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By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By G. K. Dumbauld, B. E. Morgan

Kesults of laboratory investigations of the effects of drilling muds on oil well cements are presented which show that relatively large quantities of untreated muds do not seriously interfere with the setting of cement slurries, but that relalively small quantities of treated muds seriously retard the setting of cement slurries. Laboratory results also indicate that the harmful effects of contamination with treated muds can he counteracted by the addition of activated charcoal to cements. Also described is the successful use of cement containing activated charcoal for the placement of plugs in oPel hole after previous attempts with ordinary cement had been unsuccessful. INTRODUCTION The contamination of cement slurry by dilution with drilling mud has long been considered a cause of failure in oil well cementing. The cement slurry must displace the drilling mud from the annulus between the casing and the walls of the borehole. and it is probable that some mixing of the slurry and the mud occurs even under the most nearly ideal displacement conditions. Hole enlargement, failure to center the casing in the hole, and formation of gel structure in the drilling mud increase the probability of contamination. In some cementing operations, such as the placement of a cement plug in open hole, considerable mixing of the mud and slurry is likely. Many cement failures which can be attributed logically to no cause other than contamination of the cement slurry by the mud attest the need of a better understanding of this problem. Considerable attention was given to the problem of mud contamination of cements about 20 years ago.The effects of field mud upon cement slurries prepared with different amounts of mix water were investigated thoroughly, and the data obtained were invaluable in determining the causes of the high percentage of failure in oil-well cementing at that time and in bringing about improved cementing results. Since then, many aspects of the problem have changed, due primarily to advancements in cement and drilling mud technology. Today, several types of portland cement are used in well cementing and numerous chemical additives are used in drilling muds. An excellent report on the effects of drilling mud additives on oil-well cements was issued during 1951 by the American Petroleum Institute. Data in the report revealed that many mud additives, notably organic materials in relatively small amounts, produce a marked effect on the properties of cements. Prior to this time, little information has been available on the effects of chemicals commonly used in the treatment of drilling muds upon the properties of cements. Another aspect of the problem of mud contamination of cements, which has received no attention heretofore, is the possibility of producing a cement having properties unaffected by a reasonable amount of mud contamination. In view of the need for additional information on the contamination of present-day cements by currently-used drilling Muds, the investigation described herein was initiated Several years ago with a two-fold purpose: first, to determine the capacity of cement slurries to tolerate contamination by both untreated and treated muds without loss of ability to set and develop strength within a reasonable time; and, second, to investigate the possibility of enhancing the ability of cement slurries to withstand mud contamination by incorporating additives in the cement. The data for this study were obtained by mixing drilling mud with cement slurry and testing the resulting slurry-mud mixture for rate of set and development of strength. Also, several materials were tested for their possible improvement of the property of cement slurry to withstand mud contamination; these materials were tested in both contaminated and uncontaminated cement slurries.

Jan 1, 1952

By J. Spreadborough, D. LaW. King, E. Anderson

Tmzsile tests were performed on Armco iron samples, at various ternpe.ralures and strain rates, ocer a wide range of grain sizes. Analysis of the data suggests that the plot of the lower yield stress, against d-1/2,where 2d is the acerage grain diameter, is not linear (as is often assumed) but is concave toward the d. axis over the range of d-from 7 to 53 . The different values of the parameters obtained by other workers can be explained, in part at least, by the observed curvature. This curvalure is shown to be consistent with a model of yielding based on dislocation pile-ups; however, the values of obtained by fitting our data to this model differ appreciably from the values generally reported. The equation proposed by Cottrell, viz.: is a plausible empirical fit to the experimental results. The purpose of this paper is to comment on the validity of the widely used linear relationship first proposed by all' and Petch and coworkers2"4 between ay, the lower yield stress, and 2d, the average grain diameter, for bcc metals, viz.: Many workers, see Refs. 2 to 7 and Table 11, have fitted this equation to their experimental results and have obtained acceptable fits over the relatively narrow range of grain sizes used by most of them. Indeed, in some cases, so few data points were available that any more sophisticated fit would have been irrational. In most of the interpretations,'-' oi is thought to be a measure of the friction stress accompanying dislocation movement, and ky was originally inter- preted as a measure of the dislocation locking but is now believed by Cottrell" to be a function of the dislocation creation rate. In the "unpinning" theories, k, is equated to where od is the unpinning stress and 1 is the average distance from the boundary of the grain where yielding is taking place to the nearest dislocation source in an unyielded grain. Other considerations (see, for example, Refs. 11 and 12) lead to equations with a similar form to [I] where different meanings may be attributed to the parameters. While there are doubts as to the physical significance of the parameters i and k, they continue to be used by many workers; interpretations of the variations in the behavior of ferrite materials following certain treatments, e.g., aging,'3 neutron irradiation,14 have been given frequently in terms of these parameters. Some theories of the mechanical behavior of bcc metals are based on this relationship. We have investigated experimentally the oy - d-'lZ relationship for Armco iron over a wider range of grain sizes and with more data points than those given in published results. The analysis of our data suggests that the oy—d-'" relationship is not linear but is in fact concave towards the d-'I2 axis. RESULTS AND DISCUSSION The experimental work was carried out on 3-mm-diam Armco iron rods which were prepared by wire drawing from 5-mm-diam rods. By annealing in vacuum at temperatures between 7000 and 1200°C for various times, grain sizes from 7 to 20,000 grains per sq mm were obtained, the grains in all cases being regularly shaped. Grain sizes were measured by lineal interceptand by area methods; only specimens with Amax/A values of 3 to 6 were used in the Petch-Hall plots (where A is the average area of a grain and Amax is the area of the largest grain observed). For all the specimens used, the number of grains in a cross section exceeded 50, which should be adequate to avoid grain size effects.'= Tensile tests were performed at 296", 219, and 17l°K, using

