primary recrystallization should be related to the deformation texture. The following discussions are

Jan 1, 1956

By D. D. Lambert, E. C. Simmons

Rare earth element (REE) analyses of cumulus plagioclase from the PGE ore zone of the Stillwater Complex indicate that pressure fluctuations in the magma chamber acting on a single magma cannot be responsible for features such as the reappearance of Mg-rich olivine on the liquidus. The data are more consistent with a model involving multiple injection and mixing of geochemically distinct magmas. The PGE-bearing sulfides of the J-M Reef are associated with such a reappearance of olivine, indicating that the unusual location of the ore zone may be related to the addition of new magma, compositionally distinct from magmas that produced cumulates in the Ultra- mafic zone of the complex.

Jan 1, 1984

By A. D. Hoagland

The Flat Gap mine is located on Copper Ridge in the Appalachian Valley of East Tennessee. Large zinc orebodies occupy zones of solution and collapse breccias in Lower Ordovician Kingsport limestone and dolomite. The principal ore mineral is sphalerite and the principal gangue is dolomite. The ore-bearing horizons are considerably more than 95% covered by thick residual clay. Geochemical prospecting under these conditions is an effective exploration technique which played an important role in the discovery and exploration of the Flat Gap mine. The Flat Gap mine, an important zinc deposit of the Appalachian type, is located in the Copper Ridge Belt in the Valley of Tennessee approximately 30 miles northeast of the Mascot-Jefferson City zinc district (Fig. 1). The ore is found in large stratigraphically linked deposits in solution and collapse breccias of the Kingsport, Longview and, to a minor extent, Mascot formations of Lower Ordovician age. The principal ore mineral is sphalerite and the principal gangue minerals are dolcrmite and accessory pyrite. There is local minor galena and very rare barite and fluorite. The ore-bearing horizons are covered by about 20 to 100 ft or more of residual clay except where active streams have exposed bedrock. Considerably less than 5% of the favorable host rocks are exposed in outcrop, and this nearly complete soil cover creates a serious obstacle to exploration. Comprehensive surveys of the base metal content of soils furnish a useful substitute for outcrop geology, and under favorable conditions, this technique is a very valuable prospecting tool. The analysis is carried out by a titrametric dithizone method modified after the procedure described by E. B. Sandell.' This method detects

Jan 1, 1962

By Lawson P. Entwistle

One of the important reserves of mangani-ferous iron ore is at Boston Hill, near Silver City, New Mexico. The area consists of a faulted block of gently dipping Lower Paleozoic shale, dolomite, limestone and sandstone, which has been intruded by a roughly circular mass of quartz-bearing monzonite porphyry and subordinate dikes. Prom a noselike protuherance of the intrusion radiate many premineral faults, which have localized much of the hypogene mineralization. Three important stages of hypogene mineralization can be recognized: (I) mesitite, a manganiferous iron magnesite, (2) quartz sulphides, and (3) barite-galena The carbonate stage is widespread but stronger near the intrusion. The quartz may have been derived from hydrothermal alteration of the igneous rocks. Barite-galena is most important in the Chloride Flat mining district, about one mile north, where argentiferous galena provided silver for the supergene ore. The hypogene carbonate, lean in iron and manganese, has been oxidized and consequently enriched by meteoric waters containing an excess of oxygen and carbon dioxide to form ore bodies of intimately mixed hematite and pyrolusite. The ore bodies, at one place attaining a length of 1600 ft., a width of 300 ft., and a thickness of 25 ft., are largely confined to areas of brecciation and to spreads from faults in Silurian dolomite beneath soft Devonian shale. Boston Hill comprises three rolling hills southwest of and adjoining the town of Silver City (pop. 5044), Grant County, N. Mex. The mining district covers less than 2 sq. miles. Silver City, on a branch line of the Atchison, Topeka, and Santa Fe Railway, is a supply point for the important mining communities at Santa Rita, Hurley, Hanover, Tyrone, and Mogollon. The Chloride Flat mining district adjoins Boston Hill on the north. History and Production Bonanza-type silver ores were discovered in the Chloride Flat mining district during the silver boom of the seventies and eighties, at which period it has been credited with as much as $5,000,000 production. In 1916 manganiferous iron ore was first shipped from the Boston Hill mining district to Pueblo, Colo., where it was mixed with manganese ore from Lead-ville and smelted into spiegeleisen. During 1926 and 1927 the Colorado Fuel and Iron Co. mined and churn-drilled part of the district. Mining operations ceased during the depression of the thirties, but production was resumed in 1937. Since 1916 the Boston Hill mining district has produced about 600,000 long tons of ore averaging about 12 per cent manganese and 35 to 40 per cent iron.

