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By William P. Shinn

Jan 1, 1880

By J. E. Hove

The high temperature physical properties of graphite are reviewed and interpreted in the light of present day knowledge of the mechanisms affecting these properties. The thermal and mechanical behaviors only are discussed and, whenever possible, comparisons are made with other refractory materials. Possible further studies are indicated, including some carbide work. AS long as the term high temperature implied only temperatures up to about 1000°C, the materials problems which arose could usually be handled by fairly conventional metal alloy types, such as the Co-Cr-Ni superalloys, for which there exists a great deal of technology. Perhaps this temperature can still be considered an upper limit for normal applications, but it is certainly true that the number of abnormal applications is increasing rapidly. The advent, in recent years, of ram-jet and rocket missiles and of high power nuclear reactor heat sources has raised a host of questions concerning the basic problem of what material to use in the temperature range up to 2000°C and higher. While there are, of course, many metals, in the second and third transition series, which melt at considerably higher temperatures than this, these metals are, at present, pretty well excluded from practical use by other considerations, such as re-crystallization, chemical activity, or excessive plastic deformation. The behavior of metals, from the standpoint of dislocation theory, is just beginning to be understood and thus there is some hope for the future development of very high temperature metals, but the immediate problems would most logically appear to have solutions involving the nonmetals, such as the refractory ceramics and graphite. For this reason, there is presently a great deal of engineering and experimental research being performed on the latter materials, much of this research being exploratory in the sense of gathering new property data. The situation, so far as graphite is concerned, is somewhat more fortunate than with the other refractory solids in the sense that a great deal is already known about its basic properties. This stems both from the fact that the carbon-carbon bond has been of interest to chemists for a long time (and graphite can be considered as a very large aromatic molecule, if desired) and the fact that its properties, both as a function of temperature and of radiation damage, are of critical importance to nuclear reactor designers. It is still true, of course, that such fundamental questions as why graphite remains solid to such a high temperature and why it has such a high thermal conductivity cannot entirely be answered at the present time. It is, nonetheless, meaningful and instructive to consider such problems in the light of existing knowledge. This is what the present paper will attempt to do. Before going on, it may be appropriate to classify graphite and justify its discussion before readers primarily interested in metals. Graphite is comparatively unique among materials in that there is always a property or group of properties which precludes calling it either a metal, a semiconductor, or a ceramic. It has the high electrical and thermal conductivities of a metal, but the artificial, poly-crystalline types show a negative thermal coefficient of electrical resistivity, generally characteristic of semiconductors. On the other hand, semiconductors, by definition, show an ever increasing resistivity as the temperature is lowered, whereas graphite approaches a finite, and, indeed, a rather low resistivity in the region of 10°K and, furthermore, a good single crystal of graphite has a positive temperature coefficient, as for a metal.' On still another hand, its porosity and brittleness at lower temperatures would put graphite in the ceramic class although, unlike most ceramics, it is readily machinable and has a high resistance to thermal shock. All things considered, it is probably more nearly appropriate to call graphite a metal than anything else. Although certainly outstanding in some ways, graphite has its peculiarities and, especially if the reader is unfamiliar with the data, it is probably valuable to review some representative property variations at high temperature. This review is meant to be mainly illustrative and no attempt has been made to be exhaustive. Review of High Temperature Properties At ordinary pressures, graphite does not melt, but sublimes directly into the gaseous phase at about 3700°C. Although the phase equilibrium diagram is still in some doubt, graphite will melt, at a slightly higher temperature, at pressures in excess of about 100 atm. The chief difficulty of using graphite in an oxidizing atmosphere is that the reaction rate becomes quite high at fairly low temperatures. If a threshold oxidation temperature2 is defined as the temperature at which graphite loses 1 pet of its weight in 24 hr, the value in air is 450°, the value in steam is 700°, and the value in carbon dioxide is 900°C. Efforts are presently being made to raise this threshold temperature either by impregnation with a retardant of some type (sodium tung-state and phosphoric acid, for example) or by a suitable metal or oxide coating. It is probably fair to say that, to date, these attempts have not shown any outstanding success in all respects. Most commercial graphites are fabricated by impregnating a carbon flour (say of coke or lampblack particles) with some type of hydrocarbon

