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By Arthur Phillips, C. H. Mathewson

During the past year considerable work dealing with the mechanical properties and microstructure following the anneal under uniform condi-tions of certain types of commercial rolled brass has been done in this laboratory. Since these experiments were conducted with the active cooperation of the Bridgeport Brass Co., involving free use of its product, and have thus furnished information which is characteristic of some of its special mixtures, full publication of the numerical relationships and comparative results encountered does not seem justifiable. Some of the more general features of this work are, however, available and it is our present purpose to use the material in question, along with some results of special tests, in discussing the characteristics of recrystallization as related to the degree of hardening by strain and the ordinary annealing variables. We desire to make acknowledgment of the many courtesies extended by Mr. Charles Ferry, Metallurgist of the Bridgeport Brass Co., and the value of his cooperation, which has greatly stimulated the study of brass in this laboratory. A clear and systematic presentation of the principal relations between temperature and time of anneal, the changing physical properties and microstructure and the degree of previous reduction by cold-rolling, was first made, in the case of rolled brass and copper, by the French engineer, C. Grard,' in 1909, although much fragmentary information of this general character had appeared earlier and the main facts involved were undoubtedly known to many brass specialists through their own private research. From this work, it appears that in the cartridge mixture (67 per cent. copper, 33 per cent. zinc) the properties imparted by cold-working within the limits, 13 to 75 per cent, reduction of area by rolling Original Area — Final Area 0.13 to 0.75), are not affected by anneal- Original Area " ing for a 50-min. period at any temperature below 200°C. At or in the

Jan 1, 1916

By B. M. Burchfiel

CALIFORNIA possesses such an abundance of ceramic materials other than clays, that she is quite independent of other states and foreign countries so far as these materials are concerned. Certain users import some feldspar, silica, and allied minerals, but they do so from choice and not necessity. Production is largely for home consumption, so the total volume of ceramic materials produced is comparatively small. Many small deposits of the materials here under discussion are worked by individuals, and their output sold to individual grinding companies or users. The data given here shall be confined to the larger deposits and developments because they give a truer picture of typical deposits, operations, and materials.

Jan 1, 1936

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By P. Bolsaitis, L. Skolnick

Vapor pressures of silver over ternary alloys of six different copper to gold ratios have been measured by means of the Knudsen effusion technique. The data obtained in the temperature range of 1330° to 1375° have been used to estimate the integral excess free energies of the ternary alloys and the activities of copper and gold. The results compare favorably to the predictions based on the electron cell model of alloys recently formulated by the authors. THE orifice effusion method for measuring vapor pressures of materials in condensed phases was first introduced by knudsen, and has since been used extensively for the determination of thermodynamic properties of condensed phases. The basis of the measurement is the effusion, through a small orifice, of vapor in equilibrium with a condensed phase. Assuming free molecular flow into high vacuum, the vapor pressure, P (in mm Hg), of the effusing species is calculated from the following equation:' where w (g) is the weight of effusing species lost during a run, t (sec) the time length of the run, A, (sq cm) the area of the effusion orifice, T ("K) the temperature at which the run is conducted, M the molecular weight of the effusing species, and k the Clausing factor, a constant that corrects for deviations from free molecular flow caused by the finite thickness of the orifice walls.17 The determination of partial and integral thermodynamic variables from vapor pressure data of ternary alloys is possible only if the vapor pressures of all but one component are negligible or can be esti-