Jan 1, 1949

By Lawson P. Entwistle

One of the important reserves of mangani-ferous iron ore is at Boston Hill, near Silver City, New Mexico. The area consists of a faulted block of gently dipping Lower Paleozoic shale, dolomite, limestone and sandstone, which has been intruded by a roughly circular mass of quartz-bearing monzonite porphyry and subordinate dikes. Prom a noselike protuherance of the intrusion radiate many premineral faults, which have localized much of the hypogene mineralization. Three important stages of hypogene mineralization can be recognized: (I) mesitite, a manganiferous iron magnesite, (2) quartz sulphides, and (3) barite-galena The carbonate stage is widespread but stronger near the intrusion. The quartz may have been derived from hydrothermal alteration of the igneous rocks. Barite-galena is most important in the Chloride Flat mining district, about one mile north, where argentiferous galena provided silver for the supergene ore. The hypogene carbonate, lean in iron and manganese, has been oxidized and consequently enriched by meteoric waters containing an excess of oxygen and carbon dioxide to form ore bodies of intimately mixed hematite and pyrolusite. The ore bodies, at one place attaining a length of 1600 ft., a width of 300 ft., and a thickness of 25 ft., are largely confined to areas of brecciation and to spreads from faults in Silurian dolomite beneath soft Devonian shale. Boston Hill comprises three rolling hills southwest of and adjoining the town of Silver City (pop. 5044), Grant County, N. Mex. The mining district covers less than 2 sq. miles. Silver City, on a branch line of the Atchison, Topeka, and Santa Fe Railway, is a supply point for the important mining communities at Santa Rita, Hurley, Hanover, Tyrone, and Mogollon. The Chloride Flat mining district adjoins Boston Hill on the north. History and Production Bonanza-type silver ores were discovered in the Chloride Flat mining district during the silver boom of the seventies and eighties, at which period it has been credited with as much as $5,000,000 production. In 1916 manganiferous iron ore was first shipped from the Boston Hill mining district to Pueblo, Colo., where it was mixed with manganese ore from Lead-ville and smelted into spiegeleisen. During 1926 and 1927 the Colorado Fuel and Iron Co. mined and churn-drilled part of the district. Mining operations ceased during the depression of the thirties, but production was resumed in 1937. Since 1916 the Boston Hill mining district has produced about 600,000 long tons of ore averaging about 12 per cent manganese and 35 to 40 per cent iron.

Jan 1, 1949

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10&apos; dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By J. van Lookeren

In the case of a reservoir where the oil underlies a large gas cap and overlies bottom water, production can be inzproved considerably if wells are perforated below the water-oil contact rather than opposite the oil-bearing section. The theoretical arguments for this improvement, which in some cases may be tenfold, are supported by experimental evidence. INTRODUCTION Reservoirs frequently consist of one sand body containing an oil layer underlying a thick, gas-bearing section and overlying bottom water (Fig. 1). Wells in such reservoirs are customarily opened up opposite the oil-bearing interval or, rather, opposite the lower part of this interval (Fig. 2). More often than not, it is inefficient or prohibited to blow off large quantities of gas with the oil. This im-psses a severe limitation on the drawdown, which results in low oil-production rates. Because of the small difference in specific gravity between oil and water, the latter will easily cone upwards, so that the production of water together with the oil is not prevented by this completion method. In such a situation wells should be opened deeper, in the originally water-bearing zone. The gas can be shut off by not perforating over the upper part of the interval (Fig. 3) or by a tubing hung close to the bottom of the interval (Fig. 4). Initially much water will be produced, but when steady-state conditions have been established (as depicted in Figs. 3 and 4) larger drawdowns are permissible than in a conventionally completed well, and correspondingly higher oil-production rates will result. Water cuts are only slightly higher because of the small effect of gravity on the water-oil flow distribution. CALCULATIONS The ratio of improvement has been estimated by means of approximate calculations. The completion depicted in Fig. 4 is the most convenient basis for these calculations. By postulating that vertical flow gradients can be disregarded, the Appendix shows that the well-known Dupuit formula can be obtained except for some complication due to the presence of two fluids rather than one. The Appendix makes the reasonable assumption that, for suitable boundary conditions, the oil layer occupies a constant fraction of the total fluid height throughout the reservoir. The oil- and water-production rates can thus be related to the liquid levels in the borehole as follows:

