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By Persifor Frazer

I DESIRE to say that, owing to the number of papers which have been more or less crowded at this session of the Institute, and the fact that, as one of the Local Committee, I have the distinguished honor to feel somewhat like one of the hosts, I should not tax the patience of members at this late hour, but would have my paper read by title were it in any way possible to do this. But the task I have set myself this evening is to present to the eyes of the members of the Institute certain objects which have occupied more or less of my time during the last eighteen months or two years. The objects I allude to are some of the igneous rocks of this country, which, until quite recently, have been less understood than any others. It will be well known to some of the members that some of the cooled lavas of a previous age of our planet, when not directly coarsely crystalline and granular, were considered and spoken of as " natural glasses," or perfectly uncrystalline, vitreous, or hyaline masses of matter. Among the first results of the use of the microscope was the dispersion of this fallacy. Sir David Brewster, Mr. H. C. Sorby, and William Nichol (the discoverer of the celebrated calcite prism, which bears his name), had, with greater or less success, examined sections of various rocks and minerals, both by transmitted and reflected light, and also in the form of powder. But, until the genius of Vogelsang undertook the subject, these investigations had no permanent value, nor did they constitute an independent line of mineralogical and geological research. Since the close of his labors, by Vogelsang's premature and much-lamented death, the subject has been made one of renewed interest by his brother-in-law, Ferdinand Zirkel, as well as by Rosenbusch, Tschermak, and many others abroad, and at home by the commencement of a systematic study of the traps of Connecticut by Messrs. E. D. Dana and G. W. Hawes, of New Haven, and by the splendid set of described sections of the traps of the West which have been furnished by Zirkel to illustrate Clarence King's report. I had the honor of presenting a large number of thin sections of our traps at the Washington meeting, for the inspection of the members, with the aid of a table microscope belonging to the Smithsonian Institution. Here I propose to project these sections upon the

Discussion of the paper of S. E. Bretherton, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1481 to 1487. S. E., BRETHERTON, San Francisco, Cal.:-Since preparing my paper, our chemist, F. L. Wilson, has been experimenting with Leadville, Colo., oxidized zinc ore and Leadville zinc sulphides containing lead, operating upon 40-1b. lots at a time. His results on Leadville sulphides are as follows: The raw ore contained a trace of gold, 5.04 oz. of silver, 19.1 per cent of zinc, and 7.24 per cent of lead. After roasting the ore contained a trace of gold, 5.72 oz. of silver, 0.75 per cent of copper, 21.7 per cent of zinc, and 8.29 per cent of lead. The loss in weight by leaching was 38.8 per cent. The extraction was 42.8 per cent of the copper, 80.6 per cent of the zinc, 7.1 per cent of the lead, 0.64 per cent of the silver, and no gold. The little .silver that is extracted would be thrown down with the copper when precipitating it from the zinc and both thrown hack into the residue to be smelted. There would be no trouble in smelting the residue with nearly all the sulphur eliminated and containing less than 7 per cent. of zinc. On zinc carbonates containing silicates the results are not satisfactory. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :¬The paper by Mr. Bretherton upon the application of ammonia and carbonic acid to the recovery of zinc as oxide from roasted sulphide ore is of interest to me, as the first installation of the Schnabel process for the extraction of zinc from a mixture of zinc oxide, lead oxide (with some cupric oxide), and pellets of enriched lead, produced in steaming liquated zinc-silver-lead crust of the Parkes process, was made at Lautenthal, Harz mountains, where I was chemist. In that capacity I carried out numerous experiments on the Schnabel process, was active in the erecting of the plant, and later had charge of it. After the Lautenthal plant had been in operation for some time a similar one was built at Hoboken-les-Anvers, but both have been abandoned, as the wet process could not compete with the distillation of the liquated zinc-silver-lead crust, now used universally in the Parkes process.

