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By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE use of galvanic cells for the determination of oxygen activities has spread rapidly since the suitability of calcia-stabilized zirconia as a solid electrolyte material was first demonstrated by Kiukkola and Wagner.' In many of these investigations:-7 including several at ARL, the free-energy changes for various oxidation-reduction reactions involving the oxides FexO, NiO, and Cu2O have been measured as a means of assuring that a cell apparatus is functioning properly. As a result, a large quantity of data pertinent to the calculation of the high-temperature standard free energy of formation (?GO) of these oxides has been accumulated. AGFexo has been carefully measured in many independent investigations, using a variety of techniques, and consequently is accurately known. chipmans has used this informa-

Jan 1, 1968

By John Henry Harden

This shaft, located in the northern anthracite coal-field about 2300 feet southwest from the court-house at Wilkes-Barre, in the County of Luzerne, Pa., is the property of the Lehigh & WilkesBarre Coal Company. The sinking and cribbing to the solid rock (see isometrical view on Plate IX) was conducted by Mr. W. W. Kenrick. Dimensions of the earthwork to the foundation of the cribbing, 51' 2" long, 17' 4" wide, 31' deep. Total amount of excavation in cubic yards, 998.5. Dimensions within the permanent cribbing, 45' 4" long, 11' 16" wide, 31' deep, divided into six parts by buttons 8" x 12", each division, 7' x 11' 6". Permanent cribbing 12" x 12"; temporary cribbing 8" x 10" ; backing, 3" thick ; clay puddle to exclude surface water, 12" thick; conductors, 8" x 5"; lining, 1" thick from top to bottom of the shaft. In the latter part of the year 1871, Mr. H. Murray & Son contracted with the company for the continuation of the work at the rate of four hundred dollars per yard in depth, to a point 100 feet below the Hillman seam of coal; for the succeeding 100 feet the price to be increased twenty-five dollars per yard, and so on until the bottom rock of the Baltimore seam of coal was found. The size of the shaft within the cribbing timbers is 45 feet 4 inches by 11 feet 6 inches, having six divisions of equal dimensions, 7 feet by 11 feet 6 inches, giving room for what is known as the "standard diamond " car, whose capacity when level full is 100 cubic feet, but when loaded by the miner 4 inches above the top contains 112 cubic feet." Two divisions of this shaft are intended for hoisting coal from the Hillman seam, two from the Baltimore seam, one for ventilation, and one for pumps. The works were planned for two pairs of direct-acting, high-pressure engines, twenty-four boilers, and for an estimated output of 2500 tons of coal per day from the two seams.

By Robert Sisselman

Central Sweden's Grängesberg underground iron ore mine, which accounts for more than three million tons of pellet product annually, is experiencing a major changeover to continuous block-caving. The newly-adopted method, complete with a total revamping of mining equipment, will be fully operational by 1975. For the past 15 years, Sweden's Grängesberg mine has been mined using two different methods. Those ore thicknesses of 117 ft or greater (they comprise about 70% of the total area) are worked by block-caving techniques with cross-cutting carried out on each 195-ft working level, and loading at the foot wall on each 58-78-ft level. Sub-level caving is carried out in all ore sections less than 117 ft thick.

Jan 1, 1974

By James P. Sloss

WHAT is the likelihood if any-that a real gold mining industry will be developed in the southern Appalachian region? Has the increase in the dollar value of gold from $20.67 to $35 per ounce potency to turn the trick? Suppose it be assumed that the price of gold will, at worst, not recede, and that the cost of digging ore and treating it of which the average level of commodity prices and wages is a fair index-will, at most, not exceed that prevailing in 1926. One may or may not accept these as reasonable assumptions; but one must arbitrarily remove some of the potential variables if one is to get anywhere on a problem like this. As a matter of fact, this article is not going to venture a conclusive answer to the question that has been posed; but it will endeavor to present some of the factors that have a bearing on the problem. The writer spent ten days visiting a dozen properties in Virginia and the Carolinas early in April, 1935, and in doing so got a first-hand slant on mining conditions in the domain of King Cotton.

