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By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By Edward Saibel

THE various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure, no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3,4 or on the energy required to form new surface.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agreement between calculation and experiment. It has been pointed out by several observers7 that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so - nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory Of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermo- dynamic theory of the tensile strength of isotropic bodies based on work of Born9 relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melt- ing phenomenon, Fürth obtains an expression for the rupture stress u, in the form [ ] where Q is the melting energy per unit mass, ? is the density, and µ is Poissons’ ratio. Fürth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By C. K. Leith

1 apologize for attempting to talk in a field in which 1 am by no means a specialist, but some of the problems brought up have much in common with other minerals. It touches the field in which we are all interested and it is a field in which our Mineral Inquiry has been giving special attention during the last two years. While it is the primary business, of course, of this Institute to consider the physical facts and technology of minerals, we now face the necessity of considering the minerd industry in its broader economic, social, and political relationships. We have run into a traffic jam—as though a load of hay had been spilled on the road. It makes no difference whether we are drivers or passengers, technical or nontechnical men, we have to get the load off the road before we can go farther. We are conscious of very many difficulties which are outside of the ordinary range of cost accounting or methods of mining or the usual thing with which we concern ourselves. We have extensive readjustments to make in our social and economic and political contacts. It is up to us to find out what is the matter. As a matter of fact, we do not know what is the matter in any comprehensive way. We have many suggestions as to difficulties here and there. Many people are working on the problem, but when the mineral industry as a whole is asked what is a reasonable course of procedure, what is its program, what would be a reasonable state or national policy, I think you will agree with me that we have no spokesman able to outline even a semblance of such a general policy. We sit back and criticize when somebody else steps in, as Governor Murray stepped in, and as many others of our state governors and legislators are stepping in, to do things which we do not think are reasonable. When they say, "What is a reasonable program? " we find ourselves caught napping. We have not agreed on a program. The other day in talking with one of the leaders of the western radical movement, I was twitting him on having no sound and comprehensive conservation program. He said, "What is yours, and what is the program of the mineral

Jan 1, 1932

By R. Steinitz, J. L. Orehotsky

An analysis was made of the influence of floating molten zone traversal on the purification of tungsten rods and the effect of this purification on the brittle -to-ductile transition temperature. The major impurities detectable in the original rods, i.e., molybdenum and oxygen, were reduced by zone refining from 30 to 3 Ppm. Changes in the trace amounts of other impurities could not be quantitatively determined since they were below the limit of detection. Tensile tests on 3-mil wires, drawn from these rods and recrystallized to 17,000 grains per sq mm, showed a transition temperature of 60°C for the zone Purified and 175°C for the original material. 1 HE brittle-to-ductile transition temperature is manifest mainly in the bee metals, iron,' molybdenum, chromium,3 tungsten,4 and niobium. Since many of these metals cannot be fabricated at room temperature in a commercially pure annealed poly-crystalline state, a considerable amount of work has been done on evaluating the influence of purification on the transition temperature in order to determine indirectly whether the fabricability of these metals can be improved by removing impurities. Smith and Rutherford8 showed that the transition temperature of iron is lowered significantly by zone purification. Working with chromium, Edwards, Nish, and wain7 found also that purification appreciably lowered the transition temperature. A similar evaluation has so far not been reported for tungsten, probably because of the difficulties in obtaining tungsten in a purified polycrystalline state. carlson8 and, more recently, schadler9 have purified tungsten rods by floating zone traversal, but after zone traversal, their rods were single crystals. To obtain high-purity polycrystalline tungsten, a technique has to be round for transforming the zone-purified single crystal material into a suitable polycrystalline structure. The purpose of this investigation was to obtain zone-purified tungsten in a suitable polycrystalline state and then to evaluate the effect of zone purification on the transition temperature.