Jan 11, 1913

By H. J. Rahilly

MINE FIRES, in the Butte District, have been a source of trouble and expense for the past thirty years, for while the actual fire area in most of the mines has been comparatively small, the handling of the gas has generally been a much larger problem than the actual putting out of the fire. The chief causes of these fires have been: Defective electrical equipment, incendiarism or carelessness, and spontaneous combustion. While fires from the first two causes have been numerous, they have generally been discovered and extinguished before they became very serious. Spontaneous combustion has been the cause of most of the large fires. Sufficient heat has been generated by ground movement, high rock temperatures, and decomposition to set fire to inflammable materials (tarred ropes, canvas, dry timber, manure, and hay) left in the gobs some years ago. Also, the heat resulting from the oxidation of the fine broken sulfide ore is sometimes sufficient to set fire to the timbers. In 1906, a fire was discovered on the 1100-ft. level of the Minnie Healy mine about 400 ft. (122 m.) west of the Minnie Healy shaft, which presumably originated, in one of the upper levels, from spontaneous combustion. The fire was walled off by concrete bulkheads and a pillar of ground 100 ft. (30 m.) thick was left below and mining resumed underneath. During subsequent operations, this pillar became cracked and broken and the fire passed into the new workings. It travelled downward and spread rapidly until, in 1917, it had become necessary to wall off portions of the Tramway, Leonard, and West Colusa mines on the 1300, 1400, 1500, 1600, 1800, 1900, and 2000-ft. levels, and the top of the 2200-ft. raises were sealed. The fire area now consists roughly of a block 1000 by 1200 ft. and from the 600-ft. to the 2200-ft. level. This block is composed largely of a series of parallel northwest-southeast nearly vertical veins and stringers that form a large orebody, with no well-defined walls but badly fractured and faulted, and known locally as "Horsetail Ore." These veins, or orebodies, are mined by the square-set or the rill method.

Jan 2, 1922

By Robert Gorham Morse

This paper presents the results of an investigation made in the metallurgical laboratory of Columbia University, New York City. The object of the investigation was to determine how the tensile strength, the elastic limit, and the size of the grain, of a pure medium-carbon steel are affected by heating to successive temperatures between 500° and 1300° C., with slow cooling therefrom. Since Dr. Sorby's first investigations into the microstructure of steel, the study of the subject has been continued by Professor Martens, Mr. F. Osmond, Professor Arnold, Professor Howe, Mr. A. Sauveur, Mr. J. E. Stead, and many others. Among many valuable and interesting papers I mention the following as having a special bearing upon this investigation.* " Microstructure of Steel," by Albert Sauveur, Trans., xxii., 546 (1893); Microscopic Metallography," by F. Osmond, Trans., xxii., 243 (1893); "The Microstructure of Steel and the Current Theories of Hardening," by Albert Sauveur, Trans., xxvi., 863 (1896); "The Crystalline Structure of Iron and Steel," by John Edward Stead, J. Iron and Steel Inst., 1898. II.—Statement of Experiments. Through the kindness of Mr. N. Lilienberg, New York City, round rods 3/4 of an inch in diameter were obtained, which had been rolled from one ingot. The analysis of the steel was as follows : C, 0.343; Si, 0.027; Mn, 0.221; I?, 0.0266; S, 0.0037 per cent.

Jan 1, 1900

The John Fritz Medal is awarded from time to time for notable scientific or industrial achievement by a board composed of representatives from the four engineering Societies. The members of the Board of Award for 1917 are: A. S. C. E. A. S. M. E. George F. Swain Ambrose Swasey, Charles Warren hunt, John, A. Brashear, Charles D. Marx, Frederick R. Hutton, Clemens Herschel. John R. Freeman. A. I. M. E. A. I. E. E. Gybbon Spilsbury, C. 0. Mailloux, Charles F. Rand , Paul M. Lincoln, Christopher R. Corning, John J. Carty, Benjamin B. Thayer. Harold W. Buck. The John Fritz Medal was awarded in January, 1917, to Dr. Henry Marion Howe, for his "investigations in metallurgy, especially in the metallography of Iron and Steel." The presentation ceremonies were held in the Auditorium of the United Engineering Societies' Building, New York, on Thursday evening, May 10. Mr. Ambrose Swasey, Chairman of the John Fritz Medal Board of Award, presided, and addresses were delivered by Dr. Rossiter W. Raymond, Secretary Emeritus of the American Institute of Mining Engineers, and Dr. Ira N. Hollis, President of the American Society of Mechanical Engineers. Professor Albert Sauveur, Chairman of the Board at the time the award was made, presented the medal, and the ceremonies concluded with the response of Dr. Howe.