Jan 1, 1969

Aamot, Olav Crone, (M'29) Chem. Engr., Elektrokemisk, Raadhusgt. 23, Oslo, Norway. Abadilla, Quirico A., (M'3S) Min. Engr., Dir., Bu¬ reau of Mines. Manila, P. I. Abbott, Agatin Townsend, (J'40) Jr. Engr., Phelps Dodge Corp., Morenci Branch, Morenci. Ariz. Abbott, Clarence E., (M'04) Civil Engr., V.P., Ten¬nessee Coal Iron & R.R.. Co., 1542 Brown -Marx Bldg.. Birmingham, Ala. Abel, Raymond L., (M'28) Chem. Engr., Command¬ing, Officer, Pittsburgh Chem. Warfare Procurement Dist., American Bank Bldg., Pittsburgh. Pa. Abel, Walter D., (M'32) Alin. Engr.. Div. of Cor¬porations, State of Calif., 403 California State Bldg., Los Angeles, Calif. Abele, Louis T., (M'31) 423 3rd Ave., Decatur, Ga. Abell, Leo M., (M'31) Mill Supt. & Met., Emperor Gold Min. Co., Led., Vatnkoula, Fiji Islands. Abernathy, G. E., (M'38) Geol., Kansas State Geol. Survey, Pittsburg, Bans. Abernathy, Jack H., (M'40) Peer. Engr., c/o Superior Oil Corp., National Bank of Tulsa Bldg., Tulsa, Okla. Aborn, Robert H., (M'10) Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. Abraham, A. W., (M'39) Peer. Engr., Richfield Oil Corp., 555 S. Flower St., Los Angeles, Calif. Abramowitz, William L., (J'40) Chem., Industrial Inventions, Inc., 103 Foster Se., Peabody, Mass.

Jan 1, 1942

By S. H. Ash

IN no part of the world other than a small area in Pennsylvania is anthracite mining an industry of major magnitude. As the deposits of anthracite in the United States are limited virtually to Pennsylvania, the difficulties of this industry have been commonly considered a state rather than a national problem. However, there is also national interest in the conservation and wise utilization of all the country's fuel resources and in the control of interstate waterways. The anthracite industry is confronted with a serious problem of water accumulation in many of the mines, a problem that must be solved in the near future if progressively higher mining costs are to be avoided. It cannot be solved by the operating companies without state or Federal aid, or both, owing to the magnitude of the work required, the diversity of interests of the coal and surface ownerships, the hazard to the whole mining community, and interests affected outside the mining region. 'The costs of abating the ever-increasing surface seepage to mine workings and of handling this seepage once it has occurred are beyond the eco¬nomic resources of the operating managements.