Jan 1, 1962

By John Birkinbine

A RETROSPECT of the growth of the production of pig-iron for the past half century would be the history of the invention and introduction of heated blast as applied to the smelting of iron ores. As the apparatus employed was improved in conception and construction, the economical operation of the furnaces to which it was attached was the more marked, and the production correspondingly increased. To compare the original iron box placed over a coal fire with the modern hot-blast stove, with its combustion-chamber, gas-burners, and air-regulators, would be as unfavorable to the former as to contrast the product of the little Blauöfen with the yield of the improved furnaces of to-day. But, as these little Blauöfen were the germs from which the larger plants have grown, so from the crude apparatus invented and applied by Neilson has grown, in the face of great opposition, the more economical hot-blast stoves now in use. It is not surprising that an innovation like heated blast should have received a large amount of attention from metallurgists, nor that men of recognized ability should formerly have been found both among its champions and opponents, but it is remarkable that, at the present day, with the results of careful research and thorough experiment compiled in convenient shape for perusal, there are iron¬masters who still consider it economy to allow the products of combustion to escape into the atmosphere, rather than utilize them in heating the blast, because of a supposed injury to the quality of the product. In the present state of knowledge and practice, it is proper to express as an axiom, that a well-constructed hot-blast apparatus is essential to the economic operation of an iron-producing plant. Of the interpretation of proper construction there is of necessity a variety of opinions, and, with the view of solving the problem, the apparatus for heating blast has from time to time assumed various forms. Boxes, cylinders, and pipes, placed horizontally, vertically, inclined, or in circles and spirals, have been tried ; there have been pistol-shaped pipes, double pipes, divided or diaphragm pipes, siphon pipes, and as much variety in the mains, connections, flues, and setting. It is probable that, to the introduction of the bell and hopper in

Jan 1, 1876

By Sir James Kitson

By the courtesy of the President and Council of the American Institute of Mining Engineers, I have been invited to take the chair and open the proceedings of this congress. It is a graceful compliment to those members of the Iron and Steel Institute who are your honored guests at this moment—an acknowledgment of high consid-

Jan 1, 1891

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By R. J. Evans

The Combined Metals Reduction Co.'s plant is at Bauer, Utah. It was built primarily to treat ore from the Combined Metals mine at Pioche, Nevada. Shortly after its completion, the company acquired the old Honerine mine, and ores from this mine, as well as custom ores from widely scattered districts, are now being treated at the Bauer plant. Pioche Ore The Pioche ore, which comprises about 50 per cent. of the mill feed, occurs as a replacement of an impure thin-bedded limestone. The lime beddings are separated by thin layers of micaceous shale containing appreciable quantities of sericitc and graphite. The ore is an exeeptionally fine-grained, dense mixture of minerals and gangue, assaying approximately 0.03 oz. gold, 7.2 oz. silver, 7 per cent. lead, 15 per cent. zinc, 16 per cent. iron, 29 per cent. insoluble and 1.5 per cent,. lime. Of the total lead 7 per cent. is in the form of sulfate and carbonate. Approximately 10 per cent,. of the ore consists of chert nodules impregnated with barren pyrite; the nodules average 0.8 mm. in size, and ire extrcmely hard, compared with the other constituents of the ore. Microscopic examination of Pioche ore ground to 80 per cent . minus 150 nicsh shows pyrite, sphalerite and galena still attached. Early Attempts at Ore Dressing Metallurgists, both professional and those working for private companies, have been more or less familiar with the Pioche ore sinee. 1913; in fact, a total of 35 commercial and plant laboratories expenmented with the ore between 1913 and 1921. The work during this period was decidedly negative, it being seemingly impossible to effeet a satisfactory separation of the valuable minerals into marketable products. In 1913, it was recognized that fine grinding-—that is, about minus. : 200 mesh—-was required to liberate the minerals from one another, and from the gangue, but such fine grinding was not considertd practicable at this time.

