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By Hobart M. Kraner, E. B. Snyder

THIS paper shows that volume stability, low porosity and decreased pyroplasticity are desirable for blast-furnace linings, particularly for the hearth. It shows further that a hot load test is a valuable means of testing the fusion or softening behavior of a refractory at operating temperatures. The effect of carbon monoxide on commercial blast-furnace refractories in their as-received condition and after refiring is reported, showing that many commercial blast-furnace refractories disintegrate badly but that refiring decreases the effect and certain special refractories are now available which are almost free of the tendency. FACTORS AFFECTING CHOICE OF REFRACTORIES If one were to depend entirely upon experience or trial in the selection of clay refractories, the solution of a problem would be a slow process. Furnace campaigns are so long and attended by so many variables that it is difficult to draw fine distinctions within a reasonable period of time in regard to the quality of refractories used. It could be said, of course, that if service results do not yield the proper information for intelligent choice, there is no difference in the quality of brick being considered, but this is not necessarily true. Conventional ceramic tests are designed to give the ceramic engineer information as to the refractoriness and firing temperature, which he in turn interprets in terms of volume stability, ability to withstand load at high temperature (pyroplasticity), permeability, chemical stability and resistance to the action of slag. In most refractory applications several of these factors are involved. In a particular instance, one requirement may be predominant, while in others some other factors may be of primary importance. In this country, clay refractories are generally made from mixtures of plastic and flint fire clays. The process of firing a clay refractory is one of slowly melting the constituents, and during this operation its porosity is gradually reduced. The process is arrested, of course, in its incipient stages and the progress is determined by measuring slight changes in. porosity, volume, bulk gravity, etc., that have taken place. Often the temperatures to which clay refractories are exposed in service are higher than those employed in their firing. However, if the manufacturer were to fire them at such high temperatures the brick would distort. Therefore it would be difficult for the manufacturer to fire all of his clay refractories to temperatures . at which they are to be used, although in many cases it would be desirable from the user's point of view if he would do so. The porosity of clay refractories decreases by firing, to a minimum limit, after which a further increase in the temperature causes expansion in certain clay constituents and bloating in others. -Both may occur in the same refractory containing two such clays.

Jan 1, 1944

By Stanley D. Michaelson, Norman Weisis

The purpose of beneficiation is to increase the economic value of an ore by elimination of waste rock or by separation of minerals that require separate reduction, without destroying the physical and chemical identity of the minerals. Flotation has replaced older methods of beneficiation to a very great ex- tent, nearly entirely in the case of the copper, lead, and zinc minerals and less completely in the case of such other minerals as iron, coal, and titanium. Flotation is also used to recover barite, fluorspar, feldspar, cement rock, spodumene, vermiculite, silica, beryl, and potash in the nonmetallic field, and cobalt, vanadium, germanium, antimony, mercury, molybdenum, manganese, nickel, gold and silver, cadmium, and bismuth for metals. The rapid growth of flotation to pre-eminence cannot be attributed to its low cost, because gravity, magnetic, and electrical methods may in some cases cost only half as much. But for ores containing finely disseminated minerals, these other methods are successful only in exceptional cases, for example the magnetic taconites or titanium-bearing sands. For low grade ores with coarse texture or spotty mineralization the advantages of low-cost gravity methods and highly efficient flotation are often combined, as in the beneficiation of coal and some ores of lead and zinc, phosphate, tungsten, and manganese. When an ore is responsive to either flotation or non-flotation concentration, or to combinations of the two, the choice depends upon cost of the process only when dealing with ores of low value; in other cases it is dictated by either the process efficiency or the product specification. Generally speaking, flotatio.1 is so efficient as compared with other methods of concentration that process cost is rarely an important factor in its selection. It is said, "The metal in the mill tailing has already been mined." Once the mining cost has been paid it doesn't increase total costs very much to do a thorough job of milling. With the exception of the few types of ores that are not amenable to flotation, the chief reason for preferring electrical and gravity methods to flotation may lie in the specification of the product. Flotation demands fine grinding, and specifications may not permit this with many nonmetallic ores or coal. Another reason is the size of investment-where capital is hard to obtain or the life of the property is short, the justification for a flotation plant may not exist, and one must be content to skim off the cream. y not exist, and one must be content to skim off the cream. Gravity processes often cost less than flotation because a large part of the waste rockcan be rejected without costly grinding, no chemicals are required,