Jan 1, 1969

By Goldye Leeds, Marian Balicki

A SURVEY of literature reveals the scarcity of experimental evidence relating to work hardening and reannealing of silver.'-'" With the exception of the well-known X-ray investigation of silver and other metals by W. A. Wood? the effect of progressive cold working has not been studied. The determination of thermal stability of silver in the work-hardened state by means of isochronal or isothermal annealing has been confined apparently to very high reductions only. In the survey made, no study was encountered which endeavored to produce a complete picture of the changes in various properties due to cold working and subsequent reannealing. To fill these gaps and to assemble data that could be used for the determination of activation energies and of frequency coefficients of primary recrystallization, a systematic experimental approach, which was developed by one of the authors, has been applied to pure silver. Material and Processing The silver used was Handy and Harman fine silver, with a spectroscopic analysis at the testing stage of Cu, 0.0001 to 0.001 pct; Te, 0.0001; Pb, Si, Ca, Mg, and Mn, traces. The material was supplied in the form of a rod 0.406 in. diam and was converted into test samples according to the procedure condensed in Table I. It should be mentioned that air annealing was adopted to simulate industrial practice, though it was realized that annealing in a neutral gas or in a vacuum would be preferred. The usual precautions have been taken to eliminate any structural changes and property changes resulting from the storage of the samples prior to annealing or testing. Thus the wires were kept at the fully annealed stage, and the final wire drawing, which produced the desired degree of work hardening, was done just prior to the final annealing or testing. During the short waiting period, the samples were kept in a thermosflask filled with ice. Even with these precautions some strain-age-hardening or self-annealing could occur. To test such a possibility, wires of different reductions were prepared in the manner adopted and portions of them were immediately tested. The remaining portions were similiarly tested after different periods of storage, both at room and melting-ice temperature. Within experimental error, all samples obtained from a wire of a given percentage of reduction yielded identical values. This result qualified the material for further tests and interpretations, because it showed that either strain-age-hardening and self-annealing were absent, or that these effects fully balanced each other. The final annealing was carried out in an electric resistance furnace automatically controlled to within a 10°F. It was realized that the temperature fluctuations were greater than desired for this type of work. TO diminish the errors due to fluctuations of temperature, the hot junction of the thermocouple was placed as close to the samples as possible; the time of soaking was reduced to 15 min; and the number of samples annealed at different temperatures was increased. It will be seen from Table I that some tests were performed on the same material at rising temperature. These will be discussed elsewhere. Room temperature testing was limited to the determination of some of the mechanical properties that are known to be additive in a degree sufficient to be used for indirect study of the kinetics of the reannealing process, Tensile tests, carried out on a manually operated J. Camillon machine, accurate to within permitted the determination of the ultimate stress (U.S.1 and of the 2 in. elongation, (A,). The proof stress (d,e) has been determined from a series of bend tests carried out on a Tinius Olsen Stiffness Tester by using the offset method. This involved accurate determination for each sample of load-angular deflection curves, finding a

Jan 1, 1952

By J. R. Lucas, H. E. Rutherford

The primary objective of this research was to evaluate the feasibility of ultrasonic testing for the purpose of analyzing the structure and properties of rock material. A secondary objective of this study was to determine experimentally the elastic wnstants of various rock specimens with the use of ultrasonic equipment. Elastic constants can definitely be determined quickly and accurately by ultrasonic investigation. With proper equipment there are indications that ultrasonic waves could be utilized in the detection of flaws, such as fractures and planes of weakness, measurement of thickness, and the study of structure of rock material. Ultrasonic principles have been applied in many industries for the purpose of determining the structural characteristics of various materials. The principal applications of interest here are detecting flaws, measuring thicknesses, and determining elastic constants. The main advantage of ultrasonic analysis is that it is nondestructive. It also has extreme sensitivity, high penetrability, good accuracy, rapid response, and the necessity to have access to only one side of the specimen. These various applications and advantages lead one to think that ultrasonic principles might be applied to rock material in situ for purposes of analyzing its structural characteristics. Therefore, the primary objective of this research was to evaluate the feasibility of ultrasonic testing for the purpose of analyzing the structure and properties of rock material. A secondary objective of this research was to determine experimentally the elastic constants of various rock specimens with the use of ultrasonic equipment. The term ultrasonics is given to that branch of acoustics dealing with periodic sounds whose fre- quencies are above the audible range or above approximately 15,.000 to 20,000 cps. The first practical production of this high frequency sound was made possible after World War I due to developments of electronically controlled sound wave sources. At the present, the maximum practically attainable ultrasonic frequency is approximately 1000 megacycles per sec. Sound waves of sufficiently high frequency can be made to travel in a beam with little spreading. Therefore, such a beam can explore a material and detect nonhomogeneities in it by reflection. This is the principle of the ultrasonic reflectoscope invented by F. A. Firestone' in 1942. An ultrasonic beam, on pulse-penetratink a solid material medium, produces an echo when it strikes a flaw which has different acoustical properties than the surrounding medium. This echo can be detected by the same transducer which sends out the original pulse. This principle is the basis of the important industrial techniques of nondestructive ultrasonic testing of metals and other solid material. Later developments in the field of ultrasonic testing of solid material have been mostly improvements in equipment and instrumentation. To date, most of the industrial applications of ultrasonic analysis of solid bodies have been in the aircraft, electrical, and nuclear energy fields on the nondestructive testing of metal. The one solid material similar somewhat to rock material, upon which some work has been done to apply ultrasonic testing techniques to study structural integrity, is concrete. Jones and Gatfield3 briefly summarize this work on concrete. Their basic conclusion was that the strength of concrete was a function of the change of the longitudinal sound wave velocity in the concrete. Only recently has any extensive study been made to apply ultrasonic testing techniques to rock material. Lutsch studied rock material by an ultrasonic pulse method to determine the extent and degree of fracture of rock faces. Lutsch states that the number of observed reflections is a measure of the degree of fracture and that only ultrasonic waves are able to detect fractured zones subjected to high pressure. Suzuki, Sasaki, and Siohara5 studied the characteristics of the sonic wave in rock for propagation over a wide range of wave lengths. They indicated that, in rock, the propagation constant and attenuation of the

