Search Documents

By A. M. Gaudin

Jan 1, 1962

By E. H. Herron, J. H. Perry

Mathematical simulation of reservoir behavior may be used to help understand reservoir processes and to predict reservoir behavior, thereby leading to the most economically desirable form of exploitation. In addition, simulation can be used as a tool for reservoir description to learn more about the physical nature of the reservoir and the mode of primary recovery. This use is essential in most reservoir studies and represents one of the more significant applications of simulation. Prediction of reservoir behavior provides information concerning displacement efficiency, optimum well locations, and the comparison of alternative producing processes. Since oil, water and gas all commonly occur in many reservoirs, a simulation that takes into account the simultaneous flow of three immiscible phases is a prerequisite for obtaining such information. Furthermore, a simulation that describes this flow in two dimensions provides the capability of evaluating combination gas- and water-drive reservoirs with either an areal or a cross-sectional description. Many reservoir problems require such a simulation. The objective of the research described here was to develop a mathematical model and associated computer program for accurate, efficient, and economical prediction of the reservoir flow of three phases in two-dimensional geometry. Several authors have discussed multidimensional reservoir simulation of two phases.l-3 Gottfried et al.' presented an analy- sis of three-phase simulation in one dimension. Fagin and Stewart" and Garrett6 have discussed the simulation of three-phase flow in two dimensions, but their solution techniques were different from the method discussed in this paper. In particular, previous models and computer programs have usually involved either fewer capabilities or inefficient and less rigorous descriptions resulting in limited applicability. In the following sections, we present a description of the model, an evaluation of the method, and the application to reservoir problems. Additional and supporting material is presented in the Appendix. The Three-Phase Model General Description The three-phase model consists of the mathematical description of the flow of oil, water and gas in a reservoir. Conceptually this description considers flow in all three space dimensions, but in the subject simulator it is assumed that no flow occurs in the third dimension. The model includes the effects on reservoir behavior of fluid and rock compressibility, viscosity, gravity, capillary pressure, relative permeability and gas solubility. Within the two-dimensional restriction, the reservoir considered may be completely heterogeneous and anisotropic. The differential equations governing multiphase, multidimensional flow in a reservoir are too complex to be solved analytically, so they are approximated by a system of finite difference equations and solved

Jan 1, 1970

By Samuel M. Shallcross

The principal function of the Bell limestone mine, of the American Lime & Stone Co., at Bellefonte, Pa., is to supply raw material to the company's modern rotary kiln plant at Bellefonte. Because mining costs are naturally higher than many open quarries with more favorably lying strata, it cannot compete, except to a limited extent, in the markets for road material and fluxing stone. In the broad sense, mining does have an advantage over the average open quarry when the end products are designed for and controlled by process and final inspection for the exacting demands of the industrial and chemical markets. Approximately 80 per cent of the output of the Bell mine is sold in the industrial and chemical markets. And as higher standards are set each year for construction and agricultural work, the remainder of the mine output goes to these two classes. Mining produces more fines than open quarries, and these fines are difficult to market; on the other hand, owing to absence of contaminating clay and impure rock, a greater percentage of the output of a mine is marketable. Because of the great production of fines, rotary kilns for lime burning are necessary when the stone must be mined. In 1921 the American Lime & Stone Co. operated 19 quarries and 72 lime shaft kilns spread over an area of 40 miles between Bellefonte and Altoona, Pa. At that time the lime-production capacity of the 72 kilns amounted to approximately 700 tons per day. After 15 years the company operates three rotary kilns and six shaft kilns, with a combined output of approximately 500 tons of lime per day, concentrated in its single Bellefonte plant (Fig. 1). Its only stone-producing plants are now the limestone mine at Bellefonte and a construction-stone open quarry at Union Furnace, near Tyrone, Pennsylvania. Since the middle of 1922, the management of the American Lime R. Stone Co. has been under the direction and ownership of the Warner Company, of Philadelphia. To the Warner Company's experience, gained through successful operation of lime plants in eastern Pennsylvania for many years, and the successful solution of material-handling problems