Jan 7, 1917

Application of Kutter's Formula to Gases Discussion of paper by F.-ERNEST BRACKETT, presented at the Pittsburgh Meeting and issued, as Pamphlet No. 1578-A-F, with MINING AND METALLURGY, June. 1926. C. S. WITHERELL, New York, N. Y..(written discussion).-There is no reason to doubt that the relationship between the rate of, flow and. the impelling force of all fluids can be expressed by a general typical equation that takes cognizance of all relevant factors such as density, viscosity (or its reciprocal, mobility) and nature of channel-walls. Most fluids that are commonly conveyed by flow in confined channels are so highly mobile that they may be considered non-viscous, hence for these fluids the factor of viscosity does not need to appear in the equation. Water is the outstanding example of this class of fluids and its dynamic behavior has been so thoroughly investigated that proven formulas pertaining thereto, be they rational or empirical, would naturally serve as prototypes for the other non-viscous fluids. As non-viscous fluids can be classed all gases and vapors, most unsaturated aqueous solutions, gasoline, alcohol, etc. Viscous fluids comprise those that have a sluggish flow such as most oils, tar, molasses, etc., the' high viscosity of which is due to shearing resistance between molecules, a force that must betaken into account in figuring the flow of fluids of this class.

Jan 10, 1926

Application of Kutter's Formula to Gases Discussion of paper by F. ERNEST BRACKETT, presented at the Pittsburgh Meeting and issued, as Pamphlet No. 1578-A-F, with MINING AND METALLURGY, June. 1926. C. S. WITHERELL, New York, N. Y. (written discussion).-There is no reason to doubt that the relationship between the rate of flow and the impelling force of all fluids can be expressed by a general typical equation . that takes cognizance of all relevant factors such as density, viscosity (or its reciprocal mobility) and nature of channel-walls. Most fluids that are commonly conveyed by flow in confined channels are so highly mobile that they may be considered non-viscous, hence for these fluids the factor of viscosity does not need to appear in the equation. Water is the outstanding example of this class of fluids and its dynamic behavior has been so thoroughly investigated that proven formulas pertaining thereto, be they rational or empirical, would naturally serve as prototypes for the other non-viscous fluids. As non-viscous fluids can be classed all gases and vapors, most unsaturated aqueous solutions, gasoline, alcohol, etc. Viscous fluids comprise those that have a sluggish flow such as most. oils, tar, molasses, etc., the high viscosity of which is due to shearing resistance between molecules; a force that must be taken into account in figuring the flow of fluids of this class.

Jan 10, 1926

By C. W. Spencer, B. F. Addis, G. H. Bishop, C. A. Steidel

STUDIES of the inter granular attack of metals by liquids have generally been confined to polycrys-talline specimens. This note reports the results of preliminary studies of the penetration of bismuth-rich Ni-Bi liquids into oriented bicrystal specimens of nickel. It is found that isothermal penetration follows a parabolic rate law and shows a definite anisatropy with respect to direction on the grain boundary surface. Nickel bicrystals containing < 100> tilt boundaries were grown using the Czochralski method. Relative misorientation of the parent crystals was controlled to ± 1deg. The boundaries are straight in the growth direction, i.e., the common <100>, and generally straight in the transverse direction, as shown in Fig. 1. The starting material, Inco HPM grade nickel was contained in a recrystallized alumina crucible and maintained under argon. Bicrystals typically contain 30 ppm C, less than 10 ppm S, O, N, and 50 ppm residual metallics, principally iron and silicon. Specimens, as schematically illustrated in Fig. l(c),were cut from bicrystal ingots using a thin water-cooled abrasive wheel. To insure removal of all residual strain, which accelerates the penetration, specimens were round through 600 grit silicon-carbide, chemically polished, and annealed for 4 hr at 1375°C under argon. The procedure described by Cheney et al.1 for exposing specimens to

