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By M. E. Fine, A. A. Hendrickson

The critical resolved shear stress and the strain rate dependence of the .flow stress are reported for Ag base A1 single crystals up to 6 at. pct A1 over a temperature ralzge of 4.1° to 470°K. At room temperature the solid solution strengthening is attributed brinciballv to an increase in the dislocation density on alloying. At 42°K the alloys are relatively stronger because the dislocations widen on alloying and are more difficult to cut. In a previous paper, the authors reported the characteristics of strain aging in Ag base A1 alloys.' The variation of the magnitude of the strain-aging yield drops on aging time, aluminum content, and testing temperature strongly indicated that the phenomenon is due to the Suzuki mechanism. In the present paper, the critical resolved shear stress (CRSS) and the strain rate dependence of the flow stress are reported for Ag base A1 single crystals as functions of testing temperature (4.2" to 470") and A1 content (0 to 6 at. pct). Observations on the substructure and measurements of the effect of crystal growth rate are also given. The experimental re- sults appear explainable considering that aluminum additions increase the dislocation density and dislocation width. EXPERIMENTAL METHOD The methods of specimen preparation and tensile testing were described previously.' Briefly, single crystals were grown from the melt in a vacuum (1 x lom5 mm Hg), shaped into tensile samples by a combination of abrading and acid etching, annealed at 850°C in a vacuum (1 x 10" mm &Z) for several days, and furnace cooled to 200'. The testing was done on a model TM Instron using friction grips and a strain rate of about 5 x 106 per sec unless otherwise noted. The various testing temperatures were obtained by immersing the specimens in the following media: 1) 4.2': liquid helium using the apparatus of G. Byrne;' 2) 77°K: liquid nitrogen; 3) 200"K: dry ice and acetone; 4) 415' K: ethylene glycol; 5) 460' \ to 480' : molten Stanalax. In the determination of the CRSS above 296' K, a ratio method was used; the crystals were strained initially at the higher temperature, 0.1 pct shear strain, and then tested at 296' . The ratio of the flow stress between the two temperatures was then multiplied by the average CRSS at 296' K to obtain the value of the CRSS at the high temperature. (The test at 296' showed a yield point resulting from strain aging; the flow stress at 296' K was taken as the lower yield stress.) The ratio method, we believe, is more accurate than using different crystals since

Jan 1, 1962

By L. B. Gittinger

Sulfur is a nonmetallic element widely distributed in nature. It constitutes 0.06% of the earth's crust but only a very small portion occurs in sufficiently concentrated amounts to justify mining. Sulfur occurs in practically all animal and plant life. It constitutes approximately 0.09% of the elements in the oceans; it has been found in meteorites. Sulfur was known and used by man before recorded history. The American Chemical Society approved spelling for the element is sulfur. The English spelling sulphur is used commercially in the United States. In ancient times, sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Sulfur is found naturally in the elemental form in subsurface deposits associated with gypsum and anhydrite in salt domes and sedimentary formations in evaporite basins and in solfatara-type deposits associated with volcanoes and mineral springs. Sulfur occurs also in molecular combination in ferrous sulfides (pyrites and pyrrhotite) and nonferrous sulfides (copper, lead, zinc, and nickel), and in mineral sulfates (gypsum and anhydrite); as hydrogen sulfide contaminant in natural gas; as organic compounds in crude oil and tar sands; and as pyrite and organic compounds in coal and oil shales. Sulfur resources are abundant and exist throughout the world but the extent to which they can be classified as reserves is greatly circumscribed by prevailing prices and technology. Estimates of world sulfur reserves are compiled by the U.S. Bureau of Mines. A compilation of reserves by area and source of sulfur published in 1970 and presented here as [Table 1] totaled 2.47 billion tons (Lewis, 1970). The effect of the decline in prices which has occurred since the earlier estimate is dramatically illustrated by the 1972 estimate of the U.S. Dept. of the Interior which shows world sulfur reserves of only 1.2 billion tons (Anon., 1972d). Sulfur is produced commercially from one or more sources in nearly 70 countries of the world. World production of sulfur in all forms totaled 41.6 million tons in 1971. (Sulfur statistics given in this chapter are long tons.) Native deposits, sulfides and oil and gas contributed, respectively, 31, 41, and 25% of world production (Table 2). Of the sulfur produced from native deposits, salt domes accounted for 54% and evaporite basin deposits, 44%. Volcanic deposits are of little significance except for local consumption. The past two decades have seen important shifts in the world's sulfur sources. In 1950, native deposits and sulfides each supplied about one-half of the world's production. During the 1950s, sulfur recovered from oil and natural gas grew rapidly, representing about 10% of the total by 1960. Since then, the petroleum industry has continued to increase its relative importance as a source of sulfur, representing more than 30% at 1972 year-end. Sulfur is generally classified as elemental or nonelemental for statistical purposes. Elemental sulfur is sulfur produced in the pure, uncombined form. It includes production from native deposits, as well as that recovered in the elemental form from oil and natural gas or other sulfur-bearing materials. When produced from other than native deposits, it is generally referred to as recovered elemental sulfur. Nonelemental sulfur is that which is utilized commercially in molecular combination with other elements, such as sulfides or sulfates. Elemental sulfur is being produced from salt dome deposits in the Gulf Coast region of the United States and the Isthmus of Tehuantepec in Mexico, and from evaporite basin deposits in west Texas, Poland, Sicily,