Jan 1, 1962

By Euclid P. Worden

In 1977, an article in World Mining1 reported a total of 2726 rotary blasthole drills in service. This figure included only those machines produced by three of the manufacturers building drills of this type. The total, therefore, is much higher. Rotary drilling in the mining industry is big business to the manufacturers and suppliers involved, and a significant cost item to mine operators. The time has come to take a hard look at rotary drilling technology with an eye to reducing costs by increasing drilling efficiency. The efficiency of any rotary drilling operation is best measured in terms of the rate of penetration achieved by the bit. In blast hole drilling, there are five factors which affect the rate of penetration. They are: (1) bit selection, (2) weight on the bit, (3) rotary speed, (4) hole cleaning, and (5) formation properties. Of these factors, all but one may be controlled by the operator. Looking at any one in detail may reveal possible improvements in the system. One of these factors -- proper hole cleaning - will be discussed in this paper. In order for a bit to perform at its maximum capability, each tooth or insert should strike fresh clean rock as it falls into its drilling position. If the tooth or insert lands on previously drilled cuttings, a major portion of the energy delivered to the bit is absorbed in redrilling this broken material. A major portion of the interest, therefore, should be directed to the proper cleaning of the bottom of the hole. In an in-depth study of the cleaning of large diameter holes, Allen2 reports that horizontal air velocities of 38.10 m/s are necessary to prevent the saltation of drilled cuttings on the bottom of the hole. The exact flow pattern on the bottom of the hole, however, is not generally known. The air leaves the bit through the jet nozzles and the mouths of the cones, but where it goes from there is uncertain. This problem should be investigated by the bit manufacturers because they can best utilize the results of such an investigation to provide a more effective product. Some work has been initiated in this area and competition will probably increase its intensity. Bailing velocity is the best criteria to measure the cleaning of the hole, including the bottom, and is the factor on which efforts toward improvement must be concentrated. The first consideration is "What should the bailing velocity really be?" In drilling deep holes for oil and gas, 15.24 m/s is the generally accepted figure. In blasthole drilling, the figures of 25.40 m/s for average rock to 35.56 m/s for iron ore were first mentioned by Capp3 in 1962. The recommendations are the same to this day. A number of questions could be asked in regard to the apparent disparity between these two sets of figures. Various investigators have derived formulas which support one or another of these criteria. A thesis on the subject was written by Alexander4 who derived a formula based on research which resulted in velocities in the lower end of the ranges quoted previously. He set out to compare this figure to laboratory tests and his tests indicated that the velocities given by the derived formula appeared to be high.1 Perhaps the best reason that the 25.40 to 35.56 m/s range has been used, is that these velocities seem to work. Below the accepted figures, low bit life and slow penetration rates occur. Above these figures, increasing amounts of abrasive wear on the drill pipe and stabilizers seem to appear. There is a fallacy to this entire approach, however. The entire velocity calculation is made using nominal bit and pipe sizes and compressor deliveries with no compensation made for losses in the system. Perhaps an examination of some of the things that are not presently considered could lead to some practical improvements in the operation.