Jan 1, 1962

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain&apos; and magnesia.&apos; Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann&apos;" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By Lawrence Addicks

Discussion of the paper of LAWRENCE ADDICKS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1471 to 1484. L. D. RICKETTS, New York, N. Y.--In the Southwest we have stored up millions of tons of tailings in which the copper exists partly as sulphide and partly in an oxidized condition. Mr. Addicks&apos; first paper suggests a, likely process for the treatment of such material. His second paper 1 deals with the recovery of copper from clear solutions of notable strength, and such solutions may come from the sulphating roast or direct from the leaching of completely oxidized copper ores of which vast deposits are known to exist. What strikes me particularly about the latter paper is the keen perception shown and the clear manner in which the writer has attacked the fundamental principles of the process. He calls your attention to the fact that ferrous sulphate is necessary in the electrolyte and is an ideal depolarizer; that sulphurous acid must be, used to reduce the ferric sulphate produced and thus prevent re-solution of copper at the cathode; that mechanical agitation in the cell, in order to bring the ferrous sulphate in contact with the anode and the copper in contact with the cathode, is essential to efficient work; that lead anodes are

Jan 12, 1915

By Carl Gatlin, S. Srini-Vasan

It is shown thar k k ratios cornputed on the as.sutnption that the average sandstone reservoir has a pore-size distribution characrerized by a linear 1/P saturatioN plo are in good agreewient with correspotlding k,,/k,, ratios obfairzed by Wahl, Mul-/ins and Elfrink by correlatiotz of field measurements. Methods of calculating relative permeability data have recently been reviewed and extended.&apos; It was shown that for sandstone reservoirs where &apos; is approximately a linear function of effective saturation (as suggested first by Corey&apos;) it is possible to express relative permeabilities in very simple terms. For systems wetted by connate water and producing oil and gas (gas saturation growing at the expense of oil) the expression for the The accuracy of Eq. I has been frequently confirmed in our laboratories; because of its simplicity we make routine use of it in the analytical solution of proble~ns in reservoir engineering. Nevertheless, comparisons of the k,,,/k,, ratios yielded by Eq. 1 with appropriate reservoir data have been few. The publica- tion by Wahl, Mullins and ElfrinkV of an empirical equation for k,,/k,, ratios is thus of interest since this equation is specificalljl stated to be Vased on the correlation of field measurements made on sandstone reservoirs. Not surprisingly these authors found that it was necessary to

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B&apos;) where B and B&apos; are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By D. H. Baldwin, R. E. Reed-Hill