Jan 1, 1975

By C. H. Wilson, J. W. Daly, J. J. Jakosky

Meteor Crater, Arizona, is a natural wonder which for years has been the subject of considerable discussion and study as to its origin and age (Fig. 1). Of the various theories advanced regarding the origin, two have been considered as most probable by a majority of investigators. The first theory is that the crater was formed by a meteorite or a swarm of meteoric material striking the earth at a high velocity and burying itself. The second theory is that the crater was formed by a "steam explosion" from hot solutions or gases coming from underneath the present sedimentary beds which overlie the area. In order to obtain more detailed information regarding the conditions existing at the crater, the present management decided to have a detailed geophysical examination made. The origin of the crater is of considerable scientific importance and interest. More or less active mining operations have been carried out during the past 20 years by various groups who believed that the crater was of meteoric origin, and who hoped that sufficient quantities of such material had been buried to be commercially valuable. Fragments of meteoric material found on the surface of the ground in the debris around the rim gave analysis of approximately 92 per cent iron and 8 per cent nickel, with some platinum and iridium. The material having a gross value of approximately $50 per ton, mining would be commercially profitable if sufficient quantities of the material existed in condition for mining. In the early work numerous drill holes and shallow shafts were put down, mainly in the northern portion of the crater. Pulverized material and debris caused considerable difficulty, and in an effort to overcome this the present management started a 1500-ft., two-compartment shaft on the south rim of the crater and outside of the fill zone. The intention was to sink the shaft in the solid rock outside of the crater, and then to crosscut toward the crater at a depth of 1500 ft. The work was finally stopped when a depth of 650 ft. was reached, because water poured into the shaft through large cracks and fissures in the rock. The enormous force responsible for the crater had also broken

Jan 1, 1932

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult's law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of 'TiCr, is —0.76' lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,' no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

By W. R. Shimer

(New York Meeting, October, 1913.) THE investigation herein described was carried out for the purpose of studying, both by chemical and metal-lographical means, the extent of over-oxidation of steel that can be accomplished by excessive over-blowing in a Bessemer converter. In addition there are appended some results of basic. open hearth and crucible steels. Remarks on Chemical Methods. The test block used was hemispherical in shape, 4.5 in, in diameter and 2 in. thick. Drillings for analysis were obtained by drilling through the entire solid part of the. block, carefully avoiding all cracks anti blow-holes and mixing these drillings thoroughly. Drillings were carefully examined for scale and the finest were gone over with a microscope to be sure all scale from whatever source had been. removed. Oxygen was determined by the well-known method of Ledebur, modified according to Cushman,1 with, however, the removal of the preheating tube, which was found unnecessary. This method has been found to give concordant results. Blanks run from 0.0003 to 0.0006 g. Duplicate determinations varied not more than 0.001 to 0.003 per cent. It seems to be generally supposed that the hydrogen method gives only that oxygen which is combined with iron. Whether this be true or not, the content of oxygen existing as iron oxide no doubt predominates sufficiently, so that the result obtained is sufficient to indicate whether the steel is over-oxidized or not.

Jan 9, 1913

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.' Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By A. S. Odeh