Jan 1, 1980

By J. Washburn

Two simple types of dislocation distribution were introduced into zinc crystal specimens and the effect of each on the stress-strain curve was investigated. Quantitative results were obtained for simple edge dislocation arrays and for an array of screw dislocations lying in the slip plane. A CCORDING to present knowledge, the disloca-tions present in large annealed metal crystals can be divided into two somewhat arbitrary groups: 1—single dislocation lines distributed more or less at random or forming elements of a three-dimensional network in which the distance between adjacent dislocations is of the order of 10 2 to lo-' cm and 2— widely separated planar arrays of edge dislocations forming dislocation walls or small angle boundaries within which adjacent dislocation lines are spaced at much smaller distances (lo-' to 10- hm). The former can be considered as a dislocation interpretation of the mosaic crystal proposed by Darwin and Ewaldl, ' 40 years ago to account for anomalously high integrated intensities of X-ray diffraction maxima. Small angle boundaries, although now known to be present in most single crystals used for mechanical testing, were not generally recognized by the early workers. This was partly due to the fact that only recently have improved X-ray and metal-lographic techniques been available for checking the macroscopic perfection of crystals."" It has long been known that changes in growth conditions and in annealing procedure, which might logically be expected to cause variations in the structural details of both the dislocation network and of dislocation boundaries, produce marked variations in some mechanical properties such as yield strength." However, no quantitative experimental correlations between changes in dislocation distribution and changes in mechanical properties have yet been made. Such a correlation has been difficult to obtain because, even when great care is exercised to keep the histories of a number of single crystal specimens identical, it usually has not been possible to avoid considerable variation in macroscopic per- fection.' The number and orientation of dislocation boundaries vary from specimen to specimen. This has probably been an important contributing factor to the large scatter in the results of most mechanical measurements on pure single crystals. Some recent experiments"% ith single crystals of zinc have shown that the presence of dislocation boundaries in a specimen can increase its resistance to deformation by slip. With polycrystalline aluminum and nickel, there is also evidence that dislocation boundaries within the individual grains of the aggregate can increase the resistance of the material to plastic deformation, either as measured by tension tests at room temperature or by creep tests at higher temperatures.'" " Although the foregoing observations seem to have established the fact that substructure can have a strengthening effect, the test conditions were too complex to give much information concerning the mechanism. In the foregoing cases, a network of intersecting boundaries having various orientations and boundary angles were present. Before their apparent strengthening effect can be understood, it will be necessary to isolate and study separately the effect of a number of variables: 1—boundary angle, 2—boundary orientation with respect to the active slip direction, 3—number of boundaries, 4—intersections of boundaries, 5—detailed structure of the boundaries, and 6—interaction of impurity atoms with dislocations in boundaries. The object of the present work was to study the effect of dislocation boundaries on flow stress under the following simple experimental conditions: 1— substantially pure shear deformation and 2—boundaries of controlled angle, orientation, and number. In this way, it might be possible to distinguish the important variables from the relatively unimportant ones. Experimental Procedure Stress-strain curves of hexagonal metals are generally nearly linear even out to very large strains."

Jan 1, 1956

By J. N. Ong, J. P. Ratledge, J. H. Boyce

SINCE German operators opened the Tsumeb mine in the early 1900's, continuous operation has been interrupted only by enforced shutdowns during two world wars and the depression of the 1930's. Original metallurgical practice was blast furnace smelting. This was applicable only to low zinc ore, leaving large tonnages of high zinc ore to be stockpiled on the surface. A gravity concentrator using tables, buddles, and jigs operated for several years, but differential flotation of the ore did not get beyond the experimental stage. When the property was put up for sale by the South African Custodian of Enemy Property there was an estimated 434,000 tons of ore on surface dumps. The dump material, assaying 4.48 pct Cu, 15.8 pct Pb, and 10.9 pct Zn, had become highly oxidized during a stay of many years on the surface. But these dump ores had to be used in evaluating possible metallurgy because the shaft became flooded after the 1940 shutdown and underground ore was unavailable. Many companies examined Tsumeb but quickly lost enthusiasm because of the formidable metallurgical problems presented by the dump ore. However, on the basis of extensive test work, the present company decided that differential flotation would be successful and purchased the property after competitive bidding. Geology and Mineral Association is Complex The Tsumeb mine lies near the northern boundary of South West Africa at an altitude of 4200 ft. The village of Tsumeb is 335 air miles northeast of Wal-vis Bay, territorial port of entry. The orebody is a hydrothermal replacement deposit associated with an irregular intrusion of aplite cutting folded pre-Cambrian dolomite beds. In plan the deposit is a lens of 250x600 ft maximum dimensions. In section the orebody dips 55" south from the surface to 2000 ft, below which there is a reversal in dip to 75" north. Mineralization is localized in the aplite and in the adjoining brecciated dolomite. In the upper levels the ore is largely confined to a single lens, but below the 1890 level massive sulphide ore forms north and south lenses that partially enclose a pipelike body of medium to low grade disseminated ore, part of which is of too poor a grade to mine. Drilling below the 24th, or bottom level, has disclosed that a high percentage of the mineralization from the 3000 to 3300-ft horizons is comprised of copper and lead oxides. The deep oxidation may be local, since it appears due to circulating waters in a major fault cutting the orebody. Tsumeb ranks as one of the highest grade base metal deposits in the world. It is geologically and mineralogically famous for 41 copper, lead, zinc, vanadium, and germanium ore minerals, but its complex mineral assemblage is not attractive to metallurgists. In addition, there is a gradual change in oxidation intensity from the upper levels to the lowest level now operating, which is the 24th. This is well illustrated by the copper minerals. In the upper levels malachite and azurite are predominant, in the intermediate levels chalcocite, and in the lower levels tennantite. Throughout the mine there are sufficient heavy metal soluble salts to activate zinc, and large amounts of depressants are required even for so-called clean sulphide ores. When the same sulphide ore is exposed to prolonged oxidation aboveground, as was the case with the dump ores, reagent requirements become fantastic. Plant Construction First staff members arrived at Tsumeb in March 1947, and by May essential services had been restored and mine unwatering began. In 2 1/2 months company employees built a temporary jig and sorting plant for treating existing dumps to provide a saleable product during high metal prices. Meanwhile, concentrator design and construction was contracted to a South African firm, with subcon-