Jan 1, 1928

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre-Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature1-' describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining G. CARMAN RIDLAND, Member AIME, is a Consulting Geological Engineer, New York, N. Y. San Francisco Meeting, February 1949. TP 2738 IL. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received March 30, 1949. counties cover most of the highly mineralized section of the Front Range which extends from Jamestown to Breckenridge. As far as the writer is aware, uranium has been found only in the portion northeast of Lawson. Silver Deposits at Caribou Hill: The historic silver deposits of Caribou Hill, located approximately half way between Jamestown and Central City, and 35 miles in a straight line northwest of Denver, appeared particularly intriguing as an area to prospect for uranium for the following reasons: here exists an isolated group of high-grade silver veins in the center of a mining district containing occurrences of uranium, and, in two of the well-known uranium deposits of the world, those at Great Bear Lake, Canada, and Joachimsthal, Czechoslovakia, uranium is associated with silver in similar fissure veins. An exploration program, conducted in the spring of 1945, directed special attention to Caribou Hill and was rewarded with the discovery of heavy, canary-yellow stained specimens of'pitchblende. The veins are confined to shear zones cutting a north-south, elongated quartz-monzonite stock of Tertiary (?) age lying in the axis of a major anticline of the Idaho Springs biotite schist, the oldest pre-Cambrian formation in the district. The stock is one and three-quarter miles long by more than a mile wide, and Caribou Hill is approximately at its center. The ore zones vary in width from a few inches to 15 ft, and one structure has been traced for a length of over 4000 ft. The ore minerals are galena, sphalerite, ruby silver, native silver, chalcopyrite, pyrite, and pitchblende. They occur most common-

Jan 1, 1951

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre-Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature1-' describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining G. CARMAN RIDLAND, Member AIME, is a Consulting Geological Engineer, New York, N. Y. San Francisco Meeting, February 1949. TP 2738 IL. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received March 30, 1949. counties cover most of the highly mineralized section of the Front Range which extends from Jamestown to Breckenridge. As far as the writer is aware, uranium has been found only in the portion northeast of Lawson. Silver Deposits at Caribou Hill: The historic silver deposits of Caribou Hill, located approximately half way between Jamestown and Central City, and 35 miles in a straight line northwest of Denver, appeared particularly intriguing as an area to prospect for uranium for the following reasons: here exists an isolated group of high-grade silver veins in the center of a mining district containing occurrences of uranium, and, in two of the well-known uranium deposits of the world, those at Great Bear Lake, Canada, and Joachimsthal, Czechoslovakia, uranium is associated with silver in similar fissure veins. An exploration program, conducted in the spring of 1945, directed special attention to Caribou Hill and was rewarded with the discovery of heavy, canary-yellow stained specimens of'pitchblende. The veins are confined to shear zones cutting a north-south, elongated quartz-monzonite stock of Tertiary (?) age lying in the axis of a major anticline of the Idaho Springs biotite schist, the oldest pre-Cambrian formation in the district. The stock is one and three-quarter miles long by more than a mile wide, and Caribou Hill is approximately at its center. The ore zones vary in width from a few inches to 15 ft, and one structure has been traced for a length of over 4000 ft. The ore minerals are galena, sphalerite, ruby silver, native silver, chalcopyrite, pyrite, and pitchblende. They occur most common-

Jan 1, 1951

MARSHAL Foch has been made an honorary member of the four national American societies of civil, mining and metallurgical, mechanical, and electrical engineers. The governing bodies of these societies, aggregating 45,000 members, conferred this signal honor in expression of the appreciation of American engineers for the unmatched services of this master of engineering principles. At Engineering Societies Building, in New York City, on Tuesday afternoon, Dec. 13, the presidents of the four societies presented one beautifully engrossed certificate of honorary membership in the four societies. The auditorium was filled so that not even standing room was left, more than a half hour before the cere-monies began, and the main entrance on the street had to be closed. J. Vipond Davies, president of the United Engineering Society, made the opening address. Col. William Barclay-Parsons, 'who was commander of the first engineer regiment to go abroad, addressed Marshal Foch in French. Colonel Parsons said: The art of engineering was defined a long time ago as "the art of directing the great sources of power in nature for the use and convenience of man." No better definition can be found today. Of all the sources of power in nature, the greatest, the most valuable, and at the same time the most difficult to direct, is the energy of man himself. He who can direct human energy and turn it to the service of mankind is a great engineer. You, Marshal, have directed a greater mass of human energy than any other man has ever done. And you have successfully directed this mass for the highest uses of mankind, in that you by its aid have preserved for him one of the most precious of human possessions-liberty-liberty not only for your own illustrious country, but for all the nations of the world. The four national engineering societies, of the United States now desire to make record of their appreciation of this fact and to convey to you an expression of their most profound admiration for the great leader of men by conferring on you honorary member-ship in all the societies, the highest honor in their gift and one hitherto never conferred on a single individual. Four thousand members of these societies were enrolled in the armed service of the United States, the greater part of whom had the glorious distinction to serve the common cause in France under your orders. They heard the voice and they saw the hand of the master as he led them through battle to victory. Now we desire that you will still continue to lead us, but in peace, by permitting us to inscribe your name at the head of our roll of honor, where it will be, as your deeds have been, an example to us to do better work, and where it will remain forever a noble inspiration for all future generations. Marshal, in the name of those members of the societies who served under your orders and particularly .in the name of those who fell on the field of honor in France, I salute you.