Jan 1, 1966

By W. L. Phillips

Stress-strain data are reported for sodium chloride, lithium fluoride, and magnesium oxide tested in compression at diffevent strain rates in the telrlperature range from 70° to 873°K. Quantitative equations are given for the stvain-rate dependence of the critical resolved shear stress and the initial rate of work havdening. The properties so determined are compared with results previously reported for metals. ALTHOUGH the effects of strain rate and temperature on the stress-strain characteristics of metals have been extensively investigated1,2 these effects have not been studied in detail in ionic crystals. In the only previous investigations on the effect of strain rate on the deformation of ionic crystals. Gilman and gohnston3 and Hulse and pask4 have shown that the yield stress of lithium fluoride and magnesium oxide at room temperature is proportional to the ninth or tenth root of the strain rate. CRYSTAL PREPARATION Lithium fluoride, sodium chloride. and magnesium oxide single crystals were purchased from the Har-shaw Chemical Co. The compression fixture and sample preparation have been described in detail previously.5 The detectable impurities in MgO were eight parts in 105 of Fe and six parts in 105 of Si; in LiF, six parts in 105 of Mg; and in NaC1, two parts in 105 of Fe and four parts in 10&apos; of Mg. The cleaved samples measured - 0.1 in. by 0.1 in. by 0.3 in. Prior to testing all samples were annealed at -0.8 of their melting point and cooled to room tempera- ture at 50 C per hr.&apos; Samples were strained at rates (<) of 0.1, 0.01, 0.002, and 0.0002 in. per in. per min. EXPERIMENTAL RESULTS Fig. 1 is a plot of the critical resolved shear stress a,. (extrapolation of slope of easy glide region to zero strain) of sodium chloride, lithium fluoride, and magnesium oxide tested at different strain rates as a function of temperature. In all crystals at all strain rates a, decreases with increasing temperature according to an equation of the type397 where uo is a stress constant, K is a constant, and T is the absolute temperature. The points in Fig. 1 are the average of six tests. It is evident that there is a break in the log 0,- temperature plots at a characteristic temperature T,. The constant K of Eq. [I] is dependent on strain rate, Fig. 2. The relationship

Jan 1, 1962

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll &apos;dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949

By L. M. Pidgeon, W. Curlock

FREE energies of formation of zinc sulfide and magnesium sulfide had previously been estimated to an accuracy of ± 5.0 kcal per g mol. In the present work, these values were determined experimentally. As the determinations of the free energies of formation of zinc sulfide and magnesium sulfide presented different problems, separate experimental procedures were employed for each. ZINC SULFIDE It is difficult to measure the free energy of formation of either zinc sulfide or magnesium sulfide by measuring their decomposition pressures directly, as they are very stable compounds. An attempt was made by Jellinek and zakowski3 to study the equilibrium. zns(s) + H2(g) = Zn(g) + H2S(g) [I] They passed hydrogen over zinc sulfide and analyzed the gases leaving the reaction zone for H2S. They were unable to determine the true partial pressures of the H2S by this method, as some of the H2S on being cooled from the reaction temperature, reacted with the zinc in the gas to produce ZnS. Consequently, they were unable to establish any true equilibrium data for reaction [I]. More recently,&apos; the equilibria ZnS(sphaledte) + Fe (s) — FeS(s) + Zn(g) [2] and ZnS(sphalerite) + 2Cu(s) — Cu2S(S) + Zn (g) [3] were studied. As the standard free energy of formation of Cu2S is known to * 3.0 kcal, and of FeS to ± 1.0 kcal, it should be possible upon performing equilibrium studies on reactions [2] and [3] to deduce the standard free energy of formation of ZnS (sphalerite). However, as both of these equilibria involve 2 solid sulfides, and as it is possible for these sulfides to dissolve in one another, it is necessary first to ascertain the activities of the various sulfides in these solid phases.

Jan 1, 1959

R. H. Sweetser, Sault Ste. Marie, Ont. (communication to the Secretary*):—The recent work of furnace No. 1 of The Algoma Steel .Co., at Sault Ste. Marie, Ontario, using for fuel, first all charcoal, then a mixture of charcoal and coke, and finally all coke, upsets the estimates given by Mr. Hall in the last two paragraphs of his interesting paper. Furnace No. 1 was built for a charcoal-furnace, and it was run on charcoal fuel from March 6 until July 9, 1905; then, for a week, a mixture of charcoal and coke was used, and, since then, coke alone has been the only fuel. It is to be regretted that at no time, during the run on charcoal, was there enough charcoal on hand and " in sight" to warrant blowing the furnace as hard as it should have been blown. During April and May the supply of charcoal limited the amount of blast to about 8,000 cu. ft. of air per min.; in June, to about 8,900 cubic feet. For a few days in July about 10,000 cu. ft. were blown, and then the maximum daily output, 173 tons (2,240 lb.), was reached. At all times the quality of the charcoal was poor, having been made from wood cut from three to four years before. Doubtless this furnace could have produced 200 tons of iron per day, even with this quality of charcoal, provided the supply had been sufficient; and with

Jan 1, 1906