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By William A. Johnson

THE fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems, but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state 1-3 It is doubtful that this mechanism can ever he directly ascertained, rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected Because of its relative simplicity, diffusion in a system containing only one kind of atomic species-commonly called self-diffusion-is of considerable theoretical interest It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments-of which diffusion in a chemical concentration gradient and self-diffusion are two important types-are carefully performed and inter-compared Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data † Self-diffusion implies the diffusion of something into its exact counterpart, the detection of such a process is patently impossible, and it is-necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties, neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atone down its chemical concentration gradient The first measurements of self-diffusion ii ere made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7,8 copper,2,9 and zinc 10 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness, it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By Albert F. J. Bordeaux

Alluvial gold was first discovered in Guiana in 1852, in the sands of the Arataye river, by Paulino, a Braziliaii convict. During the following years, gold was found also in the rivers Orapu, CirubQ, etc. In 1873 the famous placers of the Sinnamary system were opened: Saint-Elie, Dieu-Merci, Adieu-Vat, and Couriege. This group of mines has produced nearly $10,000,000, according to official records, not including the gold that escaped the taxes. The discoverer was a mulatto named Vitalo. Except in a few rich spots, the gold was rather evenly distributed along the creeks. In one instance, gold was found in the red dirt from the slope of a hill, which, after transport to the creek, gave an amount of 150 kilograms. The placers of the Mana system, Enfin, Elysee, Pas-Trop-Tot, date from 1878, and their production has been about %g5,000,000. In 1888, the Awa placers, along the boundary bet.ween the French and Dutch Guianas, on the Maroni and its tributaries, were discovered. They have yielded $12,000,000. The only industrial company, the Dutch Guiana Freiich Minillg Co., produced in 15 years about 2,500 kg. of gold, worth $1,500,000. From 1893 dates the famous Carsewene discovery, in territory then in dispute between France and Brazil. A settlement was made recently in favor of Brazil, by arbitration of the Switzerland State Council. Carsewene is said to have produced about $18,000,000 in six years (1894-1900), but not even one-fourth of tho production went through French Quiana and

Jan 1, 1911

Air-sand Process of Cleaning Coal Discussion of paper by THOMAS FRASER and H. F. YANCEY, presented at the New York Meeting, 1926, and issued, as Pamphlet No. 1561-F, with MINING AND METALLURGY, February, 1926. T. DEVENNY, Edgarton, W. Va.-How near the size of the sand can the coal to be treated be brought? Do you use an 8-mesh coal on that cleaner? J. J. RUTLEDGE, Baltimore, Md.-From the little I have seen of the apparatus in operation, I should say 8-mesh. In my experience in metalmine concentration work, trying to separate different minerals on one jig, sometimes I have succeeded and sometimes not. This apparatus has appealed to me; something of this kind should be useful with the silicates and carbonates of zinc. I think this apparatus has possibilities in metal mining. Recently in our coal field a screen has been introduced for cleaning coal; it is giving excellent service. When I asked the inventor why he did not take it to the metal mines, he said there was a good and sufficient reason, in a patent way. There may be reasons why it would not be applicable for metal mining; but the simplicity of it appeals to me and I cannot see why it could not be so used. T. FRASER (written discussion).-We feel that 8-mesh would be about -the minimum size of coal practicable to treat by the air-sand process. This would depend partly upon the friability of the coal. The more nearly the lower size limits of the coal- approaches the size of the sand, the more .time will be required in screening the sand out of the cleaned coal, which would mean a little more chance of breakage. In regard to the treatment of ores; this would necessitate the use of some heavier mediums than ordinary silica sand, or some other means of making the separation at a higher specific gravity than is required for coal. We are now working on a method of obtaining this effect for the preparation of anthracite coal without resorting to the use of heavier and more expensive material than common sand.

Jan 1, 1927

By Nathaniel Arbiter, Arthur F. Taggart

THE fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. EXPERIMENTAL Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,' and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: 1. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. DISCUSSION OF RESULTS Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether

Jan 1, 1943

IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph W. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr.,