Jan 1, 1922

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By Alvin Kaufrnan

This chapter will deal with the policy issues relating to mineral land disposal. The first portion of the chapter will discuss in general terms the legal systems utilized in disposing of mineral rights and the major problems encountered; the second section will comprise an analysis of the policy alternatives with emphasis on the pricing aspects. In this section, we are not attempting to provide a legal text, but simply to outline very briefly and sketchily the details of the systems. More detailed information can be obtained by contacting the appropriate governmental agency for specific information. Mining laws throughout the world are based on two major legal groupings: English Common Law and the Civil Law. These basic systems are often modified by Islamic Law and by negotiated -mixtures of these. Under English Common Law, which is embraced by the United States, Canada, and many of the members of the British Commonwealth of Nations, individuals can hold property and can extract minerals from it. The owner can dispose of minerals as he sees fit, either through contract, deed, or whatever other system is appropriate. CIVIL LAW Under Civil Law (also known as Regalian Law), mineral ownership is normally placed in the state, regardless of who owns the surface. This legal system applies in most European countries and their former colonies. It is derived from Roman law. The mineral deposits, thus, are worked under concessions. Most countries use a negotiated concession system and sometimes a combination of negotiation and competitive leasing. The negotiated system has advantages as well as disadvantages for both government and industry. In a system where the government administratively determines who is to get what, the concessions are normally large. Frequently they range up to several millions of acres and involve a considerable investment on the part of the concessionaire. There is no duplication of effort on the part of producers to obtain information, since a single concessionaire controls a given area. Consequently, less money is spent in toto because several prospective operators are not required to seek the same information. The system also has the advantage to the industry of permitting the concessionaire to select and retain the best producting area. Thus, major developmental expenditures are made on the production unit only, with a resulting reduction in the risk factor. The large initial size of the concession also minimizes the possibility of expending a large bonus payment for a barren property. The major governmental advantage of a concession is its flexibility in accomplishing other national objectives. For example, a lease could be negotiated at less than fair market value, but requiring substantial de-