Jan 1, 1959

By K. N. Han, H. Lee, M. C. Fuerstenau

An investigation of the recovery of finely-divided cassiterite and silica particles less than 1 µm (1200 mesh) in size has been carried out using packed and fluidized beds. The bed particles used included cassiterite and silica particles ranging from 44 to 210 µm (325 to 70 mesh). Effects of various system parameters on the recovery and selectivity of cassiterite fines were investigated. System parameters included pH of the slurry solution, superficial velocity, slurry concentration, and bed particle sizes. High recoveries of cassiterite fines were obtained at pH 4.0 and slow slurry flow rates. In a packed bed system, recovery of cassiterite fines was greater than 95%, while that of silica fines under the same conditions was about 35%. Although the total recovery per pass is not as good as the packed bed, the fluidized bed system exhibits good recovery in general and an excellent selectivity of cassiterite fines. There is an optimum superficial velocity, vo, for the rate of fine particle uptake and the apparent rate constant has the form of Kvo1/2- K'vo, where K and K' are system constants.

Jan 1, 1985

By Richard W. Markley

A centralized online data acquisition system has been developed by the U.S. Bureau of Mines Pittsburgh Mining and Safety Research Center for rapidly digitizing, storing, and processing experimental signals originating up to 1100 feet away from a central computer. This system, which services seven laboratories, is currently based on a CDC System 17 1/- computer with 56K of semiconductor memory, four disk drives (one shared online with a CDC 1700), two magnetic tape drives, high-speed A/D hardware, and other input/output peripherals. The laboratories are linked to the central computer by 15-pair cables and signal conditioners and to the computer's communications controller by modems and current loops. The A/D throughput rate is approximately 30,000 samples per second (9 bit plus sign resolution) and permits scanning about 30 instruments once every millisecond for up to 100 seconds, being limited only by disk capacity. The laboratories serviced by this facility conduct explosions research and include such facilities as an Experimental Coal Mine Explosion Facility (45 channels), a Constant Volume Combustion Laboratory (4 channels), and a Simulated Coal Mine Laboratory (15 channels). Personnel support includes one systems analyst, two applications analysts, one operator, and a hardware technician. The system has performed adequately for burst-type data acquisition, but due to a lack of long-term reliability (24 hours) of the real-time multiprogramming operating system and unpredictable power failures, slow phenomena signals are generally digitized and stored offline. This latter data is input to the computer through peripherals such as a high-speed paper tape reader, or high-speed asynchronous communications ports. Processing of data is done either in real-time (as soon as data is collected) or in batch mode. Smaller batch jobs are run on this computer, and all others are transmitted by means of the system's high-speed UT 200 terminal simulator to a CDC-6000 series computer.

Jan 1, 1977

By Louis D. Huntoon

After the completion, in 1905, of the Hammond Mining and Metallurgical Laboratory of the Sheffield Scientific School, Yale University, it became necessary to secure and assay a large assortment of ore-samples, and to arrange the results in such a manner as to admit of use with the least amount of work on the part of the instructor. At first, pulp-samples, together with their respective assays, were secured from the mines, smelters, and public aesayers, but this practice did not prove satisfactory. It was not only difficult to secure a suffciently large supply of material, but it was also impossible to secure the proper assortment required for instructing students. It involved considerable work for the donors to select the samples and furnish a record of the assays, and also for the instructors to examine each pulp and determine its character. Some of the samples did not contain a sufficient quantity of pulp for the student to check his work in case his first assay did not correspond to the record. In order to increase the number of samples and to vary the character of the material, pulp-samples were later mixed with barren rock and with sulphides, but this method also was unsatisfactory and has been discontinued. At present, small lots of ore are secured by gift or purchase from engineers, public assayers, and the managers of mines, mills, and smelters. These lots weigh from 10 to 100 lb. each, and are rarely finer than 0.25 in. in size. The larger samples permit of a careful study by the instructor in order to determine the best method of assaying to be followed. In universities in which assaying is taught the record of the samples should fulfill the following requirements:

Jan 1, 1910

By Pei-Yung Huang, C. R. Hayward

In order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. Choice of Slag Composition The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, avcrage :2,3 45 to 47 pct FeO; 38 to 42 pct SiO2; 5 to 6 pct CaO; 5 to 6 pct A12O3. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-SiO2-Al2O3, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the composition near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093º ± 3ºC) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the fulfil- slag is decidedly too basic. Composition K has a slightly higher melting point (1150O + 3OC) and a higher silica content, but this is preferred because the slag is saturated with respect to tri-dymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The filial slag composition, therefore, was chosen to