Jan 1, 1956

By H. R. Hose

The total crude fluorspar reserves in Western Europe, including the USSR and the Soviet sphere, Thetotalare estimated to exceed 17 million metric tons. The total fluorspar production in 1951 in Western Europe, excluding the USSR and Soviet sphere, amounted to 371,109 metric tons. The chief fluorspar-producing countries in Europe, excluding Russia and the Soviet sphere, are France, Western Germany, Italy, Spain, and the United Kingdom. TOTAL crude fluorspar reserves in western Europe, containing more than 35 pct CaF2, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author's judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de los Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use. Crystalline cubic or octahedral fluorite of CaF2 composition, with 48.9 pct fluorine and 51.1 pct calcium, has a specific gravity of 3.18. The ore in place, however, usually averages 3.0 metric tons per cubic meter owing to the quantity of other minerals asso- ciated with the fluorspar in the veins and the physical state of the fluorspar, which may vary from sugary to massive crystalline or microscopic inter-growths with barite or quartz. Barite of 4.5 sp gr, quartz of 2.66 sp gr, and chert and calcite are commonly associated with fluorspar. Other minerals usually present in lesser amounts are celestite, wad, silver, lead, zinc, copper, iron, and uranium minerals. In some cavity fillings the rhythmic deposition of the fluorspar, barite, and quartz into successive crusts may make it possible to handpick the crude ore on belts or to separate the fluorspar from other minerals while the actual mining is carried on. Where metallurgical grade lump spar is required for foundries, separation of quartz and barite may be made also by jigs and heavy media, and in some mines the lead and zinc sulphides may be separated and recovered by vibrating tables. However, except in the case of unusually high grade deposits, acid grade fluorspar is obtained by flotation. By this process fluorspar deposits grading down to 35 pct CaF2 in the crude ore can be worked at a profit when fluorspar, lead, zinc, and silver prices are high, as the sulphides of these ores can be separated from the fluorspar by flotation and concentrated.

Jan 1, 1956

By M. R. Geer, H. F. Yancey

John Grifien (Pittsburgh)—I wish to congratulate the authors on this paper, which, I am sure, will promote a clearer conception of the various criteria which have been advanced as measures of coal-cleaning performance. Their clear descriptions of the more important criteria that have been advanced and explanations of their meaning and application have been sorely needed and, if widely promulgated and followed, should remove much of the confusion which, heretofore, has been evident. I suggest that much of this confusion has also arisen from lack of common agreement as to the exact meaning of the words and terms used in our discussions of this subject. I am sure I have been equally guilty in this respect and suggest it is time that we select a committee to study vocabulary as well as criteria, so that common understanding and agreement can be had. Thus, I suggest, that the title of this paper should have used the words "coal-cleaning performance" and not "coal-washery performance." My understanding is that "washery" refers to a complete plant and it has additional functions to that of coal-cleaning, such as control of size, moisture, etc. Also, I do not agree with the authors that the formulas given in their paper, the Fraser and Yancey formulas, are necessarily the only ones that can be called efficiency formulas. When a dictionary is consulted one realizes that the words "efficiency" and "efficient" have not precise meanings but only very general ones and must be further defined for each particular use, if they are to have any precise meaning. To my mind, the first of the Fraser and Yancey formulas given should never be used as expressing "efficiency" alone but only by the fuller phrase which truly expresses the kind of efficiency it states, which is "coal recovery efficiency." For complete clarity we then need only define "coal" for the particular circumstances under which the formula is used. This would recognize the fact, fully explained by the authors, that the limits in coal qualities imposed by the market have imposed a factor—and a variable factor—which has influenced any answer obtained by this formula. Such a procedure makes it entirely practical and logical to use the values of any of the qualities of coal—ash, sulphur, phosphorus, specific gravity—or a combination of them to define what is coal for that particular use of the formula. Further, it is clear to me that the criteria to be used must be dictated by the objective in view and the use for which the data are obtained. The authors clearly point out that the Fraser and Yancey coal-recovery efficiency formula is influenced by three factors, "one is determined by the coal, one is dictated by market or use conditions, and one is an inherent characteristic of the cleaning unit itself." The formula which uses the inverse of misplaced material as a measure of efficiency is also a coal recovery efficiency formula and is influenced in like manner by these three factors. As the authors point out, both are useless in obtaining data which enables a direct and valid comparison of the performance of a given cleaning unit on two coals where the other two factors vary or of the performance of two or more cleaning units of different types unless the values of the other two factors are identical. Much of the confusion in our discussions of and literature on coal cleaning has come from failure to understand clearly this fact. Many such comparisons have been made from which erroneous conclusions have been drawn. I am, therefore, particularly glad to see the authors' emphasis on 4?-1e criteria which indicate the "sharpness of separation. I feel that these are the essential criteria