Jan 1, 1962

By A. H. Daane, J. F. Haefling

The limits of miscibility in some of the uranium rare-earth alloy systems have been determined in the temperature range 1000°to 1250°C. The solubilities of lanthanum and cerium in uranium are greater than those of the remaining rare earths by a factor of more than two. The solubility of uranium is greater in cerium, braseodymium, and neodymium than in the other rare-earth metals studied. The values found in this study are in qualitative agreement with those which might be expected if the solubility rules of Hildebrand and Scott are applicable. AS interest in nuclear reactors intensifies, many new types of fuels are being suggested in attempts to improve the economics of some of the proposed reactor schemes. To remove some of the difficulties inherent in the use of solid-fuel elements and their reprocessing, many types of liquid-metal reactors have been suggested. One of the more attractive features of several of these reactor concepts is that they include a continuous or semicontinuous process for the extraction of fission products and "bred" fissionable materials from the fuel, utilizing immiscible metal extractants. This would enable a much higher burn-up of fissionable material to be achieved and would present a very attractive economic picture. Several studies have been reported on equilibrium systems in which there exists a high degree of immiscibility between uranium and another metal that might be used as an extractant in such a processing scheme.' Two of these systems in which a high degree of immiscibility exists are those of uranium with the two rare-earth metals, lanthanum, and cerium. Since the rare earths constitute a significant fraction of the fission products, their removal is of prime importance. It is reasonable to believe that this might be accomplished by equilibrating a rare-earth phase with the contaminated uranium fuel in the liquid state. In order to make a more complete study of those systems which would be of interest either as extractants in a liquid-liquid extraction process, or as fission products formed in the fuel, the alloy systems of uranium with lanthanum, cerium, praseodymium, neodymium, and samarium were studied in some detail in the temperature range 1000" to 1250°C; less detailed studies were made with the other rare earths. In addition to being of value to the reactor program, the data obtained in this study should be of help in making a study of the role played by the electronic structures of metals in determining the nature of metallic solutions. The unique electronic structures of the rare-earth elements make them particularly interesting in this respect. EXPERIMENTAL The usual procedure for a solubility determination was to seal equal volumes of uranium and the particular rare earth in a tantalum crucible under an atmosphere of helium; this crucible was then sealed in a stainless steel jacket in an atmosphere of helium. These samples were equilibrated by repeated inverting of the crucibles in a furnace for 15 min at the desired temperature, left in an upright position for 15 min to permit separation of the two phases, and then quenched under a stream of water. In some runs the temperature of the furnace was held 50' to 100°C above the desired quenching temperature while inverting in order to insure good mixing. However, it was found that above 1200°C the crucibles were subject to failure and for these runs the furnace temperature was not raised above the desired quenching temperature. A small amount of tantalum was dissolved in the uranium and the rare earths in these runs, a maximum of 3 wt pct in the uranium phase at 1250°C and up to 1 wt pct in the rare-earth phase at this temperature. On cooling, the major portion of this tantalum precipitated as primary tantalum crystals. Any residual tantalum would probably have a negligible effect on the mutual solubility of uranium and the rare earths in each other. Samples for analysis were cut from each phase with an abrasive cutting wheel; the region near the interface between the two metals was carefully avoided. In the case of the rare earths with melting points above 1250°C no solubility data were taken on the rare-earth phase since this phase could not have achieved equilibrium in a reasonable length of time. (For the same reason no data were taken on the uranium phase below its melting point of 1132°C.) Equilibrium appeared to have been reached in the uranium phase in these cases although the rare-earth phase had not melted. To verify this, samples were melted together in an arc furnace similar to that described by Kroll.2 These samples were sub-