ABSTRACT A simplified model was employed to develop mathematically equations that describe the unsteady-state behavior of naturally fractured reservoirs. The analysis resulted in an equation of flow of radial symmetry whose solution, for the infinite case, is identical in form and function to that describing the unsteady-state behavior of homogeneous reservoirs. Accepting the assumed model, for all practical purposes one cannot distinguish between fractured and homogeneous reservoirs fram pressure build-up and/or drawdown plots. INTRODUCTION The bulk of reservoir engineering research and techniques has been directed toward homogeneous reservoirs, whose physical characteristics, such as porosity and permeability, are considered, on the average, to be constant. However, many prolific reservoirs, especially in the Middle East, are naturally fractured. These reservoirs consist of two distinct elements, namely fractures and matrix, each of which contains its characteristic porosity and permeability. Because of this, the extension of conventional methods of reservoir engineering analysis to fractured reservoirs without mathematical justification could lead to results of uncertain value. The early reported work on artificially and naturally fractured reservoirs consists mainly of papers by Pollard,l Freeman and Natanson,2 and Samara.3 The most familiar method is that of Pollard. A more recent paper by Warren and Root showed how the Pollard method could lead to erroneous results,4 Warren and Root analyzed a plausible two-dimensional model of fractured reservoirs. They concluded that a Horner-type pressure build-up plot of a well producing from a fractured reservoir may be characterized by two parallel linear segments. These segments form the early and the late portions of the build-up plot and are connected by a transitional curve. In our analysis of pressure build-up and drawdown data obtained on several wells from various fractured reservoirs, two parallel straight lines were not observed. In fact, the build-up and drawdown plots were similar in shape to those obtained on homogeneous reservoirs. Fractured reservoirs, due to their complexity, could be represented by various mathematical models, none of which may be completely descriptive and satisfactory for all systems. This is so because the fractures and matrix blocks can be diverse in pattern, size, and geometry not only between one reservoir and another but also within a single reservoir. Therefore, one mathematical model may lead to a satisfactory solution in one case and fail in another. TO understand the behavior of the pressure buildup and drawdown data that were studied, and to explain the shape of the resulting plots, a fractured reservoir model was employed and analyzed mathematically. The model is based on the following assumptions: 1. The matrix blocks act like sources which feed the fractures with fluid; 2. The net fluid movement toward the wellbore obtains only in the fractures; and 3. The fractures' flow capacity and the degree of fracturing of the reservoir are uniform. By the degree of fracturing is meant the fractures' bulk volume per unit reservoir bulk volume. Assumption 3 does not stipulate that either the fractures or the matrix blocks should possess certain size, uniformity, geometric pattern, spacing, or direction. Moreover, this assumption of uniform flow capacity and degree of fracturing should be taken in the same general sense as one accepts uniform permeability and porosity assumptions in a homogeneous reservoir when deriving the unsteady -state fluid flow equation. Thus, the assumption may not be unreasonable, especially if one considers the evidence obtained from examining samples of fractured outcrops and reservoirs. Such samples show that the matrix usually consists of numerous blocks, all of which are small compared to the reservoir dimensions and well spacings. Therefore, the model could be described to represent a "homogeneously" fractured reservoir. la this paper, the fundamental equation of flow

Jan 1, 1966

By Sidney A. Swensrud

MUCH discussion has occurred as to the use or uses which might be made after the war of either or both .of the large diameter (24 inch and 20 inch) War Emergency pipe lines built by y the United States Government during the war, to move crude petroleum and refined products such as gasoline and light distillate fuels. Indeed, the disposition and future use of these lines constitutes, in the minds of many people, one of the most important problems of postwar readjustment in the Oil Industry. The two lines, running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue normal ocean tanker movements from the Gulf Coast to the East Coast. Physically they could continue after the war to move crude or refined products, and it appears that lines of such large diameter as these, if operated at or near capacity, could move these liquids at costs per barrel which might be considered in the same general cost range as for tanker movements.1 If, therefore, we were to look forward at the end of the war to a shortage of tankers, it is probable that the continued use of these pipe lines for petroleum movements to the East Coast would be worth considering, as against building new tankers to take over the movement, provided there were no other economic or national defense reasons for restoring tanker fleets and no other better use for the pipe lines. Because of the extensive tanker construction program which has been and still is in progress, and because of our Navy's marked success in combating the submarine problem, it appears to be quite possible, however, that instead of a shortage of tankers at the end of the war, we may have a surplus instead. If this should turn out to be the case, then there would seem to be considerable doubt that these lines would continue to be used for moving petroleum or products to the East Coast at the expense of tying up tankers. It would hardly seem probable that the owner of any such tankers would ship via one of the large lines at the expense of tying up one of its own tankers, unless the pipe line tariff rate charged was lower than the out-of-pocket cost of operating a tanker as against the out-of-pocket cost of keeping it tied up. And considering that a substantial part of the cost of operating a tanker goes on even when it is tied up, it is very difficult to figure out how any pipeline tariff could be established that would be low enough to compete with individually owned tankers that otherwise would be idle. Certainly a pipe line tariff rate high enough to cover direct costs plus even a low rate of depreciation and return on the investment would be far above the out-of-pocket tanker operating costs. In view of these considerations, it has seemed desirable to examine with some care some of the various alternatives that have been suggested as to other possible uses to which these lines might be put. One of these is for transportation of natural gas to the New York-New Jersey Philadelphia area. This Eastern area, located at the destination of these lines, contains the heaviest concentration of population in the United States, and is not now served with natural gas. At the other end of the lines lie the greatest discovered natural gas reserves in the United States, if not in the world, and many