Jan 1, 1952

By P. B. Mee

The secondary re crystallization behavior of two vacuum-melted, nominally 3 pct Si-Fe alloys has been studied, one alloy being produced from pure electrolytic iron and semiconductor-grade silicon and the other from commercial-purity hot band. The vacuum-melted and vacuum-remelted alloys were found to develop {110}(hhl) and {lll)(hkl), respectively, on annealing in high vacuum and {100}(0kl) and {11l}(hkl), respectively on annealing in pure hydrogen of dew point, < — 60°C. H2S doping of the hydrogen or annealing in commercial argon was found to effect a reversal for the vacuum-remelted alloy from (111) to (100) secondary recrys-tallization, while prolonged vacuum annealing at 2 x 10-6 Tow resulted in a tertiary re crystallization from (111} to (110). The growth selection of the {lll}(hkl) component was found to be governed predominantly by the {111}/planar misorientation, the maximum deviation of the resulting secondaries being 5 deg. It is considered that the driving force for {111}(hkl) secondary recrystallization arises from the preferential lowering of ?111, possibly by phosphorus or nitrogen diffusion, just as oxygen and sulfur under certain conditions have been found to preferentially lower ?100. When heavily cold-rolled metals are annealed at high temperatures, primary recrystallization usually occurs rapidly and may be followed by considerable grain growth. However, in the presence of a fine dispersion of inclusions1"3 or with a strong matrix preferred orientation4&apos;&apos; the matrix may be stabilized and a secondary recrystallization may then be effected. Also, in vacuum-melted Si-Fe it has been shown possible to develop {100}(001) and {110}(001)6 surface energy driven secondary recrystallization textures. Further, it has been found that, on annealing very pure metals, grain growth normally ceases when a grain size approximately twice the strip thickness is acquired, due to the formation of V-shaped thermal grooves which result in an equilibrium being set up between surface and grain boundary stresses. If, however, a surface energy difference ??s, exists between adjacent grains (of the order of a few percent of the grain boundary energy ?b), then according to Mullins8 a secondary recrystallization may be effected, since the grains having lowest ?s would grow at the expense of their higher-energy neighbors. For clean bee metal surfaces ?110 should be lowest; however, for 3 pct Fe-Si (100) secondary structures have frequently been developed and have been attributed by Walter and Dunn9 to an alteration of the relative surface energies due to the preferential chemisorption of oxygen on (100) planes. Kohler,10 however, indicated that this reversal may be achieved by employing minute quantities of highly polar compounds in the annealing atmosphere, i.e., sulfur compounds, in par- ticular H2S being beneficial in (100) growth. This work has been verified by Kramer" using {100)/{110} bicrystals, while Mager12 demonstrated the importance of sulfur diffusion within the strip. Detert13 has intimated that carbon may be responsible for the preferential lowering of ?110 although no direct evidence has appeared yet to support this supposition. It must , be appreciated that the above-mentioned examples of surface energy driven secondary recrystallization were obtained with very pure vacuum-melted materials with oxygen contents (which is now known to be a critical factor") less than 35 ppm. During the course of a textural study on Si-Fe it has been found that under certain conditions (111) secondary recrystallization can be obtained by what is believed to be a surface energy growth selection mechanism. The purpose of the present paper is to briefly describe this result and to try and postulate the possible causes. EXPERIMENTAL Two vacuum-induction-melted, nominally 3 pct Si-Fe alloys were produced, one from pure electrolytic iron and semiconductor-grade silicon designated A and the other from commercial-purity hot band, designated B.

Jan 1, 1969

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse&apos;s conclusions, Barrett&apos;s results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By F. F. Skiba, J. E. Warren

An idealized miscible displacement process in a three-dimensional, heterogeneous porous medium has been studied via experimental computation based on a "Monte Carlo"&apos; model. The macroscopic dispersion which results solely from variations in the permeability of the porous system is related to the scale of the heterogeneity as well as the distribution function for the permeabilities. The interpretation of laboratory data is often subjective and may bt? misleading since ambiguities are not always recognized. Furthermore, an experiment performed on a conventional oil-field core does not yield a valid measure of Macroscopic dispersion for reservoir engineering purposes since the scale of heterogeneity that is significant in the laboratory is not significant in the reservoir. The analysis of field-performance data is discussed and it is shown that a unique characterization of the reservoir can not be obtained from this information alone. A possible method based on a minimum of data, for estimating the spatial distribution of permeabilities in a reservoir is postulated INTRODUCTION Many studies concerned with diffusion and dispersion in porous media have been undertaken because of the potential importance of miscible displacement processes for increasing the recovery of oil. The results from a large number of these studies have been published; in a recent paper Perkins and Johnstonl presented a comprehensive survey of the pertinent literature and excellent appraisal of the "state of the art". In this investigation, dispersion resulting from macroscopic variations in the properties of the porous medium is of primary interest. Dispersion, in this sense, is caused by fluctuations in the velocities of the individual fluid elements as they move through the porous system. This phenomenon is the result of inhomogeneities in the permeability and/or porosity, but it can be amplified by differences in the characteristics of the fluids involved. The objectives of this study are the following: (1) to determine the qualitative manner in which macroscopic rock properties affect the observed dispersion coefficient; (2) to evaluate the possible influence of macroscopic dispersion on laboratory experiments; and (3) to appraise the significance of macroscopic dispersion with regard to reservoir performance. Investigations of this type are essential since many miscible displacement processes, while seemingly understood from a mechanistic point of view, do not behave in a predictable manner under field conditions. Although a plausible explanation is that the process is dominated by the environment, little serious effort has been devoted either to describing the reservoir itself or to determining the probable effect of the reservoir properties on the process. This study is intended to be exploratory in nature; however, it is hoped that it will provide additional insight into the physical problem and that it will suggest areas suitable for further investigation. EXPERIMENTAL COMPUTATION MODEL To limit the observed dispersion to that which results solely from variations in the properties of the porous medium, an idealized process in which one incompressible fluid displaces another identical fluid is simulated. This simulation is achieved by means of a modified Monte Carlo method — by tracking a number of mathematical particles (tracer) through the system according to the steady-state, single-phase velocity distribution. Then the system is characterized by the distribution of the residence times of the particles. Since any number of particles can be injected simultaneously (a true delta-function distribution) and only pressure conditions are imposed on the boundaries, the model is completely determinate. Furthermore molecular diffusion, microscopic dispersion, adsorption and/or reaction are automatically precluded from the model. The heterogeneous medium is represented by a rectangular, three-dimensional array of uniform, homogeneous porous blocks which are randomly arranged; it is assumed that any two opposing faces of the system are held at fixed potentials