Jan 1, 1949

By W. A. Wood, W. H. Reimann, Maria Ronay

The basic mechanism of fatigue is studied in annealed a brass subjectecl to alternating torsion at room temperature, 100°, 200°, 300°, and 400°C, and in air. It is shown that the slip-zone micro-cracking which characterizes fatigue damage produced by small amplitudes at room temperature is progressively replaced by grain boundary cracking at elevated temperatures, replacement being complete at 400°C. Replacement occurs not because slip activity decreases hut because slip movements at elevated temperatures cease to concentrate in narrow zones and instead disperse. Decrease of amplitude at 400°C through permitting longer lives of specimens before fracture actually causes in- MOST studies of fatigue at elevated temperature have been concerned with data for design. Observations on the basic mechanism of fatigue have been largely incidental, though they have led to the interesting inference that this mechanism has features in common with that of creep.' This paper is concerned primarily with the mechanism itself. Advantage has been taken of mater- crease in pain boundary damage, an anomaly attributed to the greater difficulty at elevated tempwature of starting and propagating a crack. Surface corrosion was most pronounced along slip bands but since at elevated temperatures the slip hands showed no cracking the surface corrosion did not appear to influence onset and early spread of fatigue damage. Similarly the type of fatigue damage produced at room temperature by cyclic strain at large amplitudes, characterized by irregular mi-crocracks at zones between disoriented regions in a grain, was also replaced by mainly grain boundary cracking at elevated temperature, though not so completely. ials and procedures known to show readily how fatigue affects the microstructure of a metal at room temperature, so that direct comparison might be made with what the same procedures show when the material is subjected to fatigue deformation at higher temperatures. 1) MATERIAL This was 70/30 a brass, used extensively in previous studies at room temperature.' Specimens were turned from extruded rod to have parallel test portions 1-1/4 in. long and 7/32 in. diameter, annealed to a grain size -1/10 mm, and electro-

Jan 1, 1965

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1941 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS TECHNICAL PUBLICATIONS in Classes A-Metal Mining, 13-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every other month TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysics, are issued as separate pamphlets An Institute member is entitled to one copy of any printed TECHNICAL PUBLICATION or CONTRIBUTION Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes CONTRIBUTIONS and other TECHNICAL PUBLICATIONS will be sent upon request A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page, minimum charge, 25¢ Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1 25 domestic, $1 35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2 50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7 80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers) MINING TECHNOLOGY, $6 per annum domestic, $6 60 foreign (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6 60 foreign Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY Is mailed each month A member is entitled to one volume a year on his membership and he may purchase for $2 50 one copy of a volume not already received, additional copies of the same volume, $5 Nonmembers in the United States may purchase the volumes listed at $5 each, outside of the United States and its possessions, $5 6o Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 500 each to members, to nonmembers 50¢ current issue and $1 each, back issues Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4 00 foreign.

Jan 1, 1941

By Walter O. Snelling

Continuation of the discussion of the paper of WaltER o. SnelLIng, presented at the New York and San Francisco meetings, February and September, 1915, respectively, and printed in Bulletin No. 100, April, 1915, pp. 695 to 704 and Trans., li, pp. 657 to 671. A. C. McLaUghlin, San Francisco, Ca1.—It seems to me that Mr. Snelling's work, if it is what it appears to be, is one of the most important contributions to petroleum technology that has been brought out in the last 25 years. If his end products are what they seem to be, he has made. a discovery, which, in my judgment, will revolutionize the petroleum industry. As to industrially carrying out these processes I do not think there is the slightest difficulty, for I have had some work recently where crude oils were handled successfully at a temperature of 750" F, and pressure of 750 lb. per square inch. William A. WillIams, San francisco, Ca1.—What metal did you use, Mr. McLaughlin? A. C. McLauGHILIN.—Ordinaly seamless tubing, extra strong. William A. Williams.—Tests were made in Dr. Rittman's experimental plant at Pittsburgh, upon samples of residuum furnished by Mr. Bell, the residuum being the remainder of the crude oil after the lighter fractions had been removed. After the material had been run through Dr. Bittman's plant, yields of from 43 to 58 per cent. of material, boiling under 150" C. were obtained. The distillate had a peculiar odor, due to the presence of benzene, toluene, and other unsaturated hydrocarbons. W. N. Best, New York, N. Y.—What is the difference between the Rittman and the Snelling process or system? William A. Williams.—he fundamental difference is that reactions take place under relatively higher temperatures and pressures and with none of the oil present in its original or liquid state, while the reactions secured by Mr. Snelling and other investigators have been from the liquids in the presence of some vapors. Under such conditions as Mr. Snelling operates, the temperatures and pressures used are limited and the flexibility in the control of these variables is extremely limited when compared with the Rittman process.