Jan 1, 1941

By Richard O. Carlson

Ions of p31 and B 11 were implanted in natural insulating diamond macles. The thin (-0.4µ) layers showed sheet resistances of 107 to 1011 ohm per sq and activation energies of 0.17 to 0.34 ev above room temperature. However, no Hall effect could be measured, indicating that mobilities were less than I to 10 sq cm per (v-sec). Such low mobilities may be due to excessive scattering due to radiation damage in the bombarded layer or to very high concentrations of active compensating impurities. Annealing did not materially change the room -temperature properties, but the temperature was limited to -800°C by surface graphitization, the latter process probably being accelerated by lattice damage in our diamonds arising from the ion bombardment. A weak n-type thermoelectric power was detected after p31 irradiation, but it cannot be presumed that we have made the phosphorus ions active as donors in diamond. The natural diamonds have a high and uncontrolled concentration of impurities and, when coupled with the radiation damage and graphitization problems, would appear to seriously limit the quality of semiconductor that we can presently achieve by ion implantation in diamond. ALTHOUGH diamonds are usually thought of as insulating in terms of their electrical conductivity, it was found about 15 years ago that natural semiconducting diamonds do occur rarely, and these were designated as type IIb diamonds. These p-type semiconducting diamonds were found to be dominated by an impurity level 0.37 ev from the valence band. Evidence today based on correlation of the concentration of acceptor states from Hall effect measurements with the impurity concentrations determined by neutron activation analysis point to aluminum as the dominant acceptor impurity.' The compensating donor is believed to be nitrogen, which has a donor level 1.6 ev above the valence band.' However, only a small fraction of the total nitrogen content in the diamond is electrically active. An infrared absorption band at 7.8 p and ultraviolet absorption near 4 ev have been associated with nitrogen, the former providing a quantitative measure of nitrogen content.3 The nitrogen content is -l020 cm-3 in insulating or type I diamonds, but is less than 10'' in natural semiconducting diamonds. Much of this nitrogen is distributed in platelets oriented in (100) planes and not atomically dispersed in the diamond lattice.4 Semiconducting diamonds have been deliberately formed by incorporating impurities into the graphite charge in the high-pressure apparatus used to form diamonds.5 These manufactured semiconducting diamonds are always p-type, and while some show the 0.37 ev level due to aluminum, most such samples have been ascribed to impurity banding effects.6 The best natural or manufactured semiconducting diamonds have hole mobilities near 1500 sq cm per (v-sec) at room temperature, and those with the 0.37-ev level can be analyzed to reveal an acceptor concentration of 3 to 8 X 1016 cm-3 and a donor concentration 3 to 10 times lower.' NO bulk n-type diamonds have ever been reported, but the electron mobility has been measured as 1900 sq cm per (v-sec) by irradiating a diamond with ultraviolet to excite electrons out of the deep nitrogen donor level or other levels.7 New hope for the formation of n-type diamond has emerged from the ion-implantation method whereby desired impurities are introduced into a crystal lattice by bombardment with a high-energy beam of the impurity ion. It was found in the case of silicon that the usual donors such as phosphorus and arsenic and acceptors such as boron and gallium could be implanted into silicon. Wentorf and arrow' produced semiconducting layers on diamonds by an ionic bombardment in a glow discharge at potentials of about 2 kv. The observed typeness from thermoelectric probing seemed to depend on the atmosphere gas (nitrogen, argon, or hydrogen) rather than on the electrode material, but the nature of the conduction process in the thin damaged surface layer is completely unknown. A Russian group under Vavilov has attempted high-energy ion implantation in natural diamonds using boron and lithium ions9 and later also phosphorus, aluminum, and carbon ions.10 Their papers claim n-type layers from lithium, phosphorus, and carbon implant and a p-type layer from boron and aluminum implant, though the methods of type determination are not described in detail. Under government contract support, the Ion Physics Corp. has studied ion implantation in several semiconductors. While the bulk of their study1' was devoted to the irradiation of silicon, they did carry out a short study on boron and phosphorus implantation into natural diamonds. They did observe surface conducting layers but did not determine the typeness of the layers. For our experiments, phosphorus and boron were chosen as the dopant ions because of their respective donor and acceptor behavior in germanium and silicon. Moreover, they are the lightest mass dopants of the shallow level donors and acceptors from columns 111 and V of the Periodic Table (excluding nitrogen which is already present in diamond), and will have the largest depth penetration into the diamond lattice. EXPERIMENTAL Diamonds. As the target diamonds for our ion implantation study, we chose commercially available macles, which are flat, twinned diamond crystals. By scanning through the stock of a wholesale distributor

Jan 1, 1970

By James Park

The principal gold-bearing formation is of volcanic origin, consisting of a great accumulation of andesitic lavas, tuffs, breccias and agglomerates of lower Tertiary age. These rocks everywhere bear evidence of having been subjected to the prolonged leaching-action of thermal waters, doubtless accompanied by steam and acid vapors. They are found in all stages of decomposition or alteration; and in many mines the hard blue andesite can be seen to pass by a series of almost insensible gradations into a soft, or fairly hard, greyish yellow or blue

Jan 1, 1900

THE Institute assembled in the library of the Sheffield Scientific School at 8 o'clock, Tuesday evening, February 23d. Prof. G. J. Brush greeted the members present on behalf of the Government of the Sheffield School in a few words of cordial welcome, to which President Raymond responded. Dr. Raymond then delivered an address on the History of the Relative Values of Gold and Silver. The Council presented, through the President, a list of names of persons duly proposed for members and associates, with recom¬mendation for election. The following gentlemen were unanimously elected: *Prof. George J. Brush, - New Haven, Conn. *Prof. Oscar D. Allen, - New Haven, Conn. *C. Constable, - New York City. *Leven S Goodrich, - Oxmoor, Jefferson Co., Ala. *Charles J. Nourse, - Columbia, Lancaster Co., Pa. *J. W. Mickley, - Hockendauqua, Pa. *Hugh Alex. Crawford, - St. Louis, Mo. *General Ario Pardee, - Hazleton, Luzerne Co., Pa. †N. W. Lord, - New York City. †J. Holme Maghee, - New York City. *George E. B. Jackson, - Portland, Me. *Charles W. Watkis, - Salt Lake City, Utah. *Charles E. Hall, - Philadelphia. *Charles J. Duval, - San Francisco, Cal. †tJoseph Gorlinski, - Salt Lake City, Utah. *Alfred Wartenweiler, - Salt Lake City, Utah. †Wilmot J. Bowen, - Salt Lake City, Utah. *Joseph Stokes, - Trenton, N. J. †Jason P. Brown, - Boston, Mass. *William Davis Hartshorne, - Bethlehem, Hunterdon Co., N. J. *Henry Williams, - Spanish Bar, Clear Creek Co., Col.. *Robert Forsyth, - Chicago, Ill. *S. T. Wellman, - Cleveland, Ohio. *H. C. Walton, - Chicago, Ill. *Andrew Roy, - Columbus, Ohio. *James H. Rittenhouse, - Providence, Pa. * Members. † Associates