Jan 1, 1937

By Robert M. Funk, James E. Lawver

The development of a laboratory and pilot-scale high-tension electrostatic flowsheet for the production of iron-ore super concentrates having silica contents in the range of 0.1% is presented, A variety of hematite and magnetite ores were tested with this flowsheet, and the pertinent metallurgical data are given. The applications and limitations of this process are brought out in terms of both practical and theoretical considerations. There have been many new developments in the past few years that have required mineral beneficiation engineers to consider new techniques for iron-ore concentration. Developments in iron powder metallurgy, and particularly the making of sheet metal directly from high-purity iron-ore concentrates, and the concept of using metallized pellets as a substitute for scrap in electric-furnace steelmaking have created demands for what is commonly referred to as iron-ore superconcen-trates. In most cases, specifications for superconcentrates are that they contain less than 0.1% total gangue, with some applications requiring less than 0.05% gangue. To produce these concentrates, new and modified processes are being developed, and the three methods receiving attention as the primary concentrating methods are: 1) Magnetic separation in which dry rotor-type equipment is used for magnetite and the high-intensity magnets are used for hematite. 2) Amine flotation. 3) "High-tension" electrostatic separation (or, elec-trodynamic concentration). This paper examines the high-tension electrostatic process in terms of its limitations and abilities for the production of iron-ore superconcentrates. A technically effective and simple flowsheet was developed through laboratory and 5 and 100-ton pilot-plant studies for the production of concentrates containing from 0.02 to 0.20% SiO, with iron recoveries between 85 and 90%. The process is also shown to be economically feasible. Laboratory Test Program Separation Characteristics: The suitability of the electrostatic high-tension method for iron-ore supercon-centration stems from the fundamental mechanism governing the process, i.e., particles are separated on the basis of differences in electrical conductivities. This conductivity is a characteristic property of minerals, and if the difference between the conductivities of two min- erals is great enough, then their separation can be performed by a high-tension machine. As shown in Figs. 1 and 2, the critical factor is the time necessary for the particle charge density, which is established by a corona discharge field, to decay to a level such that the centrifugal force acting on the particle exceeds its electrostatic, or image, force. At this point, the particle can leave the rotor at some trajectory and fall into an appropriate product receptacle. This decay time is directly proportional to electrical conductivity, and the process variables, such as feed rate, rotor speed, electrode configuration, and rotor composition, are selected to optimize the ability of the separator to resolve different conductivities. Table 1 lists the measured conductivities for some of the iron and gangue minerals used in developing the flowsheet. These results were obtained by using the conductivity cell described by Lawver and Wright.' The discharge curve of most minerals that lend themselves to super concentration by high-tension is so fast that the

Jan 1, 1971

Joseph W. RichaRds, South Bethlehem, Pa. (communication to the Secretary*): The hold experiment of Mr. James Gayley in drying the blast used in the Isabella furnace has attracted the attention of the whole metallurgical world, and has given rise to a wide discussion of the reasons for its great success. Mr. Gayley and the capitalists who backed him in his work deserve congratulations on the success of the venture, not only because it succeeded, but because they have been rewarded far beyond the maximum that could be expected from theory or probability. To state the case in its simplest terms, all that could have been predicted was: (1) that the removal of the moisture from the blaet would result in the saving of the heat required for its decomposition, representing from 3 to 5 per cent. of the heat-value of the coke used; hence about that quantity of fuel might be saved; (2) that the furnace would be somewhat more independent of variations in the weather; (3) that the campaign would be a little hotter; and (4) that the speed of the blowing-eugines would be decreased, at least in amount proportionate to the reduction in temperature of the air led to them. I do not think anyone anticipated a much larger output per day. The results actually attained were: (1) the furnace made an increase of 24.86 per cent. in the output of pig-iron per day; (2) it consumed 19.6 per cent. less coke per ton of pig-iron made; (3) the blowing-engines were run 15.8 per cent. slower; and (4) the saving in power made up for the power required to run the refrigerating-plant. In addition, the blast was hotter; the waste-gases cooler, because of their smaller volume; and there was a greater proportion of carbon dioxide to carbon

Jan 1, 1906

By E. J. KENNEDY

METHODICAL AND EFFECTIVE: thus may be characterized the fall meeting of the Iron and Steel and Institute of Metals Divisions at the Hotel Statler, Buffalo, N. Y., on Oct. 4 and 5. Approximately 200 registered. Interest centered 1111 the technical papers which were keenly followed, with substantial discussion: During the entire week of the National Metal Congress (Oct. 3 to 'i), there were also other sessions of interest' to metallurgists, directed by the America11 Society for Steel Treating, American Welding Society, Production Division of the Society of Automotive Engineers, the Iron arid Steel and Machine Shop Practice Divisions of the American Society of Mechanical En,' the Wire Association and the American Drop Forging Institute. The National Metals Exposition at the 174th Regiment Armory was well attended.

