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By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970

By Persifor Frazer

CONTENTS. PAGE 1. Committee House of Commons Report (1843).......521 2. Clark (1880).............521 3. Schröder and Schertel (1884).... . 521 4. Committee House of Lords Report (1887).......523 5. Vita (1890).............524 6. Irvine (1890-1)............524 i. Cramer (1891)............525 8. Bailey. Cohen. Tatham and Hartog (1891))......525 9. Morrison (1891)............525 10. Brunner (1891)............525 11. Bell (1892).............585 12. Oades (1892).............526 12a. Purcell (1892)............526 13. Sennett (1892)............526 14. Bulier (1892).............526 1.7. Wiesner (1892))...........526 16. Thomson (1892)............530 17. Fletcher (1892)............530 18. Committee Engineers' Club Report (1892).......530 19. Cohen and Hefford (1892)..........531 20. Discussion Soc. Chem. Ind. (1893). ..532 21. Reuss (1893).............532 22. Thomson (1894—5) ...........535 23. Clowes and Feilmann (1895). ...536 24. Callan (1895)...........536 2.5. Wright (1895)............536 25A. Mabery (1895)............536 26. Re- (1896). ..........536 27. Herman (1896)............ 537 28. Cohen and Russell (1896).......... 537 29. Dennstedt and A hrens (1896). ..537 30. Cohen (1897). ...........537 31. Drehschmidt (1897)........... 538 32. Pfeiffer (1898). .........538 33. Fritzche (1898)............ 540 34. Ost and Wehmer (1899)........... 540 35. Donkin (1899). .........541 36. Beilby (1899)............. 643 37. Berthelot (1900)............ 544

Jan 1, 1908

By Zay Jeffries

From the title of this chapter the reader could expect an attempt to outline the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the field of atomic energy would have been missed. Yet what a vast change this has made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to the atomic energy field. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without even a pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1959

By H. K. Shearer

Drilling for oil and gas in Arkansas in 1934 showed more activity than in any year since 1929; with a total of 96 completions, including 36 oil wells, 1 gas well and 59 dry holes. Of the producers, the lone gas well and 35 oil wells were in old fields, and one wildcat producer opened a new pool. Of the dry holes, 16 were in or near fields and 43 were wildcats. The total reported initial daily production of the oil wells was 9013 bbl., averaging 252 bbl. per well. Active drilling operations numbered 65 at the close of the year, compared with 26 at the beginning.

Jan 1, 1935

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

"The Washoe Smelter is situated about two miles east of the City of Anaconda. The smelter site includes about 240 acres and peculiarly adapts itself in topography to the efficient handling of material. By reason of its being on a hill side it is possible to make the level of delivery of the product of one building the level of the charge floor of the next succeeding one.THE ORES: The ore treated comes principally from the Butte district and is hauled by the Butte, Anaconda & Pacific railway, a distance of twenty-eight miles, in trains of fifty 50-ton bottom-dump cars to the railroad yards at East Anaconda. At this point these trains are• split up according to their destination,—that is, as to whether they go to the concentrator and sampling mill ore bins, or to the storage bins. In each case they are made up into trains of eight or sixteen cars, according to the size of engine to be used, and are carefully weighed before delivery to their respective bills.Some idea of the magnitude of the works may be obtained from the following figures:Amount of ore that can be treated in 24 hours…12,000 tonsLime rock from adjacent quarries…2,300 tonsCoke used…500 tonsCoal for reverberatory use…500 tonsCoal for power use…50 tonsWater, per minute, 35,000 gallons.Men employed in and around Anaconda, 3,000. Monthly payroll for above, $300,000.00."

Jan 1, 1913

By B. J. Guarnera

There have been major changes in the makeup and nature of the uranium exploration industry in recent years. Significant price increases precipitated an increase in exploration activity-according to the Department of Energy, exploratory drilling in 1977, by 140 companies, was almost 8 million m (26 million ft). This represents a 37% increase over the prior year's drilling. Projections for 1978 indicate at least 9 million m (30 million ft) of exploratory holes will be drilled in the US. Exploration expenditures in 1979, including land acquisition, drilling, and other costs, were estimated by DOE at over $236 million. Domestic expenditures for 1978 are estimated at over $250 million.