Jan 1, 1875

By W. Kennedy

THROUGHOUT northeastern Texas we have an extensive series of iron-ore deposits, occupying portions of nineteen counties and having approximately an actual ore-covered area of 1000 square miles. The existence of these ores has long been known. Kennedy* says: "Iron-ore is distributed in profusion throughout Texas, being found almost everywhere except in the level region of the coast." Before this, C. Newell† had mentioned the existence of these ores thus: " Iron is found in abundance in the eastern, northern and middle portions of Texas;" and in 1849 Edward Smith‡ said: " We met with immense hills of iron which were said to be, and appeared to be, of excellent quality, in Cass and Titus counties.. . .. It is well known that Texas abounds with iron of first-rate quality." In 1859, Dr. Shumard? reports that detailed surveys had been made in several counties, and says: " Our labors have demonstrated the important fact that we have a vast iron-region in the eastern part of the state, embracing considerable areas in Cass, Harrison, Rusk, Panola, Smith, San Augustine and Shelby counties. The ore-deposits belong to the Tertiary era and consist chiefly of hematites and limonites, of which there are several varieties. We have also found in this district extensive beds of carbonate of iron." Dr. Shumard gives no very exaggerated description of Cass county§ as it then existed when he says : " Cass county alone is capable of supplying a number of furnaces with an abundance of excellent iron-ore for many years." Of Rusk county he says: "Our de-

Jan 1, 1895

By Gill Montgomery

At this moment in the history of the world, the all- pervading and universally most important fact is that the world population is beginning to outgrow its food supply, and the United States has suddenly lost its ability to give away huge food surplus to any nation in the world with a food shortage problem. This, of course, means that, all of a sudden, our government must completely reverse its former bureaucratic stance regarding crop controls and agricultural price supports, to out-right incentives to increase farm production and bring more idle land into food-growing use.

Jan 2, 1967

Meeting of May 22, 1914.-President Thayer. announced the appointment of the following Committee on Arrangements for the San Francisco meeting of 1915: Charles W. Merrill, Chairman; F. W. Bradley, Abbot A. Hanks, S. B. Christy, and H. C. Hoover. President Thayer announced the appointment of the following Committee on Organization for the Utah-Nevada Local Section: R. C. Gemmell, Chairman; C. D. Blood, Lafayette Hanchett, Ernest Gayford; Duncan MacVichie, and George W. Riter. The President of the Institute offered $100, to be known as the "President's Prize," to be used as prizes for the best papers submitted by members of the Affiliated Student Societies, to be divided as follows: First Prize, $50; Second Prize, $30; Third Prize, $20. A committee, consisting of J. F. Kemp, Chairman; W. L. Saunders, and T. T. Read, was appointed to report on the conditions to govern the award. The President announced the appointment of the Committee on Mining and Milling Methods, the personnel of which is shown on a subsequent page of this Bulletin. The following were appointed on the Advisory Committee to the U. S. Bureau of Standards, to represent the manufacture of the various non-ferrous metals as indicated: Copper, F. L. Antisell; Nickel, David H. Browne; Lead, H. O. Hofman; Aluminum, J. W. Richards; Zinc, G. C. Stone. It was voted to hold a meeting of the Institute under the auspices of, the Iron and Steel Committee, the Committee on Petroleum and Gas, and the Committee on Coal and Coke, in Pittsburg, Pa., Oct. 8, 9, and. 10, 1914.