Jan 1, 1944

By Francis O. Blackwell

There are few industries in which power is more important to successful operation than mining, and none in which it is so difficult to ohtain power cheaply. Fuel is usually expeusive in mining districts, ana the ma chinery may be widely scattered and located in places difficult of access. The work is often so intermittent and variable as to prevent the economical use of steam. Mining operations are likely to exhibit accumulations of comparatively small and inefficient engines, numerous boilers and long lines of wasteful steam-pipes. Conlpressed air, as a means of transmitting power, is so handicapped by losses in the compressors and piping that it is limited to short distances and to the operation of apparatus requiring power, without regard to cost. To-day, electricity is rapidly replacing other methods of power-distribution, primarily because it is practically independent of distance. By selecting a potential proportional to the length of transmission, the cost of electric conductors and the e5ciency are the same for all distances within reasonable limits. For instance, a given amount of power can be delivered either 528 ft. away at 100 volts, or 50 miles at 50,000 volts, with the same total of copper per H.P. and with exactly the same loss of power in the transmissioo-circuk. This independence of distance permits the selection of the place most advantageous for power-development as a site for an electric power-plant, and the co~~centration there of the generation of all the power required within a radius of many miles. The powel.-site may be at a fall of water, if one is available, or a steam-plant can be built where fuel and supplies are cheapest, or where suflicient water is available for boiler-feed and condensing purposes.

Jan 1, 1904

By B. A. Rogers

THE etching effect which is produced on a piece of polished iron or steel when it is heated in hydrogen or in a vacuum seems to have been observed first by Osmond,1 who believed that he could distinguish four systems of grain boundaries on a piece of steel which had been heated in hydrogen. In a number of other investigations, samples of pure iron were found, after heating, to have complex networks in which two or three systems of grain boundaries could be detected. It was further noticed that samples that had been polished plane before being placed in the furnace were, after treatment, roughened and undulating over their entire surfaces. From a comparison of the temperature of heat treatment with that of the A 3 transformation, it was concluded that the changed appearance of the samples was definitely related to the latter phenomenon. Certain other deductions were made but these are not of importance here and only observations on the appearance of the samples will be reviewed. Ewen2 heated a strip of polished iron in a vacuum in such a way that one end was maintained at a temperature of 1000° C. and the other at 580° C. On the cooler end there was outlined a simple polyhedral network, and at the hotter there appeared the complex system of lines and the undulating surface characteristic of iron which has passed through the A3 transformation. He found that in going from the cooler toward the hotter end the sample maintained much the same character of surface up to the beginning of the transformed area, but that near this region double grain boundaries were of frequent occurrence. Rawdon and Scott' concluded that the simple type of network brought out by heating a sample of pure iron in a vacuum was of the same type as that developed by ordinary etching methods. They also confirmed the observations of

Jan 1, 1929

By Stephen Taber

A vein may be defined as an aggregation of mineral matter, more or less tabular or lenticular in form, which was deposited from solution and is of later origin than the inclosing rock. This definition differs from the one found in many text-books in that no assumption is made as to the origin of the space occupied by the vein or the manner in which the mineral matter was deposited. In the present paper the writer purposes to discuss the mechanics of vein formation, and does not wish to begin by begging the question. The origin of ore deposits has been diligently investigated in recent years, but, while much has been written concerning the chemistry of the process, the physical side of the question has received less attention. The source of the ore minerals; the chemical composition of ore-bearing solutions; the relative importance of magmatic and meteoric waters as agents of concentration; and the causes of mineral precipitation have all been discussed at length. On the other hand, little has been written concerning the mechanics of vein formation, and the theories given in text-books today are essentially the same as those developed by the early Cornish and Saxon miners. Early investigators often regarded both veins and dikes as igneous in origin, but today the theory that vein minerals have been deposited from solutions, either liquid or gaseous, is firmly established. The latter view is supported by the fact that many vein-forming minerals are not found in unaltered igneous rocks; by evidence obtained in the laboratory regarding the solubility of minerals; by the presence of many ore minerals in hot-spring waters; by the occurrence of some veins in regions consisting exclusively of unaltered sedimentary rocks; by evidence as to the temperature at which some minerals are formed; and by the absence of mineral segregation due to difference in specific gravity. There is still, however, much difference of opinion as to whether certain tabular-shaped masses should be classed as veins or as dikes. Some of the earlier investigators have also advocated the theory that veins are contemporaneous in origin with the inclosing rock, while others have believed the vein minerals to represent a recrystallization or transforma-