Jan 10, 1978

By G. C. Stone

AS the term "hardness" is used with many different meanings, it should be understood that it here means resistance to deformation by compression. It was determined by measuring the pressure, in pounds per square inch, necessary to reduce by 20 per cent., the length of cylinders 1 in. (25 mm.) in diameter by 2.6 in. (66 mm.) long. The tests were made at Columbia University on an Olsen 400,000-lb. machine, the load being applied at a constant rate of speed 0.0319 in. per min. The results were obtained by Messrs. Rigg and Williams, and some of them were given in a paper read at the Sixteenth Annual Meeting of the American Society for Testing Materials, in June, 1913. The remainder of the results were obtained in subsequent experiments by the same authors. In all cases, the results given are the averages of three or more closely concordant tests. All of the spelters tested were of standard commercial grades and all were of compositions making them good deliveries. The accompanying table gives the results arranged in the order of increasing hardness:

Jan 1, 1919

New York State Museum, Albany, N. Y. D H. Newland, State Geologist. A complete list of publications or the latest lists of available publications will be sent upon application. A series of Bulletins on The Mining and Quarry Industry of New York are available as follows: Bulletin 51 (1910), 15 cents; 161 (1911), 20 cents; 166 (1912), 20 cents, 174 (1913), 20 cents; 190 (1915), 15 cents; 277 (1925-26), 50 cents; 295 (1927-1929), 40 cents. Another series discusses the Geology of the State by Quad¬rangles, available as follows: Bulletin 153, Broadalbin Quad (1911), 25 cents; 154, Sche¬nectady Quad. (1911), 20 cents, 170, North Creek Quad . (1914)

Jan 1, 1933

By John V. Beall

GOING west from Denver on Route 6, the direct road to Grand Junction, one gets the first glimpse of mining a few miles east of Denver near Idaho Springs where the workings of defunct gold mines are visible on the sides of mountains along the highway. One enterprising company is turning a profit by showing tourists through the mine and mill and then selling them gold samples on the way out. We have always known that mining people are ingenious, but this proves it. About five and a half hours fast driving west from Denver brings one to Rifle, Colo., which is the site of the oil shale mine, retorting plant, and refinery of the U. S. Bureau of Mines. As you drive up to the mine, you can see a portal high on the face of the cliff in front of you where the mine surface plant literally hangs by its toenails. Below, the retorting plant and refinery gleam in the sunlight. Up at the mine, Fred Wright will show you how the oil shale is extracted in two benches (a third bench would be used for commercial mining) by the room-and-pillar method. In mining the top level, an underground crew of thirteen men have been able to produce 1500 tons of shale in each eight-hour shift. To do this, the mine is thoroughly mechanized. The mining method is de- scribed in the September issue of Mining Engineering.

Jan 1, 1949

By R. J. Wysor

Since the outbreak of the European war, few problems of raw-material supply have commanded more nation-wide attention than potash. It is well known that before the war the domestic production of potash was an insignificant percentage of the imports. The average annual importation of raw potash salts for several years prior to 1914 was slightly over 300,000 net tons, and of other potash manure salts about 700,000 tons. The sudden and almost total cessation of these imports created a unique and stringent situation. Methods of recovering potash from feldspar and other native mineral sources, and reclamation from hitherto waste products, have received a marked impetus. Soaring prices have been a keen incentive to research and industrial development. Although several brief articles concerning the possibilities of potash recovery have appeared in recent trade journals, it still may be a matter of some surprise to the average technical mind that potash might be reclaimed as a profitable byproduct in the manufacture of pig iron. At the present time it may be of special interest to present some data, largely of a technical nature, on this subject. A fairly thorough search of the literature reveals a number of articles concerning salts of the alkali metals in the blast furnace. Many of them deal with the theoretical rôle of alkali cyanides in the furnace. Several discuss the probable effect of the alkalies on the furnace brickwork. Two or three ambitious patents have been granted for reclaiming potash or other products from blast-furnace gas. However, we have heard nothing further as to the practical application of these patents. Little literature of importance has appeared during the last 10 years concerning alkalies in blast-furnace practice, and I have discovered no record whatsoever as to the actual sale or commercial disposal of flue dust for its potash content until this was inaugurated in our plant at Bethlehem. A bibliography of the most important articles discovered is appended. About 4 years ago, in the course of investigating blast-furnace stove efficiencies, I analyzed the fine, yellowish fume of which a considerable