Jan 1, 1932

By Robert S. Williams

NO new ferrous alloys have been produced in the last five or six years that are as outstanding contributions to civilization as were the high-speed steels of the early part of the century or the stainless steels announced at the close of the World War. There have been, however, many developments of major importance having to do either with modifications of existing alloys or with new methods of treatment of older iron or steel alloys. Only a limited number of these new developments can be discussed and their selection does not necessarily imply that these are the most important but merely that they are of general interest rather than perhaps of greater importance in highly specialized fields.

Jan 1, 1939

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

AH pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process, but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open-circuit roughing and closed-circuit roughing are best defined by the diagrams. Special Test Data Given in Table I: For the Erie and Reserve commercial plants, Table I reflects routine conditions. Pilotac, the experimental plant, has been run with several flowsheets, including those followed at Erie and Reserve's commercial operations. Pilotac data for these last two flowsheets are similar to commercial plant results and are not repeated in Table I; statistics are given, however, for special test conditions. using other flowsheets. when the objective was to 'to extra-grade concentrate, Variations Among Taconites: Although crude ore tributary to these plants is generally classified as taconite, there are important differences in mineralogy and fineness of dissemination.

Jan 1, 1959

By Cadwallader Evans

MY endeavor in this paper will be to tell something of the accomplishments and current problems of the anthracite producer and to suggest some of the avenues for technical development that seem to me to be the most necessary and likely to bear fruitful results. The several subjects, that I find of most interest will be taken up individually with brief reference to the future trend. Underground Mining and Loading ?In this field great progress has been made in the last twenty years, beginning with the introduction of the scraper system. The electrical hoists for the operation of scrapers have been improved, and give little trouble, but there is an open field for the improvement of the auxiliary apparatus, particularly in the application of roller-hearing sheaves to the guiding of scraper ropes. Also notable in the last six or seven years is the introduction of shaker chutes, so that far more anthracite is now loaded over them than by scrapers. This trend should continue to be manifest, particularly if those who are looking ahead and who are charged with the development of this specialty continue constantly to study and improve the mechanical design of their shakers.

Jan 1, 1938

By F. Seitz

STAFF: Editor, Gerhard Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Managing Editor, James J. Burke THE METALLURGICAL SOCIETY: John Chipman, President; W. R. Hibbard, Jr., Post-President; C. C. Long, Vice-President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. Maddin, Chairman; Dennis Carney, J. C. Fulton, J. H. Hollomon, T. B. King, C. C. Long, W. 0. Philbrook, J. D. Sullivan, David Swan, and F.L. Vogel. Review and selection of manuscripts is under the supervisian of the following Publications Committees: Extractive Metallurgy D ivis ion: T. 0. King, Chairman; S. J. Dick inson, R. P. Hermsdorf, R. Schuhmann, Jr., and H. H. Kel logg. Institute of Metals Division: F. L. Vogel, Choirmon; R. L. Smith, Vice Chairman; R.W. Balluffi, J. H. Bachtold, A Servi, C.D.Graham, Jr., C. G. Goetzel, F. E. Joumot, Jr., G. E. Pellissier, Paul Gordon, Jock Washburn, Harold Margol in, A. U. Seybolt, I. R. Kromer, R. A. Meussner, R. W. Guard, M. Harmon, J. N. Hobstetter, Dean Starr, P. Shewmon, R. Gordon, J. 0. Betterton, and E. Morgan. Iron and Steel Division: W. 0. Philbrook, Chairman; F. C. Langenberg, C. W. Sherman, J. Wagstaff, and E. J. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1959 by the Americon Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . .Second class postage paid at New York, N. Y. , ond Ann Arbor, Mich. Volume 215, Number 3

Jan 1, 1960

By Max Boehmer

(Pittsburg Meeting, March, 1910.) AFTER 30 years of development and after an output of $350,000,000 in value of gold, silver, lead, zinc, and copper, there has not been published a satisfactory explanation of the origin of the immense deposits of the Leadville district. The original examination find survey of Leadville by members of the U. S. Geological Survey was a most magnificent piece of work, but their attempt to explain the origin of the ores was based upon the then-accepted theory of lateral secretion, originated by Sandberger, which theory was afterwards disproved in many cases by further development in numerous districts. This theory contended that the ore in the veins had been leached by surface-waters from the eruptive rocks in the immediate vicinity, and it had its origin in the fact that the neighboring eruptive rocks all contained, to an appreciable degree, the several metals found in the ore-deposits. But the practical miner, reasoning in a simple manner from the condition of things as he found them underground, soon discovered the fallacy of this proposition. He reasoned that, in the case of the Leadville deposits, this theory could not be true, because, if the ores were leached from the overlying eruptive rocks by surface-waters, they would as a matter of necessity be controlled by the action of gravity, and the main bodies would collect in- natural depressions of the underlying limestone, and at all points where such depressions existed. But this was not in accord with the channels of ore as he found there ; and hence the theory of lateral secretion in this district was never accepted. Another objection to it consisted in the fact that large areas within the ore-bearing district contained no ores whatever, although their formation was the same, and the same limestones were covered by the same thick sheet of