Jan 1, 1976

By Leonard Bernstein, Harry Bartholomew

MANY of the properties of metals and alloys are structure dependent. Not the least of these is the grain structure. For example, in producing alloy bonds between silicon or germanium and gold-alloy foil at temperatures above their eutectics (which are, respectively, at 370" and 356°C) but below the melting points of the individual constituents, it was found that wetting was more complete with a fine-grain structure than with a coarse-grain structure. In cases where the assemblies were held together for long periods of time at elevated temperatures, wetting was not as critically dependent on the grain structure as was the case for shorter periods of time. When liquid phase forms, it first forms in the grain boundaries due to the fact that most of the impurities are concentrated at the grain boundaries and that most impurities tend to lower the melting point of the gold alloy somewhat. In addition, grain boundaries are at high-surface free-energy levels and are thus in a more favorable condition to initiate good wetting. A fine-grain structure will have more grain boundaries per unit area than coarse-grain structure thereby making wetting somewhat easier. To make the grain structure of an alloy sys- tem visible, a satisfactory method for differentiating between the different grains of which the system is composed must be employed. For the alloy bonding system previously described, the grain structure on the foil surface is of primary interest. Conventionally used etchants for the gold-alloy system will not adequately delineate grain boundaries in their structures. For this reason an alternate method is proposed for those cases where such a determination is necessary. Foil between 0.0005 and 0.005 in. thick has been used in this determination. The equipment used in this investigation was described in a previous publication.' Essentially, it employs a resistance-type filament which can be heated up very rapidly and cooled very rapidly. A thin refractory material is placed on top of the heating element. This refractory material may be molybdenum, tantalum, tungsten, or even ceramic but its thickness should be less than 0.010 in. to minimize the temperature gradient across it. The gold-alloy foil is placed on top of this refractory material. The temperature of the heating filament is raised to 900°C and cooled down to below 100°C in 5 to 10 sec. During this cycle, the foil can be observed to plastically deform due to its own weight. With no further chemical etching, this assembly is then viewed under a standard metallurgical microscope and the grain size measured. Fig. 1 is a Au-1 pct Sb alloy at 400X magnification and Fig. 2 is a Au-1 pct Ga alloy at 130X. This technique has proved to be an adequate means for controlling processing conditions in producing large quantities of gold alloy foil.

Jan 1, 1963

By H. J. O’Donnell, B. C. Parks

IN 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.l The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogenation properties of certain American coals. In the years following adoption of Thiessen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring instrumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. PETROGRAPHIC COMPONENTS AND TYPE CLASSIFICATION OF COAL Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1948

W. H. Blauvelt, New York, N. Y.—One thought lias been running through my mind during the wholc of this meeting and that is that the scientific and the practical men must recognize very clearly their interdependence. The value of scientific classification of coal is going to be of the very greatest importance to the users, the practical men. Is not the scientific investigation and the great amount of work that is being done in a measure at least lost to the world? Therefore the scientific investigations and the practical needs of the users should bo brought as close together, and the work should be done as closely together, as possible; that is, the scientific man should know what the practical man needs, and the practical man should not feel that the scientific man is merely a theorist. Scientific investigation is going to have a great effeet and be of great valuc to the practical man who is trying to solve his problems. In the subject which I discussed' for instance, we must look to the scientific man to tell us why coal cokes in one way and not In another and why certain coals will do certain things and others, which appear on the surfacc to be generally similar, do not act in the same way. Need or Physical Data on Coal H. J. Rose, Pittsburgh, Pa.—There is a subject which is a sort of hobby of mine; that is, the need for what might be called critical tables of constants for coal. The chemist has big volumes giving constants, such as the density, solubility, specific heat, thermal conductivity and all other physical and chemical data that have been determined for chemical compounds. Data arc also available on many common materials, for example, the density, hardness, modulus of rupture or maximum crushing strength of swamp white oak as compared with some other wood. In fact, physical data for practically cvery hype of wood commercially produced in the world can he found. In the same way the metallurgical man has handbooks giving the properties of alloys, etc., but we havc very little tabulated information about coal. Our principal reference works are the volumes published by the U. S. Bureau of Mines on the proximatc and ultimate analysis and calorific values of coals of the United States. That is 3 pioncer work of enormous value, but we have reached the point where we need more diversified information. Mr. Fulweiler raised the question of the relative strength of the different coals and cokes. Dr. Campbell and Dr. Ashley wanted to have some information on the resistance of coal to air slacking. It was brought out in the discussion that we want to know something about the coking properties of coal. There are any number of physical tests that we need, such as the thermal conductivity of certain coals, the coefficient of expansion, or the coefficient of friction; or other constants. A smattering of such information is scattered through the literature; for instance, a research worker in Wales will report a coefficient of expansion on Wclsh coals and one in South Africa will report something else for one or two kinds of African coals, hut it is difficult to find the information that is needed on our own coals. Would it not be worth while to consider collecting reliable critical

Jan 1, 1930

By L. C. Graton

THE Federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of Federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal indus-tries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Be-cause of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final

Jan 11, 1919