Jan 1, 1965

By R. E. Cook

This work presents the development and application of equations of the form developed by Martin1 to describe gravity segregation performance during natural depletion. One-dimensional depletion analyses are applied to several hypothetical reservoirs. Considerable attention is given to the changes in saturation distribution in the dip direction resulting from depletion at various rates. Vertical gas saturation distribution within a sand having vertical permeability is studied to illustrate conditions which provide For low gus-oil ratio production from wells selectively completed away from sand tops, as observed from well performance. Results of performance calculations are shown graphically and illustrate the rate sensitivity of the gravity segregation mechanism and the influence of reservoir geometry and withdrawal distribution. It is shown that for sufficiently high depletion rates gas saturation distribution in the dip direction is characterized by the formation of two discontinuities, or saturation "fronts"; the updip front being the gas-oil contact of the secondary gas cap and the downdip front occurring at a position dependent upon the reservoir depletion rate, withdrawal distribution and reservoir geometry. The gas saturation in the region between fronts is shown to continually increase with time, while that downdip from the lower front remains very low and relatively stable. The effect of increased depletion rate is to reduce the region of stable gas saturation and thus enlarge the portion of the reservoir producing with continually increasing gas saturation. Special attention is given to the performance of reservoirs having sufficient vertical permeability to permit liberated gas to segregate vertically within the sand section before proceeding in the updip direction. It is shown that reservoirs of this type are far less sensitive to depletion rate due to the mechanical control of producing gas-oil ratios afforded by selective well completions away from sand tops. It is shown that gravity segregation performance is adversely af- fected by decreasing reservoir cross-section area in the updip direction. It is also shown that down-dip withdrawal concentrations can restrict gas segregation rates in the dip direction. INTRODUCTION The natural depletion performance of several large producing reservoirs in Western Venezuela has unmistakably shown the significant role that gravity forces play in governing the gas-oil ratio behavior of individual wells and the over - all pressure-production performance of the reservoirs. Analysis and prediction of the natural depletion performance of these reservoirs is of great importance in determining the economics of pressure maintenance operations. In 1957, a method for the analysis of pressure maintenance performance was presented by Martin1 which, in the original and more general form of the equations involved, provides a physically sound basis for the analysis of one-dimensional gravity segregation performance during natural depletion. The work reported herein is an application and extension of Martin&apos;s outstanding developments to a series of hypothetical reservoirs in an attempt to explain the general behavior of the gravity segregation mechanism and the influence of such parameters as depletion rate, reservoir geometry and withdrawal distribution. The study considers two types of flow: "distributed flow", where vertical permeability in the reservoir is zero and fluids flow only in the dip direction while uniformly distributed over the sand thickness; and "segregated flow", where vertical permeability is sufficient to permit gas to segregate against the sand top before proceeding updip. This latter type of flow has been recognized as an important mechanism active in the massive sand reservoirs of Western Venezuela. ANALYSIS OF ONE-DIMENSIONAL DISTRIBUTED FLOW SYSTEMS For an inclined reservoir having zero vertical permeability, the velocities of oil and gas flow at any point in the reservoir can be derived from Darcy&apos;s equations as