Jan 1, 1914

By Carl Henrich

Aspen, the flourishing mountain- and mining-town of Pitkin county, Colorado, is located in the valley of the Roaring Fork, 11 miles above Glenwood springs, where that stream empties its waters into Grand river, a tributary of the Colorado. The Roaring Fork heads on the western slope of the Sawatch range near Grizzly peak, and runs in a general northwesterly direction to its junction with the Grand river. Of its numerous tributaries, Castle creek joins it just below the town of Aspen, the town being built on an extensive flat hounded on the northeast by the Roaring Fork and on the west by Castle creek. The latter heads at the junction of the Sawatch and the Elk mountains and flows northward between the two chains, until it empties into Roaring Fork. Opposite the town of Aspen, Hunter creek, coming westward from the western slope of Mount Massive, joins the Roaring Fork. About a mile north of Aspen, the bed of Hunter creek is at least 300 feet higher than that of the Roaring Fork at Aspen. Hunter creek forms thus, at its mouth, one of the best water-powers in Colorado. A portion of it is now utilized for electric lighting in Aspen, while in the near future, the whole of this magnificent natural power will be applied, through electric transmission, for hoisting, pumping and ventilating at different mines of the district. The mountain opposite the town of Aspen, on the east side of Hunter creek (which near its mouth flows southerly), is called Smuggler mountain, from the famous mine at the foot of it. On the other, or western, side of Hunter's creek (see map, Fig. I), a higher mountain rises, on the slope of which the regular dip of the Triassie or Upper Carboniferous red sandstone strata, alternating with white layers of the same rock, can be clearly seen from town. This mountain is called Red mountain, from the prevailing color of its rocky

Jan 1, 1889

By W. G. Jewitt

YELLOWKNIFE, the most northerly Canadian gold mining district, is once more in the throes of a boom. Touched off by spectacular and well-publicized diamond-drilling results on the property of Giant Yellowknife Gold Mines, Ltd., mining companies and the general public are competing for mining claims and for the shares of companies owning mining claims in the area, with little regard for values. Such a stock-market boom has various unfortunate consequences but undoubtedly one beneficial result is that considerable amounts of money are made available for serious development. The Yellowknife mining area lies on the north shore of Great Slave Lake, in the Northwest Territories, at a latitude of approximately 62°30' north. The topography is a low-relief phase of that usual in the Canadian Laurentian shield. Roughly, one third of the surface is lake-covered, one third muskeg or overburden, and one third is bare

Jan 1, 1944

By W. R. Shimer

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

Jan 9, 1913

By L. B. Gittinger

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

Jan 1, 1975

By G. P. Bowman, D. F. Howard, R. K. Saxer, J. R. Myers

This study was undertaken to redetermine the phase diagram of the lead molybdate-bismuth molyb-date salt system. A portion of this diagram was originally determined by Zambonini in 1920, and more recently by Beale. Thermal analysis and X-ray methods were used to define this system. The diagram was found to be a simple eutectic type with an eutectic at 11 mol pet lead molybdate and 634OC. A maximum solid solubility of 6 mol pet was found at the lead molybdate end of the diagram. Solid solubility at the bismuth molybdate end of' the diagram appeared to be quite limited and possibly nonexistent. These results generally agree with those of Beale, but differ significantly from those of Zambonini. MOLTEN salt systems have been vigorously investigated since World War 11. Much of this work has been performed as pure research; however, consideration has recently been given to their possible use as coolants in nuclear reactors. Because of this application and other potential applications, it was decided to reinvestigate the lead molybdate-bismuth molybdate phase diagram. This diagram was originally determined by Professor F. Zambonini of the University of Turin in 1920.' In 1961, a portion of this diagram was redetermined by Beale.2 With the quality equipment and high-purity materials available today, it was expected that discrepancies between the results of this present investigation and Zambonini's work would be obtained. This investigation was conducted in two parts. First, the general shape of the phase diagram was determined by cooling-curve analysis. Next, the primary solid-solution phase at the lead molybdate end of the diagram was investigated by means of X-ray diffraction techniques. EXPERIMENTAL PROCEDURE High-purity lead molybdate, assaying 99.993 pet, and high-purity bismuth molybdate, assaying 99.989 pet, were employed during this investigation.* The results of a spectrographic analysis of the two salts are presented in Table I. Twenty-two experimental compositions were prepared for cooling-curve analysis. Compositions selected are presented in Table 11. Several randomly selected samples were analyzed chemically to check that the compositions of the prepared specimens were within the limit of