Jan 1, 1916

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By HOMER L. WILLIAMS

WHILE some of the mining companies have been pumping a small amount of water for some time, it is only in recent years that large quantities of water have been encountered in the Tonopah district. The water appears to be in different zones or belts so that the draining of one property does not necessarily affect the one adjoining. Consequently, each company has its own pumping plant and its own conditions. The companies panes handling the largest amount of water are the Tonopah Extension Mining Co., Halifax Tonopah Mining Co., West Tonopah Consolidated Mining Co., and Great Western Consolidated Mining Co. The Halifax shaft is on the eastern end of the district and the other three properties on the western. The ore-bearing formation occurs at greater depth on -the eastern and western ends, hence the water problem in these properties.

Jan 1, 1921

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By F. Z. Schellenberg

(Pittsburg Meeting, March, 1910.) SYSTEMATIC exploitation in the Pittsburg coal-seam on a large scale is simple where the boundaries of the property do not interfere by forcing drainage-, ventilation-, and transport-lines of entries to be run to particular confined fronts. A prime condition governing development is the natural direction of the seam's perpendicular cleavage-planes, giving long lines of smooth faces near together and parallel, bearing about 65° to the left of the meridian and therefore crossing the basins. The gradients of dip into the basins change from 10 per cent at the east rim to practical flatness northwestward across the great coal-fields, a hundred miles wide; the clip being halved in rate at each successive crossing-over of an anticlinal crest. Elevations above sea-level on this transverse section, in scope of present development, differ by 1,000 ft. between low trough and high outcrop. Local irregularities of dip are found, but the main feature to be recognized is the pitch of the basins-the general rise northeastward at 20 ft. per mile, from 100 ft, below sea-level at the low point near the. SW. corner of Pennsylvania to 1,500 ft. and more above tide, and the appearance then, at the surface, of the lower coal-seams carried in the next deeper-lying thousand feet of rock-measures; below which series come the oil- and gas-sands of Oliphant's charted column of strata, reaching down altogether 3,000 ft. below the Pittsburg coal-seam. Because of -the general regularity of occurrence of the coal-seam, the mine-map depicting the courses of economic operation to be undertaken and the steps in controlled exhaustion, need be but a projection of two dimensions on the horizontal plane of space, and this for the most part composed of natural, almost unbroken lines, on the face and on the end of the coal, co-ordinating rectangularly.

Jul 1, 1910

By A. J. Heckler, J. A. Peterson

A capsule technique was successfully employed to investigate the effect of nickel on the activity of nitrogen in Fe-Ni-N austenite in the temperature range 600" to 1200°C. This technique consisted of equilibrating nitrogen among various Fe-Ni alloys within a sealed silica capsule. Nitrogen transfer among the specimens occurred by N, gas at 900°, lOOO? and 1200?C. Nitrogen gas pressures within the capsules were estimated to be as high as 22 atm. The activity coefficient of nitrogen, fN , in Fe-Ni-N austenite is adequately described by the linear interaction equation: log . wt pct Ni where the standard state is chosen such that fN = I as wt pct Napproaches zero in binary Fe-N. This relationship was determined over the temperature range 873" to 1473°K and for nickel contents of 0 to 35 wt pct. ALTHOUGH chemical thermodynamics of liquid iron alloys have been extensively studied, experimental data for the solid state are needed. These thermody-namic data will provide a basis for understanding phase transformations, precipitation reactions, metal-gas equilibria, and so forth. The interaction of sub-stitutional alloying elements with the interstitial elements is of particular interest. In this investigation the thermodynamic behavior of Fe-Ni-N austenite has been studied. The solubility of nitrogen gas in iron austenite is known to obey Sieverts&apos; law up to about 65 atm.1-6 In addition, the solubility of nitrogen in Fe-Ni austenite has been investigated5"8 using the classical method of equilibrating Fe-Ni alloys with nitrogen gas at 1 atm. A capsule technique similar to that used to study the activity of carbon in alloyed austeniteg&apos;&apos;&apos; was employed in the present work to determine the effect of nickel on the activity of nitrogen in Fe-Ni austenite over the temperature range 600" to 1200°C. EXPERIMENTAL PROCEDURE A series of Fe-Ni alloys up to 35 wt pct Ni was vacuum melted and cast into 1 by 3 by 6 in. ingots. Chemical analyses at the top and bottom of each ingot demonstrated that the ingots were homogeneous with respect to nickel content. The nickel contents are given in Table I. Additional chemical analyses showed that wt pct Si < 0.05, s < 0.01, C < 0.01, Al < 0.006, 0 < 0.004, Mn < 0.002, and P < 0.002. A 2 in. section of each ingot was cold rolled to 0.015 in. The material was then decarburized to a carbon content of less than 0.004 wt pct. A portion of the material of each nickel content was nitrided to various levels in a H2-NH3 gas atmosphere to provide a source of nitrogen during subsequent equilibration. The experimental technique consisted of equilibrating the series of Fe-Ni-N alloys in a partially evacuated sealed silica capsule at the temperature of interest. Both Vycor and quartz capsules were used. In general, the final equilibrium nitrogen content for each Fe-Ni alloy was approached from both higher and lower nitrogen levels. The criterion for establishing that equilibrium was attained was that the final nitrogen content for each Fe-Ni alloy was the same irrespective of the initial level. A schematic drawing of the sample configuration in a capsule is shown in Fig. 1. The samples were arranged so that there was a minimum of physical contact. The samples were also dusted with a fine, high purity alumina powder to help prevent sticking. Several different types of furnaces were used in this study. In each case, a thermocouple was placed immediately adjacent to the capsule during equilibration and the temperature was controlled to within *4?C of that reported. At each equilibration temperature, the following times were found to be more than sufficient to attain equilibrium: 600°C-250 hr, 900°C-150 hr, 1000°C-150 hr, and 1200°C-50 hr. After equilibration the capsules were quenched in water and the nitrogen contents of the specimens determined by a Strohlein analyzer. Analyses of samples after equilibration at 1000" and 1200°C showed no silicon pickup from the silica capsules. RESULTS AND DISCUSSION Transfer Mechanism. The mechanism by which nitrogen was transferred among specimens in an initially hydrogen flushed and partially evacuated capsule equilibrated at 1000°C was investigated. After equilibration the gas in the capsule was collected over water and an estimate of the pressure at temperature