Jan 1, 1960

By J. T. Burwell, J. Wulff

As is well known, the alloys of iron containing 18 ± per cent chromium, 8* per cent nickel and less than 1.2 per cent carbon exhibit the same allotropic modifications as iron. The face-centered cubic or gamma phase is stable at high temperatures and the body-centered cubic or alpha ferrite is presumably stable at room temperature. The transformation from the gamma phase to the alpha phase in alloys of the above composition (18-8 or stainless steel) is sluggish; even moderately rapid cooling permits the retention of the gamma phase. Cold-work, however, causes the transformation from gamma to alpha to occur at room temperatures. It is difficult, nevertheless, to induce complete transformation regardless of the method of cold-working. Since metallographic polishing is very effective in transforming the surface austenite to ferrite, as indicated by the magnetic studies of Buehl and Wulff,1 it was decided to investigate the phenomenon by electron diffraction methods. Apparatus The apparatus used (Fig. 1) was a hot-filament type employing movable slits, similar to that described by Germer.2 The sample-to-photographic plate distance was 69 cm. and the accelerating voltage 30 kv. Since electrons do not in general follow geometrical paths, it is necessary that either the electron source or the sample be movable in a plane normal to the beam. In this case the sample is fixed and the electron source is movable. The source is adjusted until the shadow of the sample appears in the brightest part of the beam as viewed on the fluorescent screen, then the slits composing the two pinholes are inoved into position one by one. The system is evacuated by means of a mercury diffusion pump backed up with a Cenco Hypervac oil pump. Pressures lower than 10- mm. of Hg are read on a calibrated ionization gauge.

Jan 1, 1939

By Casimir Constable

DURING the years 1875 to 1879 I had charge of the Rockwood furnaces and mines, situated forty miles from the nearest railway communication at that time, and one hundred miles north of Chap tanooga, Tenn., by the Tennessee River. The small furnace with old-fashioned stoves, then in blast, was built under great difficulties by General Wilder. The early conditions were somewhat as follows: The ore was fossil ore of the Clinton group ; very fine and generally wet, without other admixture. The coke had a large amount of ash, and the fur" nace appeared to be badly scaffolded at times. On many days only a few tons of iron could be obtained. The founder generally id creased the revolutions of the engine when signs of chilling appeared,. The cinder at such times was black, very scoriatious, often closely resembling mill cinder. When the pressure was increased (the joints being the old-fashioned rust joints), leaks in the blast-pipe occurred It was noted that when the blast was stopped, and the leak bolt imperfectly remedied, the furnace improved a little. This set me thinking on the right track; and I took the responsibility of be coming my own founder for a time. A scaffolded condition had existed, and the situation was a trying one. Strange to say the negroes proved excellent furnace-men. Conceiving the hearth of the furnace to be similar to the grate area of a steam-boiler, capable of disposing of but so much fuel per hour, and requiring only a corresponding amount of air, it follows that an excess of air will burn the fuel not yet arrived at the hearth!, and raise the melting-point far above the tuyeres. This might pro duce scaffolding or at any rate choke the boshes, and leave less fuel to be consumed in the hearth. Thus for the time being less ail;. would be needed, as the continued burning of fuel in and above the boshes, would only aggravate the trouble. This condition of affairs accounted for the black cinder; the heat above having melted ore not yet perfectly reduced. This view decided me to reduce the revolutions of the engine; thefurnace finally became gray, as might have been expected. Any attempt to increase the speed produced black cinder and hard iron ;