Jan 1, 1964

By Gerard Matthes

Only in recent years has any practical headway been made in the application of aerial photography to geological problems, and up to the present time its principal value to the geologist and mining engineer has been in "areal geology;" i. e., the study of formations as revealed at the surface. The object of this paper is to set forth briefly the principal advantages that may be derived from aerial photographic data in geological work and to serve in a measure as a guide to those who may be contemplating its use. Geophysical prospecting has for object the locating of mineral under the surface. Inasmuch as the geologist's chief complaint in life is a dual one—inability to see under the surface and inability to visualize comprehensively what he does see on top of the ground—geophysical prospecting coupled with aerial photography should do much to lessen his burdens. To what extent aerial photography can be made a useful adjunct to geophysical prospecting remains to be proved, but the inference drawn here is that it holds many alluring possibilities. To avoid disappointments, it should be stated at the outset that to the geologist or mining engineer an aerial photograph or mosaic is only a tool, the efficient use of which he must set out to master. Upon his skill and ingenuity in applying it to particular problems will depend largely the value of the results that he will obtain. Under the most favorable conditions an aerial mosaic, or even a few loose photographs, because of the exceptionally comprehensive oversight which they afford of field data, such as dips and strike observations at isolated outcrops, local indications of faulting, mineral and fossil finds, greatly facilitate study and correlation, save much tedious foot work, and may repay their cost many times. Even so, types of country may be found where the most skillful use of the best of pictures will produce results so meager as to render the cost of aerial photography entirely unwarranted. Between these two extremes will be found endless variations and possibilities. Hence no set rules can be promulgated. The safest procedure is to treat each case as a separate problem and to carefully weigh the relative advantages and shortcomings of aerial photography before embarking on its use.

Jan 1, 1928

By R. T. DeHoff, F. N. Rhines

The problem of determining the number of particles of a phase distributed randomly in unit volume c an opaque matrix from measurements made on random plane sections is closely investigated. A formalized derivation for the general case is presented. Applications of this formal result are made to specific types of aggregates dispersed in a matrix; circles, particles with flat circular ends, cylinders, and constant shape aggregates of ellipsoids of revolution. Quantitative measurements of the average geometric properties of these aggregates are developed. In 1953 R L. ullman' developed a technique for determining, from measurements made on random plane sections, the number per unit volume, Nv, of particles imbedded in an opaque matrix. Using meas urements previously developed for volume fraction, vV,' and surface area per unit volume, .SV,= he was able to determine average volume, average surface area, and average dimensions of particles, independent of size distribution, for spheres and circular disks,' as well as for uniformly sized cylinders of any axial ratio.4 The technique is mathematically rigorous for the cases studied. Recent studies of this problem have yielded rigorous solutions for the general case of cylinders, permitting evaluation of NV independent of size distribution and with all axial ratios intermixed. Generalization to shapes having flat, circular ends has been deduced. A solution has also been obtained for the ellipsoid of revolution, independent of size distribution, but requiring a constant axial ratio in the generating ellipses. In the following derivations, as in Fullman's work, it is assumed that the problem is purely a combination of geometry and probability theory,that is,eithe the particles to be measured are imbedded randomly in the matrix, or a sufficient number of random plane sections are taken to make the sample representative. A relationship exists between the number of par- ticles of a given size and shape that may be situated in unit volume (Ny) and the number of intersections a random plane can be expected to make with these particles (Na). It is the purpose of the following section to derive this relationship. The probability of Intersecting Convex Bodies. Consider a convex, closed surface, that is, one for which no two surface normals point in the same direction, situated at some arbitrary position and orientation in a cube of material that is one unit long at each edge. It is not necessary to assume that this surface is symmetrical. Let planes be constructed in the cube parallel to the top face and at random distances from it. Those planes which lie between the two planes which are just tangent to the top and bottom of the surface will intersect it. The probability that a plane will intersect the body may be defined as the limit of the fraction of planes that lie between the two tangent planes as the total number of planes constructed becomes infinite. This fraction, in the limit, is equal to the distance between the two tangent planes, DV, divided by the total length over which planes are constructed, which has been taken as unity. If the body is now rotated to a new orientation, applying the same argument, the probability of intersection is again numerically equal to the distance between tangent planes. Let DV ($, 0) be defined as the distance between tangent planes of a convex body as a function of orientation, Fig. 1. The probability, Pr, of intersecting the body with a randomly oriented and randomly positioned plane, is then equal to the average value of DV (0, $) over all possible orientations. It may be easily shown that for a system of spherical coordinates the probability of finding an orientation between Q and Q + de, $ and $ + d$ is (1/4n) sin $ dB d$, so that This relationship may be applied to each body in an aggregate of convex bodies. In particular, if the bodies in an aggregate are classified according to size and shape, and the ithsuch class is considered, Eq. 111 may be applied to this entire class, the probability of intersecting any body in this class being