Jan 7, 1914

By H. A. J. Wilkens, H. B. C. Nitze

From time to time papers treating of specific cases of Southern gold-mines and mining have appeared in the Transactions of this Institute, as well as in other journals and publications. Mr. George I?. Becker, of the United States Geological Survey, made a reconnaissance of the Southern Appalachian gold-belt during the fall of 1894; the results of his investigations are published under the title of "A Reconnoissance of the GoldFields of the Southern Appalachians," in the Sixteenth Annual Report of the Director of the United States Geological Survey, 1894-95 : Part III., " Mineral Resources of the United States." Mr. Becker has treated the subject mainly in a scientific geological manner. We present this paper to the members of the Institute as requested by the Secretary last May, with the object of covering the ground from a more practical and technical standpoint. The notes for this paper were made in a large measure from personal observations, gained chiefly during the past summer on a trip through the field. In connection with this trip we collected a suite of typical hand-specimens, representing the gold-ores and wall-rock from the more important localities. This collection forms a part of the exhibit

Jan 1, 1896

By S. Kobayashi, A. E. Armenákas, C. Mylonas

Earlier work1-4 has shown that commercial mild steels under static loading at the lowest natural operating temperatures fracture in a brittle manner only when damaged by a suitable history of straining. Notched and then compressed plates have fractured in subsequent tension at loads as low as 10 pct of the limit load and precompressed smooth bars at a subsequent extensional strain as low as 0.01. The comparison of the average net fracture stress with the flow limit stress was shown to be an excellent criterion of brittle or ductile behavior of mild steel structures when only loads and general stress levels are known. The present investigation shows that the deformation at fracture is a far more sensitive measure of brittleness than the fracture stress. Both criteria, deformation and stress, are used to determine the amount of uniform precompression of two mild steels, ABS-B and Project E-steel, resulting in brittle fracture under the strong constraint of a subsequently machined severe circumferential groove. The fracture stress equaled or exceeded the theoretical flow limit Ól = 2.680., ('based on the elevated yield stress at each prestrain) up to prestrains of about 0.20 and then fell off to about 1 at prestrains of 0.60. Yet a prestrain of only 0.05 reduced the elongation at the shoulders by a factor of about 4. The total plastic elongation of a region surrounding a sharp notch in prestrained steel deternines whether or not fracture will be initiated in large structures, hence is a direct and realistic measure of the remaining ductility and provides an excellent test of the material's resistance to embrittlement. ALMOST all engineering structures of mild steel which failed in service in a so-called "brittle" manner exhibited appreciable local plastic deformation (more than 1 pct) and a mixture of "cleavage" and "shear" fracture surfaces. Furthermore, the peak local stress in an advancing crack is always high. Such simple criteria as pure cleavage, absence of plasticity, or fracture stress, so useful in other fields, are insufficient to characterize brittleness in engineering structures at ordnary temperatures. The "brittle)' behavior of engineering structures is caused by the limited ductility at cracks or notch regions, as shown by recent work at Brown University summarized and extended in Refs. 1 to 4. It was also shown that the local ductility of mild steel may be catastrophically reduced by a suitable strain and temperature history similar to those which may occur in real structures. Localized yielding begins at the notch roots at low loads but is contained by surrounding elastic regions. The plastic strains are hence small. They increase slowly with the load up to the flow limit or limit load for an ideally plastic material. Unrestricted plastic flow then occurs. At such strains the real material locally st rain-hardens and fractures. With work-hardening materials no flow limit exists, and the transition from low to high plastic strains is gradual but increases more rapidly at loads close to the flow limit of an equivalent perfectly plastic material. When the available ductility is sufficient for reaching the limit load, the behavior is normal or "ductile". With insufficient ductility, fracture will occur at a low load and will be defined as "brittle". Accordingly the sufficiency or not of the ductility at a notch is reflected in the magnitude of the fracture load or average net stress as compared with the limit load or flow limit. The application of this criterion gave surprising results. Service failures under semistatic loading occurred mostly below the limit load, hence were "brittle". On the contrary all static tests with undamaged commercial mild steels reached the limit load in spite of the deepest notches and temperatures below Charpy impact transition (say about -30°F or higher). Notched bars showed no brittleness even under fully dynamic axial loading up to 1.5 x107 psi per sec at -23°F and about 2.5 x l06 psi per sec at -ll0°F, but broke in a brittle manner at -200°F and l03 psi per sec.' To propagate a fracture at low load, experimenters had to trigger it by superimposing a strong dynamic impact at a notch cooled by liquid nitrogen as in the Robertson5 or Esso tests.' Once started the cracks would run through warmer regions of smaller stress. Obviously the ductility of the apparently undamaged commercial steels was "sufficient" in the laboratory tests but not in the service fracture, where it must have been reduced by some embrittling procedure of fabrication or service. These conclusions were confirmed by the achievement of low static stress (brittle) fracture initiation in unwelded steel after a local reduction of ductility by simple prestraining. Symmetrically notched plates of undamaged mild steel cooled below the Charpy V-notch transition range were tested in central static tension: Undamaged plates withstood loads of limit intensity, but when subjected to prior in-plane com-pressive prestraining perpendicular to the notch axis and to accelerated aging, the plates fractured completely or partially at very low static loads, as low as one-tenth of the flow limit.2-4 However, damage could not be easily related to the strongly variable prestrain around a sharp notch. To obtain easier strain measurements, it was decided to use axially precom-pressed bars and bent bars. Final testing was done by