Jan 1, 1917

By Ernest F. Burchard

A Reconnaissance of the manganese- and chrome-ore deposits of Cuba was made by the writer, as a representative of the U. S. Geological Survey, in company with Mr. Albert Burch of the Bureau of Mines, under instructions of the Secretary of the Interior, in the spring of 1918. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the island. The object of the study was to obtain authentic information for use of the United States Government as to the location, character, quantity, and availability of the manganese- and chrome-ore deposits in Cuba. Accordingly, the work comprised examination of such deposits as seemed to be of promise, without regard to stage of development, with a view to a determination of the quantity and quality of ore likely to become available for shipment during 1918 and 1919, and of the tonnage of ore in reserve. Wile it was possible to visit most of the deposits that seemed to be of promise, there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Moreover, the necessity for paying particular attention to the ore deposits and the mines precluded the possibility of making more general studies of the geology of the region, and of making satisfactory collections of country rock and of fossils, and so for other details as to the geography and geology of Cuba the reader is referred to the report by Hayes, Vaughan, and Spencer.l Mr. Burch returned to the United States about 10 days in advance of the writer, who continued, in company with Sr. Montoulieu, investigations of reported deposits in Pinar del Rio, Matanzas, and Santa Clara Provinces. On his arrival in Washington, Mr. Burch submitted to the Director of the Bureau of Mines a summary of the results of the work to date. Later the writer published, as Press Bulietin 190. 380 of the U. S. Geological Survey, a statement concerning the chrome and man-

Jan 1, 1920

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By Arthur Forsyth

A SEARCH through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1.

Jan 1, 1940

By G. V. Kurdjumou

STAFF: Editor, Gerhard Derge Acting Editor, Paul G. Shewmon Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Karl L. Fetters, President; J. S. Smart, Jr., Past-President; R. C. Cole, Vice President; R. L. Hennebach, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: W. 0. Phil-brook, Chairman; H. L. Bishop, R. C. Cole, J. N. Hobstetter, W. A. Krivsky, E. R. Morgan, F. C. Langenberg, R. E. Lund, Paul Queneau, L. L. Seigle, R. L. Smith, and T. V. Wainwright. Review and selection of manuscripts is under the supervision of the following Publications Committes: Extractive Metallurgy Division: R. E. Lund, Choirmon; M. E. Wodsworth, Vice Choirmon; D. H. Boker, Jr., G. M. Bell, R. E. Grace, W. A. Krivsky, R. A. Lewis, Chorles O'Neill, A. W. Schlechten, R. E. Shinko~ke~, and W. W. Stephens. Iron and Steel Division: T, V. Wainright, Choir- mon; ti. L. Bishop, R. E. Boni, T. E. Doncy, D. W. Murphy, Johonnes M. Uys, J. B. Wogstaff, ond R. G. Word. Institute of Metals Division: J. N. Hobstetter, Choirmon; P. A. Beck, J. J. Beckar, G. F. Boiling, J. O. Brittain, J. 0. Clark, R. 5. Davis, A. E. Dwight, R. W. Fountain, L. R. Girifolco, J. C. Gurlond, H. S. Kolish, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, H. H. Johnson, Jr., R. R. Nosh, T. N. Rhodin, R. H. Richrnon, H. C. Rogers, W. Rostoker, O. Sherby, C. W. Spencer, L. Slifkin, J. K. Stanley, R. Steinitz, H. C. Stumpf, ond R. Swolin. PuUlished bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street, New York 17, N. Y. Telephone PLaZa 2-6800. Subscription $30 peryear for non-AIME members in United States and North, South, and Central America; $32, foreign; $30peryear$7.50 for AIME members. Single copies, $6.00, single copies foreign, $6.50. The CentralAmerica;AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1962 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . .Copyright.Registered cable address, AIME New York . . . Indexed in Engineering Index, Industrial Arts Index, and Chemical cableaddres .. . AlME class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 224, Number 3.