Jan 1, 1883

By B. F. Koch

COPPER reverberatories develop large amounts of exit gases of a temperature in the neighborhood of 2000°F. The gases are not only of a noxious nature but must usually be disposed of at considerable heights above the yard level by a stack. Handling these gases at the temperature mentioned would require rather expensive construction of conveying flues and stack. Moreover, wasting such amounts of heat is certainly most uneconomical. Numerous investigations have indicated that waste heat boilers of the water-tube type are the most practical and economical means for utilizing that heat although the gases are heavily laden with rock dust and copper-bearing slag, which upon cooling form hard deposits on the surfaces of dampers or heat absorbing elements placed in the gas stream. Avoiding Slag and Dust Deposits Based largely on the experience of the paper industry in burning black liquor, a waste heat boiler design was developed a few years ago, providing not only extensive water-wall surfaces for cooling the gases below the fusing point of the slag but also settling out, as far as possible, the solidified particles of slag by creating low gas velocity. Matter carried in a stream of gases or air has a tendency to maintain its original direction upon a change in the direction of the flow of the conveying medium. Reverberatory waste heat boilers installed at Hurley and Morenci endeavored to utilize that tendency for the elimination of slagging particles at predetermined places and before they would strike the tube banks of the boilers. Both installations were successful in minimizing the slagging of boiler tubes and thereby minimizing the need for hand lancing. However, the low draft carried at the up-take of the reverberatory furnaces resulted in a positive pressure in the upper part of the furnace of the waste heat boilers, causing the emission of gases from lancing doors and making more difficult the already unwelcome work of cleaning the boilers by handlancing. Attempting to correct this nuisance as much as possible, the overall height of the Chuquicamata waste heat boilers has been reduced to the minimum considered necessary to obtain proper water circulation in furnace walls. Moreover, it is attempted to solidify slag and dust particles by providing large amounts of water-cooled surfaces before the gas stream reaches super-heater and convection banks of the boilers. The furnaces have been made as deep as an economical and practical arrangement of headers for water

Jan 1, 1952

By George Burgess

I. INTRODUCTION THE suggestion has often been made that it would be highly desirable, at least for certain grades of steel, to be able to control more certainly, by pyrometric measurement or otherwise, the temperatures of the operation of the open-hearth and other furnaces used in the manufacture of steel and iron. That the properties of the ingot and finally of the finished steel product are intimately related to the final temperatures attained by-the metal inn the furnace and to the temperature of casting, has been recognized by metallurgists for a long time, and this question has been very thoroughly treated, especially by Prof. Henry M. Howe, and by A. W. and H. Brearley.1 It is the object of this paper to demonstrate that in so war as casting temperatures of furnaces, steel ingots, and similar operations involving the temperatures of streams of iron and steel are concerned, well-known pyrometric methods s may be easily applied-if certain recently determined corrections are made and precautions taken-with a relatively high degree of accuracy. Greater but not insurmountable difficulties will be encountered in. the case of open-hearth furnace temperatures, while for" those of the converter type a ready solution does not seem practicable. It appears that certain essential data have always been lacking in reporting observations such as those of Le Chatelier in 1892. Thus the correction to be applied for the characteristic radiation-or emissivity¬has hitherto not been adequately taken into account nor the limitations of the several possible pyrometric methods clearly recognized.

Jan 2, 1917

By J. T. Burwell, J. Wulff

As is well known, the alloys of iron containing 18 ± per cent chromium, 8* per cent nickel and less than 1.2 per cent carbon exhibit the same allotropic modifications as iron. The face-centered cubic or gamma phase is stable at high temperatures and the body-centered cubic or alpha ferrite is presumably stable at room temperature. The transformation from the gamma phase to the alpha phase in alloys of the above composition (18-8 or stainless steel) is sluggish; even moderately rapid cooling permits the retention of the gamma phase. Cold-work, however, causes the transformation from gamma to alpha to occur at room temperatures. It is difficult, nevertheless, to induce complete transformation regardless of the method of cold-working. Since metallographic polishing is very effective in transforming the surface austenite to ferrite, as indicated by the magnetic studies of Buehl and Wulff,1 it was decided to investigate the phenomenon by electron diffraction methods. Apparatus The apparatus used (Fig. 1) was a hot-filament type employing movable slits, similar to that described by Germer.2 The sample-to-photographic plate distance was 69 cm. and the accelerating voltage 30 kv. Since electrons do not in general follow geometrical paths, it is necessary that either the electron source or the sample be movable in a plane normal to the beam. In this case the sample is fixed and the electron source is movable. The source is adjusted until the shadow of the sample appears in the brightest part of the beam as viewed on the fluorescent screen, then the slits composing the two pinholes are inoved into position one by one. The system is evacuated by means of a mercury diffusion pump backed up with a Cenco Hypervac oil pump. Pressures lower than 10- mm. of Hg are read on a calibrated ionization gauge.