Jan 1, 1970

By C. F. Weinaug, P. M. Blair

Many difference equations used to approximate reservoir flow problems treat the phase pressures implicitly but not the mobility-density coefficients. Such difference equations are neither wholly explicit nor implicit, but might be described as mixed. Mixed equations are relatively easy to apply. But the associated time truncation error is relatively large, and when used to solve problems characterized by high flow rates, these equations may be unstable for practical size time steps. This paper outlines the development of a completely implicit difference analogue for reservoir simulation, along with a Newtonian iterative method for solving the resulting nonlinear set of algebraic equations that arise at each time step. While this implicit equation requires two to three times more work than does the mixed equation, it is shown to markedly decrease the time truncation error and to yield a stable solution for much larger time steps than does the mixed equation. INTRODUCTION Calculation of multiphase, multidimensional flow in porous media is generally accomplished by numerical methods that involve approximating systems of partial differential equations by systems of partial difference equations. The early development of difference equation techniques was directed toward the solution of linear differential systems. However, the equations of multiphase fluid flow through porous media are highly nonlinear in that mobility and density often are strong functions of pressure and saturation. Thus, solution of the flow problems by difference equations involves solving sets of algebraic equations whose coefficients change from step to step of the calculations. Current practice is to evaluate most coefficients at the beginning of a time step and then to apply difference methods well suited for solving linear problems. At least two major difficulties arise from the use of this practice. First, evaluation of coefficients at the old time level and evaluation of pressures at the new time level results in larger time truncation errors near displacement fronts than if all quantities in the distance derivative were evaluated at the same time level. Second, evaluation of mobility coefficients at old time levels results in an unstable difference equation in regions of high flow rate. The first of these difficulties often results in optimistic recovery behind the displacement front, and the second requires the use of small time steps or special techniques in solving coning problems1 or problems of gas percolation.2 Evaluation of all quantities in the distance differences at the new time level results in a completely implicit difference system. Such a difference system has a lower time truncation error than equations in which mobilities are evaluated at the old level and pressures evaluated at the new level. The algebraic equations resulting from the fully implicit difference equation are, in this case, nonlinear and require some iterative method for their solution. This paper develops fully implicit difference equations for two-phase flow in porous media, describes their solution by Newtonian iteration, and gives examples of problems more easily solved by the new method than by previous methods. EVOLUTION OF DIFFERENCE EQUATIONS FOR NONLINEAR PROCESSES The completely implicit difference equation used in these calculations results from evolution beginning with explicit difference equations, proceeding through what we will call "mixed" equations, and arriving now at a completely implicit equation. Let us illustrate the evolution by considering different analogs of the nonlinear equation