Jan 1, 1962

By David Sinclair

THE dimensions and shapes of mine structures may at present be determined by (1) field experience, (2) structural calculations, and (3) barodynamic tests.§ None of these, however, provide information as to the stresses, their direction and distribution in a mine structure. For the design of pillars, the placing of openings relative to working places such as gangways, haulage levels, etc., this information is desirable. Photoelastic methods provide this and, while relatively new, their appli-cation in all engineering fields is assuming increasing importance. This paper, therefore, will present the method with a few applications to mining, and with sufficient reference for further study by the reader. PART I THE PHOTOELASTIC METHOD The photoelastic method of stress measurement determines the stress distribution in a two-dimensional model by optical means. It makes use of the fact that when a piece of isotropic transparent material, such as glass, celluloid, or Bakelite, is stressed and viewed in polarized** light a picture is seen which indicates by its color bands of light, or fringes, the magnitude of the stresses, their direction and their distribution.

Jan 1, 1940

By Paul D. Martinka

Coal is the principal energy source for the American Electric Power System (AEP System), which generates and delivers more electric energy to its customers within a seven-state area than any other investor- owned electric public utility. The company expected to burn 21.5 million tons of coal in 1968 at its coal-fired, steam-electric generating stations. About 4.3 million tons, representing 20% of the firm's total annual requirement, was the expected yield of its captive coal mines; the other 17.2 million tons were to be purchased from commercial mines in Ohio, West Virginia, Virginia, Kentucky, Indiana, and Illinois. American Electric's largest captive coal mining operation is conducted by Central Ohio Coal Co., a subsidiary of Ohio Power Co., at the Muskingum mine in the Meigs Creek No. 9 coal field of southeastern Ohio. The mine was started in 1953 to produce the coal requirements of the Philo and Muskingum River generating plants of Ohio Power Co., and it has been supplying their annual requirements in the range of 2.5 to 3.5 million tons since that time. The Muskingum River plant is one of the major steam-electric generating stations on the AEP System. This plant began operation in 1953 with a 215-megawatt unit and now has five generating units with a total plant capacity of 1,495 megawatts. The addition of the 615-megawatt Unit 5 in the summer of 1968 increased the total annual coal requirement of the plant from 2.6 to 4.4 million tons. In order to produce the additional 1.8 million tons of coal for the Unit 5 addition and to exploit the remaining coal reserves at the Muskingum mine most economically, Central Ohio Coal Co. has undertaken a $41 million expansion and modernization program, involving the world's largest dragline and an electric railroad.

Jan 1, 1969

By William H. Bassett, C. J. Snyder

Cable sheaths made from common lead have been used to protect underground cables since the beginning of the power-cable industry. Only within the last few years, however, has a systematic study of the production methods and of the causes of failures in cable sheathing been undertaken. Recent increases in the use and demands for service made upon power cables have emphasized the importance of high-quality cable sheaths. It was customary for the users to attribute the cause for their sheath failures to the lack of purity of the lead, but this contention has not been borne out by field and laboratory inspection of the sheaths. During the past two years the writers have had an opportunity to examine various types of sheaths that were removed from power cables after failure. These samples were obtained from various parts of the country and represent, it is supposed, the production of the principal cable manufacturers. Aside from corrosion, the common field difficulties can be classified either as mechanical or structural, as outlined below, and when structural irregularities are found they can all be attributed to manufacturing causes and in no way reflect the purity of the lead. Clasxification of Cable Sheath Failures Other Than Corrosive Mechanical Irregularities A. Splits caused by excessive internal pressure B. Injuries such as nail holes, cuts, tsars, etc. C. Intercrystalline cracks caused by vibration Structural Irregularities A. Splits C. Voids in wall of sheath a. Caused by imperfect welds a. Blisters 13. Holes through sheath b. Laminations a. Caused by yellow oxide inclu- D. Questionable structures sions in sheath wall a. Prominent flow lines b. Blowouts by entrapped gases b. Large areas filled with suboxide during manufacture c. Scattered yellow oxide or dirt C. Caused by inclusions of dirt and

Jan 1, 1933