Jan 1, 1935

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By Oliver Bowles, Carl A. Gnam

THE construction industry normally contributes extensively to the general economic welfare of all sections of the country. Billions of dollars are spent for materials and labor, and the success or failure of many business enterprises depends upon the volume of construction. The steel, aluminum, copper, cement, brick and tile, lime, gypsum, stone, sand and gravel, and several of the less prominent mineral industries are vitally concerned. Of great interest, therefore, is the accumulation of needed construction following the relative inactivity of the past five years, the recent moderate revival in building, and the prospect of a broader and more definite upturn. One may judge the magnitude of possible expenditure for construction by what has occurred in the past. The peak years were 1925 to 1928, inclusive, when the annual values of con- tracts awarded amounted to over six billion dollars. In marked contrast was the 1933 total of about 1% billion, the lowest level shown in the Federal Reserve Board Index, which goes back to 1919, and the more favorable 1935 figure of about 1.7 billion. An increase of nearly four billion over the 1935 volume would be necessary to equal the peak year 1928.

Jan 1, 1936

By D. L. Martin, E. R. Parker

DURING the heat-treatment of silver specimens for tensile tests it was observed that the bars blistered and became brittle when heated in a hydrogen atmosphere. [ ] To check this unexpected result, a wide variety of commercial silvers were heated in hydrogen at 850°C, Only a few of the materials developed blisters, the most severe of which is the tube pictured in Fig. I. The microstructure of a cross section of the tube is shown in Fig, 2. The embrittlement is extremely severe at the edge; the blisters result from the severe deforma- [ ] tion of the surface material by large underlying gas pockets, The effects resulting from hydrogen embrittlement of silver have been observed by numerous investigators over a long time1,2,3 although it was only recently that a clear explanation was offered ,4 However, the damage resulting from hydrogen embrittlement has not been generally recognized; and it is of advantage to know more about this phe-

Jan 1, 1943

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By L. C. WYMAN

THIS paper discusses what mining reports should contain when presented to the California State Corporation Department, to accompany applications for the sale of stock to the general public, but the principles involved apply to mine financing everywhere. Such reports should &apos;be as clear and concise as possible, endeavoring to tell the truth in as few words as necessary. Should the engineer be aware that his report is to be used in connection with the sale of stock to the general public, he should consider the public as his client as well as the person who actually employs him. It is always required that the engineer be favorably known and of recognized standing. The following points should be given careful attention : 1. A legal description and location of the property. 2. Transportation conditions, and how they may be expected to affect the operating costs. 3. A brief history of the property, its production record as to tonnage, grade, and character of the ore should be given. Should the property have suspended operations for any reason, this should be given. Any details of former operating costs should be given, especially as to how any improvement could be made, due to better methods which might be employed.&apos; 4. The main geological features and whether they are such as to lead the engineer to believe that the mine may possibly &apos;be exhausted or the ore of such grade as to be no longer profitable. If he considers them favorable, he should give his reasons for the belief that further development work may produce profitable results. A map showing these features should be submitted, and it is not necessary that such map be highly colored or contain any more than the essential matters. 5. Other mines in the district, or those with similar

Jan 1, 1929

By Charles Macdonald

It may seem to be almost unnecessary to occupy the time of the Institute in further consideration of a question which has been so comprehensively treated in papers already on file in our own Transactions and in those of the American Society of Civil Engineers. Unfortunately, however, the results of these concerted efforts have not been materially to increase our stock of Knowledge in the direction sought for; and as the necessity for this information is becoming.more and more apparent as the demand for structural materials increases, it is believed that by continuing the agitation by means of discussions in this and kindred societies, whose members are vitally interested in obtaining reliable data as to the properties of the materials they are called upon to work with, public opinion may be educated up to the importance of exerting such an influence upon the law-makers of the country as will result in the formation of a competent board, with adequate means at its disposal, to carry out this great work in a manner alike acceptable to the makers and users of the materials in question. It may be proper in the first place to glance briefly at what has been attempted thus hr, then to indicate some of the more important lines of needed investigation, and finally to consider reasons why government aid may with propriety be sought for in carrying on the work. At a convention of the Society of Civil Engineers held at Chicago June 5th, 1872, it was, on motion of General William Sooy Smith, resolved, that, " Whereas, American engineers are now mainly dependent upon formula for the calculation of strength of the different form of iron and steel, not based on experiments upon American materials and manufacture; and " Whereas, There differ greatly in many of their ch~racteristics front thoae of foreign production, both in their nature and forma: therefore,