Jan 1, 1970

By Robert F. Mehl

THIS essay is an attempt to present the elementary facts and ideas concerning the growth of crystals, especially of metals. Freezing, like all heterogeneous processes, is a process of nucleation and growth; it manifests itself in metallurgy primarily in the freezing of ingots. The preceding paper in this volume discusses nucleation; the paper to follow describes ingot solidification. The present paper will treat of the growth of nuclei to large crystals, embracing a long series of phenomena, many of which are familiar to metallurgists.† Crystal growth, it will be immediately noted, occurs not only in the freezing of metals, but in the freezing of all substances; and it is a prominent and familiar phenomenon in crystallization from solutions, aqueous or otherwise, and in crystallization from the vapor phase. It will be necessary to include such systems in this discussion, for so much of value to metallurgists has been learned from their study. Apart from this, so far as metals are concerned, it will be simpler to limit the discussion to the freezing of pure metals and of solid solutions. Other types of freezing-eutectic, peritectic, etc.-will be excluded, though they have much of interest and of importance. BASIC MECHANISM OF FREEZING Ideally, nucleation and growth processes can best be considered from the point of view of isothermal reaction and upon the assumption of random nucleation. In. such an ideal case, nuclei form at random, and at a characteristic rate either constant or changing with time, and grow to spherulites at a characteristic rate, constant or changing with time, Fig. I.. On the simplest assumption, the reaction rate-in this case the rate of freezing-is a resultant of these two component rates. The reaction rate equation may be written in terms of these two component rates. The formation of pearlite from austenite closely approaches this ideal case. The ideal case forms a very useful point of departure in considering real cases. Various factors of reality produce deviations from this assumed ideality. In freezing, the isotropic medium, the melt, passes to the anisotropic solid, the crystal. Crystals are lattices of atoms, and the unit cell is often referred to as a crystal unit. Rosenhain, many years ago, represented the nucleation and growth process on freezing in the manner shown in Fig. 2, feeling, intuitively, that there must be some crystal unit in crystal growth. It now appears that this may be true, though his picture requires much elaboration. The greatest deviation from ideality lies in the nonisothermal nature of the freezing process in metals. To approach this properly it should be recalled that many nonmetallic substances freeze slowly. Tammann, to whom we owe the classic approach, studied complex organic materials in which (as in the case of eutectoid steels at high

Jan 1, 1951

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

By H. N. Eavenson

Prior to 1907 nearly all coke was made in beehive ovens, and most of the gas produced was made in the old-style gas retorts, and while there were a few coke plants in southern West Virginia, southwest Virginia and Kentucky operating on high-volatile coals the proportion of the total product made by them was small and usually was used locally. The greater part of the coke made, and the coal gas produced, came from the Pittsburgh seam of western Pennsylvania and northern West Virginia, which was then regarded as the standard coking and gas coal of the country, and the best coal available anywhere for these purposes. With the advent of the byproduct oven and the building of coke plants at the furnaces, the restriction of the use of one grade of coal for making coke was removed and the use of mixtures of low-volatile and high-volatile coals began. The change in the locations of the coke plants removed the necessity of using Connellsville coal and also made sources of gas available to the public utilities other than of their own manufacture. Most of the first oven plants were built at points distant from the Connellsville region and this afforded an opportunity for the use of coals from the southern Appalachian fields, which were then at approximately equal distances from the ovens. Since that time development has been made on a number of seams of coal of great purity in southern West Virginia, southwestern Virginia and eastern Kentucky, which have been largely used for gas, cokemaking and metallurgical purposes where low amounts of ash, sulfur and phosphorus are determining factors. These coals are much lower in the objectionable elements than most of the coal shipped from the Pittsburgh seam, or than any northern coal, and when blended with low-volntile cod produce coke in byproduct ovens that is not excelled for any purpose by any coal mined in this country, and is equaled very seldom. Coal from several of these scams is shipped in great quantities without beneficlation and is lower in ash and sulfur than any but the best washed product from the Pittsburgh seam in the north. The writer has made a study of these coals to ascertain their relative qualities and the areas and reserves of coal available in each of them. No attention has been paid to the coals of Alabama, which do not compete with any of these coals, and no coal of equivalent quality is found in

Jan 1, 1934

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951