Jan 1, 1920

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

By John D. Sullivan

Leaching of copper ores is a comparatively old art, probably dating back to medieval times. The leaching of mixed oxidized-sulfide ores, however, is modern. The first modern plant leaching mixed ores was at Ajo, Ariz., where commercial operations commenced in 1917. While the ore at Ajo was primarily oxidized there was always some sulfide present. The Inspiration leaching plant, which was put in operation in 1926, may be considered the first plant constructed for the extraction of both sulfide and oxidized copper. The pioneers in leaching mixed ores had a difficult task before them since they had very little fundamental data on the chemical and physical factors of leaching. For the very large amount of painstaking experimental work that was done before building the Ajo and Inspiration leaching plants the reader is referred to the original articles.' For a period of several years the writer worked on problems connected with the chemistry and physics of leaching mixed oxidized-sulfide ores. This paper summarizes the experimental work and discusses various factors involved in leaching ores. It also presents many data heretofore unpublished. Among the new data are those on chrysocolla, pages 518 to 519, inclusive; dioptase, page 519; covellite, page 529; virtually all those on chalcopyrite, pages 531 to 533, inclusive; enargite, page 533; and tetrahedrite and tennantite, pages 534 and 533. The oxidized copper minerals of commercial importance in American ores are azurite, Cu3(OH)2(CO3)2; malachite, Cu2(OH)2CO3; chrysocolla, CuSi03.2H2O; tenorite (or melaconite), CuO; and cuprite, Cu2O. Dioptase, CuSiO3.H2O is less common. Brochantite, CuSO4.3Cu(OH)2, while the chief mineral in the ore at Chuquicamata, is not of major importance in the United States. Metallic copper, while chemically not so, is frequently classed as an oxidized mineral of copper. The most important sulfide minerals are chalcocite, Cu2s; covellite, CuS; bornite, Cu5FeS4; and chalcopyrite, CuFeS2. Less important complex sulfides are enargite,

Jan 1, 1934

By Clarence A. Seyler

The technical difficulties of cutting thin sections of coal for examination by transmitted light have hitherto restricted the investigation of the important subject of the microstructure of coal to the few possessed of the requisite skill and time. Apart from this, the method fails with anthracites and other coals rich in carbon, owing to the opacity of the material. Occasional use of the method of polishing a surface, with or without etching, has been made, but it was not until Winter' published an account of his results that attention was seriously directed to the method. In May, 1923, a specimen of dull anthracite came into my hands; I tried Winter's method on it and the presence of megaspores and other vegetable structures became clearly visible. A preliminary notice was published by me;2 but I soon abandoned the use of Schulze's solution, having found that a mixture of chromic and sulfuric acids gave far better results. In the meantime Turner and Randall, in America, had independently developed the method of flame etching, as applied to anthracite, with great success. I have spent a year studying the method of chromic etching, which gives excellent results with bituminous coals and camels, as well as with anthracite. For anthracites, I have used the chromic method and Turner's method of flame etching, whichever was the more convenient or as a check one on the other. The polishing is done, according to metallurgical practice, by the use of a polishing machine and successively finer emery paper, followed by polishing on cloth moistened with a suspension of levigated green oxide of chromium, and a final rubbing on "selvyt" (a cotton velvet polishing cloth) moistened with alcohol. The polished sample is examined by reflected light with a 2/3 and 1/6 in. objective. Bituminous coals usually show considerable structure, and even anthracites show it faintly in places. The sample is then etched by immersion in a boiling solution made by adding 10 c.c. of concentrated sulfuric acid to 30 C.C. of a saturated solution of chromic acid; enough water is then added to dissolve

Jan 1, 1925

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride'-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strain-aging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that, wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 72o°C. The time of treatment is relatively short (about 3 hr, to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say aimost 30 per cent by volume. At this temperature. the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a verv low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,-ooo lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantiallv constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1944

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By F. M. Jardine

I1944 the cry was for higher production more tons, more metal. New plants were built, capacity of old plants was increased and millmen all over the country were treating tonnages far above normal, sacrificing recoveries to vet that extra metal from extra tons. The list of "critical minerals," at first long, has been scratched until there remains, not a list, but only an item or two. Stocks of all metals and minerals, with possibly one or two exceptions, are now entirely adequate and numerous plants have curtailed or suspended operation.

Jan 1, 1945