Jan 1, 1939

By John Eash

DURING recent years nickel has had an increasingly important role as an alloying element in the copper-tin bronzes. Nickel additions not only produce better casting alloys but also make alloys whose properties can be varied by precipitation hardening; thus leading to increased commercial application of copper-nickel-tin alloys. Recent investigations have indicated a decrease in the solubility of tin in the alpha phase as the annealing temperature is lowered and as the nickel content is increased within certain limits. A further change caused by the nickel additions is produced in the excess phase of the copper-tin bronzes. The alpha plus delta eutectoid is replaced by a clear precipitated constituent in the alloys containing up to 15 per cent tin and not less than 1 per cent nickel. This paper has a dual purpose. The first is to present a new determination of the alpha-phase boundary in alloys containing from 0 to 20 per cent nickel, together with the liquidus and solidus temperatures above that field. The second purpose is to give the equilibrium conditions existing in alloys exceeding the alpha phase containing up to 31 per cent tin and 5 per cent nickel, so that the disappearance of the alpha plus delta eutectoid constituent may be explained. After considering the earlier investigations of the related alloy systems and the experimental procedure used in this investigation, the alloys will be discussed in groups as separate quasibinary systems containing constant amounts of nickel. The systems considered contain 0, 1, 2, 3, 5, 10 and 20 per cent nickel. The straight copper-tin system was reinvestigated in order to establish a foundation on which to build the remaining material. The 1 per cent nickel alloys studied give the relations existing in the region of the eutectoid transformation between the copper-tin system and the 2 per cent nickel copper-tin system which has been investigated in detail. The thorough examination of the latter system was made since 2 per cent of nickel is representative of the commercial additions to the cast bronzes and also because it is sufficient to produce

Jan 1, 1932

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By George Enos

As the coating formed affects the corrosion rate, duplicate samples of eight non-ferrous alloys were placed in flowing mine water. The alloys tested were as-cast or as-rolled and machined or polished. The paper describes the tests and gives the corrosion losses and the appearance of the samples at the end of the test. AN IMPORTANT factor affecting the rate and nature of corrosion of metals and alloys is the film, or coating, formed on the surface; and this may accelerate or retard corrosive action once started. The formation of films and coatings is intimately associated with the chemical composition and physical constitution of both the metal and the corroding medium. A film or coating may be either the corrosion product resulting from oxidation; that is, an oxide or salt, or a deposition of suspended matter from the corroding media upon the surface of the metal, or a mixture of both. The coating may adhere tightly or loosely to the surface of the corroded metal. In short, a film or coating is the reaction product of the corroding medium and the metal, which adheres to the surface of the metal and with which may be intermingled material from the attacking media not concerned in the chemical reactions. As the, terms film and coating are used by different writers for very different things, distinction is made between the two, by the present writers, on the basis of thickness. Thus, a film is defined as a corrosion product or deposition, on the surface of a corroded metal, that is of such thickness that it cannot be measured by the metallurgical microscope. A coating, on the other hand, is of such thickness that it can be measured. If the resolving power of the 2 mm. (equivalent focal length) apochromatic oil immersion objective (N.A. 1.4) is taken as the limit of the microscope, the limiting resolution is two lines that are 0.0002-0.0004 mm. apart. It is thus possible to measure coatings that are greater than 0.0002-0.0004 mm. thick. This thickness is equivalent to 200,000-