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,&apos; Mc Quillan,&apos; Van Thyne et dl.,&apos; and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger&apos; discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95&apos; *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined for the system gadolinium-nickel. Nine intermetallic compounds have been found at compositions corresponding to the following gadolinium-nickel ratios: 3:1, 3:2, 1:1, 1:2, 1:3, 2:7, 1:4, 1:5, 2:17. The GdNi and GdNi5 compounds have congruent melting points of 1300&apos; and 1500°C, respectively while the remaining compounds melt in-congruently. Eutectics exist at 15 wt pct Ni, 31 1/2 wt pct Ni and 87 wt pct Ni with melting points of 6703 8803 and 1220°C, respectively. IN a continuing investigation of the properties of rare earth alloys, a study has been made of the gadolinium-nickel system. Previous work encompassed the iron containing alloys and a subsequent paper will deal with the constitution of the gadolinium-cobalt system. Vogel,1 examined alloys of nickel with lanthanum and cerium. R3Ni, RNi, RNi2, RNi3, RNi4, and RNi5 compounds were found. Endter and Klemm,2 Fulling et al.3 Heumann,4 and Nowotny5 found the 1:2 compositions of this series to exist in a C-15 (face-centered cubic) structure, and the 1:5 compositions in a hexagonal system. Jepson and Duwez6 more recently examined these 1:2 and 1:5 compositions and generally confirmed earlier data while Wernick and Geller7 most recently have given additional data on the GdNi5 compound. Comparisons with our results will be made in the appropriate section of this report. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been given in our earlier paper.8 Chemical analyses of the alloy samples were made by dissolving the specimen in nitric acid, precipitating the gadolinium as hydroxide and the nickel with dimethylglyoxime. Both precipitates were ignited to oxide and weighed. RESULTS Microstructure— Metallography of alloy specimens in this series has been conducted on both arc-melted and annealed materials. Etchants used have been 5 pct nital with approximately 10 pct distilled water added, for high gadolinium samples; Carapella&apos;s ferric chloride solution for intermediate compositions; and Marble&apos;s (copper sulfate) reagent for high nickel content alloys. Because of difficulties encountered in the grinding and polishing of specimens containing 40 to 75 wt pct Ni, no photomicrographs were made of such specimens. The microstructure of an arc-melted 5.3 wt pct Ni alloy is shown in Fig. 1. Light etching primary grains of gadolinium are embedded in an eutectic matrix. The microstructure of an alloy of 9.55 wt pct Ni alloy, Fig. 2, annealed 50 hr at 700°C, consists almost entirely of the intermetallic compound Gd3Ni. The structure of an arc metal alloy of approximately 19 pct Ni, Fig. 3, consists of grains of the compound GdNi embedded in the Gd3Ni2-Gd3Ni eutectic. The arc-cast structure of the 38.7 wt pct Ni alloy is shown in Fig. 4. Large primary grains of a compound rest in a matrix structure of coarse GdNi-GdNiz eutectic. Because of the occurrence of several peritectic compounds in the central region of the diagram, identification of the primary structure in this alloy is not certain. As has been indicated above, microstructures of alloy specimens containing between ca 40 and 75 wt pct Ni have not been photographed. These specimens were highly brittle, and macro- and micro-cracking were impossible to control in the grinding and polishing procedures. Prolonged annealing did not alleviate this condition. Visual observations in small specimens did, however, provide evidence for a multiplicity of phases and peritectic dissociations of compounds although rationalization of structures was not possible.

Jan 1, 1962

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,&apos; the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.&apos; It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By W. Hodge, A. F. Haskins, R. M. Evans

Refractory boron compounds are shown to resist corrosion by molten zinc. Coatings were made from ferroboron and manganese boron by several methods: welding, hard facing, and pack diffusion; and techniques of coatings are very important. Mechanical failure of the diffusion coatings can be partially eliminated by applying them to type 416 chromium steels rather than carbon steels. Welded coatings made with a tungsten arc are better than those made by other welding methods. Sintered compacts of mixtures of iron and chromium borides developed strengths of about 30,000 psi. They resisted corrosion of zinc at 600°C and oxidation at higher temperatures. MOLTEN zinc rapidly attacks common metals of construction. The rate of attack is greatly amplified at temperatures over 500°C. However, there are many applications where it is necessary, or at least advantageous, to use metal construction, such as for galvanizing pots and zinc smelter equipment. Condensers and agitator linings used in continuous zinc smelting processes are eroded and corroded by violently agitated molten zinc. Pumps, tubing, and other parts to permit transfer of molten zinc would be desirable in many zinc handling operations. The development of metallic materials which are resistant to molten zinc also might permit its use as a heat-transfer medium in modern high efficiency power plants. In reviewing previous work on zinc-resistant metals, it was evident that most of the available data refer to corrosion at temperatures just above the melting point. Tungsten and high Mo-Fe alloys containing more than 80 pct Mo resist corrosion by molten zinc.&apos;, &apos; Imhoff states that because chromium is not attacked by zinc, chromium plating improves galvanizing pot life." Nitrided cast iron has been used in die-casting machines&apos; where the molten alloy is 96 pct Zn and 4 pct Al. Other metals that have been suggested as of possible value for zinc resistance are columbium, tantalum, and titanium.V he corrosion of steel by zinc has been discussed by many authors,z, "2 None of these materials resisted corrosion by molten zinc at the temperatures used in this investigation, i.e., 600" to 700°C. I. Exploratory and Resistant-Coating Tests To make a study of zinc-resistant metals, exploratory tests were conducted to sort out roughly those materials which seemed most worthy of further development. This preliminary study included both solid metals and surface coatings. Exploratory Corrosion Tests in Molten Zinc—In initiating a study of this problem, numerous samples of metals and alloys were evaluated by dynamic corrosion tests made at 440 °C. Each metal was tested in its most readily available form, which, because of shape and size, was often unsuited for standard corrosion testing. The equipment used for dynamic corrosion testing of all materials, except in a few initial experiments, is shown in Fig. 1. Samples were tied to tungsten rods with tungsten wire, immersed in the zinc, and revolved at 12 rpm about the circumference of a 4 in. diam circle. Speed of travel was about 12.5 fpm. The molten zinc was protected from oxidation by an atmosphere of carbon monoxide, or, at a later period in the program, by a 9:1 mixture of nitrogen and hydrogen. When the effect of both molten metal and atmosphere was desired, the zinc level was lowered. Special high grade zinc was used in all of the corrosion tests. Corrosion losses for materials tested are shown in Tables I and 11. Whenever the materials were available in suitable form, the losses are reported in mils per year. It was recognized that weight losses on irregularly shaped specimens did not show the corrosion rate but the important consideration—poor resistance to corrosion—could be determined readily.

Jan 1, 1956

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962