Jan 1, 1962

Albert Sauveur, Cambridge, Mass. (written discussion).— In his introductory paragraph, the author states that he has come to bury Beilby, not to praise him. The paper, however, gives the impression that while he may have dug the grave, Beilby is still at large. I am not one of those whom the author calls enthusiastic supporters of Beilby's amorphous theory and in support of this claim quote from a book I am writing: "Attractive as the amorphous theory is, and notwithstanding the ability with which it has been presented and the renown of its sponsors and supporters, it should not be accepted without reservations as a demonstrated fact.... So long as it explains more satisfactorily than other theories a greater number of phenomena in which it may play a part, we should use it in preference to others as the best available. Let us avoid the danger, however, into which too many fall, of accepting as indisputable truths, statements and theories emanating from those whom we hold in great esteem. It is not what those men themselves would wish us to do. I am entitled, I think, to occupy a position in the middle ground. Neither should Howe be classified with the enthusiastic supporters for he has written that the theory should be classed rather among the precious working theories than among those firmly established," a very wise and prudent statement. Jeffries, on the other hand, I would not hesitate to describe as an enthusiastic supporter. The author reproaches the advocates of the amorphous theory with having taken whatever properties they needed and with having assigned them arbitrarily to the hypothetical amorphous phase. He then applics their method to small crystals. If the existence of an amorphous phase is assumed, its greater tenacity and greater hardness is satisfactorily explained in the words of Howc: '(This greater strength is natural, because the amorphous state lacks the cleavages and slip planes which weaken crystalline substances." Can the greater strength and hardness claimed for small crystals be as satisfactorily explained? Nor do I think that the cold deformation of metals through successive slips within the crystalline grains can he accounted for as acceptably by the "small crystals theory."

Jan 1, 1923

Albert Sauveur, Cambridge, Mass. (written discussion).— In his introductory paragraph, the author states that he has come to bury Beilby, not to praise him. The paper, however, gives the impression that while he may have dug the grave, Beilby is still at large. I am not one of those whom the author calls enthusiastic supporters of Beilby's amorphous theory and in support of this claim quote from a book I am writing: "Attractive as the amorphous theory is, and notwithstanding the ability with which it has been presented and the renown of its sponsors and supporters, it should not be accepted without reservations as a demonstrated fact.... So long as it explains more satisfactorily than other theories a greater number of phenomena in which it may play a part, we should use it in preference to others as the best available. Let us avoid the danger, however, into which too many fall, of accepting as indisputable truths, statements and theories emanating from those whom we hold in great esteem. It is not what those men themselves would wish us to do. I am entitled, I think, to occupy a position in the middle ground. Neither should Howe be classified with the enthusiastic supporters for he has written that the theory should be classed rather among the precious working theories than among those firmly established," a very wise and prudent statement. Jeffries, on the other hand, I would not hesitate to describe as an enthusiastic supporter. The author reproaches the advocates of the amorphous theory with having taken whatever properties they needed and with having assigned them arbitrarily to the hypothetical amorphous phase. He then applics their method to small crystals. If the existence of an amorphous phase is assumed, its greater tenacity and greater hardness is satisfactorily explained in the words of Howc: '(This greater strength is natural, because the amorphous state lacks the cleavages and slip planes which weaken crystalline substances." Can the greater strength and hardness claimed for small crystals be as satisfactorily explained? Nor do I think that the cold deformation of metals through successive slips within the crystalline grains can he accounted for as acceptably by the "small crystals theory."

Jan 1, 1923

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By T. Sterry Hunt

I HAVE in a previous communication called the attention of the Institute to the geognostical relations of the crystalline iron ores belonging to the Eozoic rocks of North America, at which time I noticed (1) those associated with the gneisses of the Laurentian series, (2) those of the crystalline schists of the Huronian, as seen in Northern Michigan and in many localities along the Appalachians ; (3) those of Southeastern Missouri associated with petrosilex porphyries and schistose rocks, and presumed to be nearly of the same age with those of the Huronian schists; and (4) the highly titaniferous ores of the Norian or Labradorian series from Essex County, N. Y., and from various parts of Canada. It may here be remarked that, although the presence of titanium is most marked in the Norian ores, this objectionable element is sometimes found in the schistose ores of the Huronian, and to a lesser extent in certain Laurentian magnetites. The ores of each of these geological divisions have their individual peculiarities, which serve to distinguish them to such a degree that the magnetites and specular ores of the Laurentian are as dissimilar to those of the Huronian as are the crystalline silicated rocks of the two series. As it happens that these mineralogical dissimilarities correspond to differences in composition and in adaptability to different processes of manufacture, which, in the present condition of the iron industry, are objects of special consideration to metallurgists, it will be seen that these geognostical distinctions become of great practical importance. During the past year I was desired by the Geological Commissioners of Pennsylvania to devote a few weeks to certain geological studies in the eastern part of the State, in the course of which I was enabled to make, with regard to its crystalline iron ores, some observations to which I desire to call the attention of the Institute. I may mention, in passing, that the great South Mountain belt, from the Schuylkill to the Delaware, is composed of Laurentian rocks, in which are found the characteristic ores of the series like those of the Highlands of New Jersey and New York, and of the Adiron-