Jan 7, 1924

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

Jan 1, 1904

By Orson Cutler Shepard

The term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 1934l. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner: . . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1939

By Orson Cutler Shepard

The term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 1934l. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner: . . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1939

By Russell W. Mumford

LITHIA compounds have a place in pharmaceutical and other chemical industries and lithium minerals in glassmaking and ceramics. The metal, although rare, is used to a minor extent in alloys. During the nearly 50 years of production of lithium minerals in the United States, the silicate mineral spodumene has continued as the chief source of raw material for the manufacture of lithium salts. Although twice as much lepidolite, a lithium mica, has been mined, most of it has been used in the making of certain types of glass. Amblygonite has been an additional but minor source of lithium compounds. Triphylite, petalite, and zinnwaldite have also been utilized in the past. All of these commercial lithium minerals contain low percentages of lithium (Table 1). In 1938, a new raw material for manufacture of lithium compounds made its appearance. This product was crude dilithium sodium phosphate (Li2NaPO4), obtained as a by-product of manufacture of potash and soda chemicals from the brine of Searles Lake, California. Searles Lake, which is now dry, lies in the extreme northwest corner of San Bernardino County, California, and consists of a large mass of salts. It was estimated by the United States Geological Survey that the crystal body contained about 25 pct voids, which are filled with a saturated brine. The brine consists mainly of the sulphates, chlorides, carbonates, and borates of sodium and potassium. Several other acid radicals, including phosphates, are present. Lithium is present in the brine in an amount corresponding to 0.01 15 pct Li2O. In the course of evaporation of water from the brine, during the process of manufacture of sodium and potassium chemicals, dilithium sodium phosphate crystallizes out and is recovered by a flotation operation. The lithium concentrate is filtered and dried and is then ready for shipment. It analyzes from 19 to 21 pct Li2O and now constitutes the highest known grade of crude lithium material. It is and will continue to be a major source of lithium for manufacture of lithium products. The variation in lithia content of the commercial minerals as mined is due to replacement of the lithia by soda and potash, to partial alter-

Jan 1, 1949

By Orson Shepard

THE term "electrocapillary amalgamation" is used in this paper to designate amalgamation processes that depend upon electrocapillary phenomenon; i.e., the action of an electric current upon the surface tension of mercury at the contact with aqueous solutions. Electro-capillary amalgamation is selected as a name for these processes because the electrocapillary phenomenon has been found to be the effective agent in the use of sodium amalgam, as well as in the various processes using an electric current from a source outside of the amalgam. Amalgamation processes that depend upon supplying an electric current to the amalgam from an outside source, such as batteries and generators, have previously been called electrical amalgamation processes. There has been a tremendous amount of experimental work done on amalgamation processes involving the use of an electric current, as shown by the large number of patents issued on these processes: the earliest in 1885 and the latest in 19341. Regardless of all the experimental work, the fundamental principles causing the operation of electrocapillary amalgamation processes have not been described. The explanation usually given is that an electric current keeps the amalgam bright and clean. Patent No. 328532 states: It is well known that when amalgam plates are used for collecting gold and silver from their ores the surfaces of these plates are liable to become tarnished or sickened by certain substances contained in the ores or in the current of water which is employed to carry the ore over the plates, and that in this condition they are unfitted for amalgamating the particles of gold and silver. To prevent this and to keep the surfaces of the amalgamation plates always bright and in a better condition for catching and amalgamating the particles of gold and silver I employ electricity in the following manner:. . . A similar explanation is given 49 years later, in patent No. 1953364: The sodium (Na) ions lose their charge at the cathode becoming sodium atoms, which do not react with the electrolyte, but follow the grounded electrical current through the mercury body producing in their passage sodium amalgam and liberate themselves in the amalgamation compartment when brought in contact with the fed

Jan 1, 1936