Feb 1, 1910

Jan 1, 1967

Jan 1, 1923

Jan 1, 1923

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By John V. Beall

Since the U. S. Metals Refining Co. works was established, around the turn of the century, near the town which is now called Carteret, N. J., it has grown to be a major producer of refined copper and the main source of that special brand known as "oxygen-free high-conductivity copper." Owing to the complex metallurgical problems arising from handling a variety of raw materials such as copper concentrate from Matahambre, Cuba, copper and brass scrap from the New York area, and domestic blister copper, the organization is geared from top management down through its 2000 employes to maintain a high degree of flexibility in plant operation. The Company is a subsidiary of The American Metal Co. Charges for the smelter furnaces, one reverberatory furnace and one blast furnace, are made up in. bedding bins so that they may be tailored to the production of a constant grade of blister copper. The reverberatory furnace smelts the .sulphide charge, which may be a blend of ten different materials but principally the Cuban concentrate, and the matte from the process is poured into a converter. This reverberatory is 80 by 20 ft, silica lined with a slag bottom, fired by pulverized coal, and continuously side-charged from the top by bottom-dump cars which keep the side walls covered. It produces a 40 to 50 per cent copper matte. The fuel-charge ratio is 4.35 tons of solid charge per ton of coal. The furnace has a capacity of 10,000 tons of charge per month and produces from 5000 to 6000 tons of slag per month which must be disposed of. About 5000 tons of converter slag is produced monthly and returned molten to the reverberatory furnace. The converter gases go through a spray chamber to a Cottrell precipitator and thence to the flue system. Smoke from the

Jan 1, 1948

By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By J. L. Green

Virginia-Carolina Chemical Corp., in its Florida Operations, uses both roller mills and ball mills in dry grinding of phosphate rock. The roller mills have been in operation since 1954 in the Mining Department. The ball mills were installed and put in operation in 1960 in the Harding Concentrate Superphosphate Plant. The roller mills in the Mining Department are used to grind phosphate rock for outside customers. This involves short notice orders of varying grinds, grades and types of rock. The ball mills grind phosphate rock for use in V-C's own phosphoric acid and concentrated superphosphate plant. These mills grind generally two types of rock for one grind. In 1959, a 10% speed-up was made in the operating speed of the roller mills. This paper deals with the operational gains and resulting cost savings which evolved from this speed-up, and compares the present operations of the roller mills and of the ball mills in grinding phosphate rock. In January 1959 it was decided to determine the feasibility of reducing the grinding cost on the roller mills, per ton of rock ground, by speeding up the mill 10%. At this time, one mill was completely reconditioned so it would be in top condition. Extensive tests were then run both before and after the mill speed-up to determine the resultant cost savings. These tests showed that, due to this 10% speed-up, the mill capacity was increased approximately 20% and grinding power costs per ton were reduced approximately 10%. Table I shows the results of these tests. Each test run actually represents several of the same type rock and grind, averaged together. Each test run lasted approximately three hours. The validity of these runs has been confirmed by subsequent operation in grinding over 1,000,000 tons of phosphate rock. Accurate records have been kept on power consumption and repairs as well as tons produced. Two types of feed rock were used for the tests — pebble phosphate rock and flotation phosphate concentrate rock. The pebble phosphate rock size is approximately 80-90% plus 20 mesh. The flotation concentrate phosphate rock size is approximately 15% plus 20 mesh and 95% plus 100 mesh. The same two types of rock feed were used for all the test runs. Test Nos. 1, 2, and 3 were run at the original mill speed of 85.5 rpm on the vertical shaft. Test No. 1 was run with a feed of high grade flotation concentrates; the desired fineness attempted was 70% passing 200 mesh. Tests No. 2 and No. 3 were run with a feed of low grade pebble. Test No. 2 was run for a desired fineness of 70% passing 200 mesh. Test No. 3 was run for desired fineness of 50% passing 200 mesh.

Jan 1, 1963

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957