Jan 1, 1970

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

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis&apos; reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

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

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis&apos; reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By M. C. LYNN

RECENT completion of a $40,000 lubricating oil plant will make it possible for students in the School of Petroleum Engineering at the University of Oklahoma to carry out on a large scale the entire process of refining crude oil, from the time it is received in tank cars and pumped through the 1/4-mile University pipe line to storage tanks on the campus until the various products appear in finished form. This plant is part of a $100,000 expansion program which this school has been carrying out during the past year. Two years ago the Oklahoma State Legislature appropriated $50,000 for the School to use in improving its laboratory facilities. A few months later a $30,000 PWA grant was ob-

Jan 1, 1937

By C. A. Schempp

STUDY of the adaptability of Tintic Standard ores to concentration dates back to somewhat before January, 1921, when the chloridizing mill at Harold, Utah, was put into operation. The operation of this mill has been fully covered in the TRANSACTIONS (Vol. 73). The process consisted essentially of a chloridizing roast followed by a percolating leach with a nearly saturated solution of common salt, acidified with sulfuric acid; precipitation of silver on sponge copper, and of copper and lead on tin-plate cuttings. This mill was built to treat the low grade siliceous ores having an average content of

Jan 1, 1933

By Nicholas J. Grant, Laszlo J. Bonis

Two dilute nickel alloys in each of the systems Ni-Al, Ni-Ti, Ni-Cr, and Ni-Si u:ere internally oxidized at 700° to 900°C for time periods up to 100hr to establish the oxide particle size, depth of oxide penetration, and the change in oxide particle size with depth. Fine (-270) mesh alloy powders were then intevruzlly oxidized, hydrogen sintered, compacted, and extrmded, yielding bar stock for tensile tests at room temperature and creep-mpture tests at 815° to 1093°C. Recrystallization studies were made up to 1400OC. ReCENT studies have clearly indicated that oxide dispersion strengthened alloys exhibit outstanding elevated temperature properties, espe- cially in long-time tests. Certain structural parameters must be observed to achieve optimum properties, namely, micron or submicron interpar-ticle spacing, submicron oxide particle size, and a high level of stored energy.&apos;-5 A number of processes have been utilized to obtain the desired structures, but certain of them appear to offer greater promise. Thus far the most promising method is the internal oxidation of dilute alloys consisting of a relatively noble solvent metal and a readily oxidizable solute element.3&apos;6)7 Several important principles governing internal oxidation have been established in earlier studies;&apos; however, these principles are as yet not adequate to permit alloy development studies. Much of the earlier work was performed on relatively coarse wires or in idealized systems. As a result, there are still a number of unanswered questions which require considerable additional work: a) How does oxide particle size change with depth of penetration of the oxide? How does this vary with the specific type of solute element? b) What is the effect of solute content on the average oxide particle size?

Jan 1, 1962