Jan 1, 1876

By O. E. Kiessling

A GROWING uneasiness in the oil fields indicates that doubts are arising as to the efficiency of the present technical, economic and legal arrangements affecting production. Recent documents of the federal government, debates in state legislatures, editorials in the daily press and statements of oil company executives re-echo the notion that the present methods of producing oil satisfy neither the business man nor the public. Such intimations are of utmost importance, since oil is a vital clement in modern industry and dependence upon it increases as new uses develop. SECTION I-PRESENT SCHEME OF COMPETITIVE EXPLOITATION IS WASTEFUL The oil industry has convinced itself, for very good reasons, that the present scheme of competitive exploitation results in losses, both in terms of quantities of oil and in terms of profits. The story of these losses is familiar enough, and it is necessary only to distinguish and summarize briefly certain factors that are of importance to the following argument. Oil pools are exploited under a competitive economic system based on private ownership and contract; the hope of profits attracts capital and enterprise, and competition is supposed to serve as a regulative factor. Whether such a scheme of industrial organization works is partially dependent on the ability of the producer to withhold or produce is commodity as he sees fit, in accordance with the dictates of market demand.

Jan 1, 1927

By Basil B. Zavoico

During 1938 the Russian oil industry, while able to increase its production 4.69 per cent above the preceding year, was not successful in correcting some of its basic difficulties, and the industry's position as it entered 1939 was unsatisfactory. The internal political difficulties of 1937 and 1938 took a toll in the oil industry as they did elsewhere in the U. S. S. R., further complicating the solution of the problems facing it, most important of which still remain: lack of experienced and responsible leadership, able to make quick decisions; undisciplined and migratory labor; and insufficient and often unsatisfactory quality of the various equipment needed by the industry and its ineffective distribution. Recent developments in the U. S. S. R. suggest that during 1939 the management will be granted more latitude and hence somewhat better results may be anticipated from the executive branch, provided, however, the "purges" do not recur. The labor should be better disciplined and should not shift as easily, owing to the introduction, at the close of 1938, of individual labor passports to all workers in the country, the principal purpose of which is to correct those two deficiencies. It is not anticipated, however, that the service of supply will show any appreciable improvement in 1939, partly because of inherent difficulties and partly because the manufacturers of heavy machinery are working primarily and necessarily for munitions. Production Production of crude oil during 1938 is estimated at 224,714,000 bbl., as compared with 212,742,000 bbl. in 1937, an increase of 4.69 per cent but 12.76 per cent below the planned output. While there were no major readjustments in the source of supply of crude oil, both the older districts, Baku and Grozny, were barely able to maintain their 1937 levels of production, the increased output being supplied primarily by the fields of Maikop and Ural Permian Basin districts. While exploration work was outstandingly successful in 1937, in 1938 no discoveries of any

Jan 1, 1939

By Basil B. Zavoico

During 1938 the Russian oil industry, while able to increase its production 4.69 per cent above the preceding year, was not successful in correcting some of its basic difficulties, and the industry's position as it entered 1939 was unsatisfactory. The internal political difficulties of 1937 and 1938 took a toll in the oil industry as they did elsewhere in the U. S. S. R., further complicating the solution of the problems facing it, most important of which still remain: lack of experienced and responsible leadership, able to make quick decisions; undisciplined and migratory labor; and insufficient and often unsatisfactory quality of the various equipment needed by the industry and its ineffective distribution. Recent developments in the U. S. S. R. suggest that during 1939 the management will be granted more latitude and hence somewhat better results may be anticipated from the executive branch, provided, however, the "purges" do not recur. The labor should be better disciplined and should not shift as easily, owing to the introduction, at the close of 1938, of individual labor passports to all workers in the country, the principal purpose of which is to correct those two deficiencies. It is not anticipated, however, that the service of supply will show any appreciable improvement in 1939, partly because of inherent difficulties and partly because the manufacturers of heavy machinery are working primarily and necessarily for munitions. Production Production of crude oil during 1938 is estimated at 224,714,000 bbl., as compared with 212,742,000 bbl. in 1937, an increase of 4.69 per cent but 12.76 per cent below the planned output. While there were no major readjustments in the source of supply of crude oil, both the older districts, Baku and Grozny, were barely able to maintain their 1937 levels of production, the increased output being supplied primarily by the fields of Maikop and Ural Permian Basin districts. While exploration work was outstandingly successful in 1937, in 1938 no discoveries of any

Jan 1, 1939