Jan 1, 1882

By Frank Firmstone

In a paper read at the meeting in Cleveland, Ohio, in 1875,* I showed that as a result of changing from open-topped to close-topped furnaces at the Glendon Iron Works, there had been a decided falling off in regularity of working, which we attributed to the very different distribution of the materials in the new method of filling. Subsequent experience has, on the whole, confirmed the opinions then expressed, and in 1881 we decided to try the modification of the Langen charger, shown on the accompanying drawings, thinking by its use to approximate to the distribution obtained by dumping the barrows at six equidistant points in the circumference of the open-topped furnaces. The top of the furnace is closed by a ring-shaped " bell," as we still call it, the outside of which is cylindrical and rests by the turned lower edge on the bored seat of a " loose ring," supported by the lower part of the hopper. The inside of the bell is an inverted frustrum of a cone, the central opening in which is closed by a cylindrical plug, which is prolonged into a pipe to carry off the gas.? This center-plug is connected by rods and chains to sectors on the ends of a forked lever, to the other end of which is attached, by a wire rope, the piston-rod of the blast-cylinder used in opening the top. The rods connected to the center-plug pass loosely through the apexes of triangular frames, to the other angles of which the bell is attached; it thus being suspended by four points when the top is open. When the materials are dumped out of the barrows into the hopper, a part is thrown over the crest of the bell into the space between it

Jan 1, 1885

By G. D. Tranter

THE importance of ladle and teeming practice and its relationship to the yield and quality of the product has focused considerable attention on this phase of open-hearth operation. Inherently bad steel cannot be perfected by manipulation during teeming, but through the proper handling of "off heats" serious losses, which in many cases arise, can be greatly minimized. Conversely, good steel can be ruined as a result of poor workmanship in the -pit, and rendered unsuitable for application to orders where exacting surface and physical requirements are essential. Sufficient evidence has been secured to warrant careful investigation of pit operations when an abnormal number of basic defects develop in the semifinished product or are found on the inspection table. This paper is written from the standpoint .of the problems involved in making satisfactory ingots for sheet rolling. Furthermore, since rimming steel is almost universally used for manufacture of sheet, the data presented herein refer particularly to that type of steel. Going back some 30 years in open-hearth .history, the word "pit" properly described the hole into which the ladle was lowered to receive the metal tapped from the furnace. The working space was necessarily limited, and the disposal of slag and metal overflowing the ladle or lost because of breakouts presented a serious problem. The equipment, of course, was rather crude in the light of present-day development. Often no ladle stands were provided, the ladle being hung on the crane beneath the runner. When delayed taps occurred, the ladle was often held in position for many hours, thus tying up pit operations and causing delays to adjacent furnaces. Because of crowded conditions, slag thimbles were not used and a network of cast-steel triangles and old tapping bars, placed before the heat was tapped, was the means for removing slag from the hole. Furnaces of different capacities were used

Jan 1, 1935

By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific Northwest shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others.

Jan 1, 1950

By E. H. Griswold, C. E. Beecher

DURING 1931 the petroleum industry has faced the most hazardous periods of its existence, caused by large potentials, overproduction, and demoralized markets. Two state governors actually resorted to the use of the militia in an effort to restore a semi-stabilized condition within the industry, to prevent waste of the states&apos; natural resources, and to restore prices to a level that would yield the states a reasonable tax revenue. These conditions have made it necessary to put into effect most. stringent economies and have produced a spirit of cooperation between companies to an extent that never before existed. The necessity for unified action on such matters as proration and the advantages to be gained by unit operation are being realized by the oil industry as a whole. Fewer wells have been drilled and wildcat operations almost eliminated: development and operation costs have been greatly reduced and more attention is being paid to efficient recovery methods. The net work of oil pipe- lines has grown rapidly especially in the area of East Texas. The construction and operation of natural gas and gasoline pipelines into areas far distant from the source of supply has been one of the outstanding accomplishments. Refining efficiency has continued to increase and the public is being supplied with a better grade of gasoline at a lower price. The unreasonable tax which state politicians have succeeded in placing on gasoline has encouraged tax evasion and unfair competition by un- scrupulous dealers and has misled the public as to the true price of gasoline.

Jan 1, 1932

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein&apos;s study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,&apos; and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.&apos;.&apos; In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes&apos; upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies&apos; is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By I. M. Roberts

The war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-%urnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. Coking Characteristics OF Coals Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By I. M. Roberts

The war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-%urnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. Coking Characteristics OF Coals Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944