Six compositions of polycrystalline ZY-0 alloys, containing up to 4.2 at. pct 0, were tested in tension between 77° and 600° K. The data obtained from each of the compositions corresponded closely to a rela-ion between yield stress and absolute temperature of the form In s/so = BT, where oo is the yield stress extrapolated to zero degrees and B is a constant. In agreement with others who have observed this relationship, it is shown that the activation energy may be expressed as Ho In so/s. In the present specimens Ho is approximately 18,000 cal per mole and is apparently independent of temperature and composition inside the limits of the investigation. It is also demonstrated that this form of activation energy cowesponds to a strain rate sensitivity parameter RT/Ho. Oxygen was also noted to have an effect upon the operative deformation mechanisms. With increasing oxygen concentration there was an increased tendency to observe both nonbasal slip and cross-slip phenomena. Oxygen does not seriously inhibit twinning more than it does slip. Twins were observed in all specimens tested. It is becoming increasingly evident that interstitial atoms in solid solution are able to interact strongly with mobile dislocations. Stein, Low, and seybolt,&apos; have shown that, if the carbon concentration in bcc iron is lowered below the solubility limit, its flow stress temperature dependence is markedly reduced. This suggests that carbon atoms in interstitial solid solution may be responsible for the pronounced temperature dependence of the flow stress normally observed in iron. This view has recently been challenged by Leslie and sober2 who observed a strong flow stress temperature dependence in iron to which a trace of titanium had been added in order to remove carbon atoms from solution. Since the interstitial concentration must be reduced below approximately 1 ppm in order to produce a pronounced effect on the flow stress temperature dependence,&apos; studies of the effect of interstitials on the flow stress in iron necessarily involve serious experimental difficulties in alloy preparation. There are other metals, however, in which strong effects of interstitial solutes upon both the flow stress and its temperature dependence are observed. Of particular significance is zirconium which, according to Domagala and Mcpherson, 3 is capable of dissolving 28.6 at. pct O. The O-Zr alloy system is an almost ideal system for studying the interaction of interstitial atoms with deformation modes since it is possible to form alloys capable of study over an extensive range of compositions. Mills has made such a study using single crystals oriented primarily for single prismatic slip4 and has found an effect of oxygen concentration on the flow stress temperature dependence analogous to that observed in iron due to carbon by Stein, Low, and Seybolt. The present paper is specifically concerned with the effect of oxygen on deformation in polycrystalline zirconium. Although plastic flow in this type of specimen is much more complex than that reported for the single-crystal work, and involves both slip (on several different types of planes) and mechanical twinning, the results of this investigation are in general agreement with the single-crystal observations concerning the effect of oxygen on the temperature dependence of the flow stress. In addition, they also demonstrate that oxygen affects the acting deformation systems. This is in contrast to single-crystal results4 that showed only single slip on a prism plane. EXPERIMENTAL PROCEDURE Material. High-purity hot-rolled zirconium strip, 0.2 in. thick by 4 in. wide, of 0.10-mm average grain diameter, was used for forming alloys. It was obtained from the Carborundum Metals Co., Akron, N.Y., whose analysis indicated the major impurities were, in wt ppm: Hf, 540, C, 145; Fe, 100; and 0, <80. The plate texture was similar to a wire texture, with basal planes generally parallel to the rolling direction and basal poles randomly distributed about the rolling direction. The heat treatments described below did not appreciably alter the basic texture. specimen Preparation. Small threaded-end tensile specimens were machined from the plate with axes perpendicular to the rolling direction. These transverse specimens had gage sections 1 in. long by 0.060 in. in diam. The small gage section diameter was dictated by the fact that the alloys were formed by dif-

Jan 1, 1969

By R. Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested. THE physically dissimilar components of bituminous coals often are easily recognized mega-scopically. Under the microscope, reflected light or light transmitted through thin sections reveals the presence of the different components, even when these are intimately mixed. Optical methods for the quantitative estimation of the relative abundance of the various components, both by means of thin sections and by particle count, have been fully described.&apos;. &apos; It has long been recognized that there are chemical and physical differences between the various petro-graphic components of bituminous coals, although analytical differences usually are small.:&apos;. &apos; Only in the case of fusain have chemical differences been used for quantitative determination of a component. C. C. Hsiao and associates, at the Mineral Industries Experiment Station of the Pennsylvania State College, have described a method of analysis which is based upon the differences in the rate of nitric acid (8N) oxidation, fusain, and the other components of coal."," The reproducibility of their method and its applicability in checking microscopic determinations of fusain content have been supported by several independent investigations.&apos;. " The writer has proposed the use of differences in oxidizability for the estimation of other components." "&apos; The results of the oxidation of whole coals and of float-and-sink fractions of coals were reported. In most cases the plots of the logarithms of the percent dry, non-fusain, organic residue from oxidation, against time, revealed the presence of at least two distinct components. Both components appeared to oxidize according to a first order law, but the reaction constants for the components were distinctly different. One or more of the dull density fractions were found to contain but one component, and some of the lower rank coals oxidized in such a way as to suggest the presence of three components. A suitable way to check the identity and significance of the components delineated by oxidation would be to analyze a sample of coal both by the nitric acid oxidation procedure and by a microscopic method. The writer was wholly unfamiliar with either of the microscopic techniques commonly used, and to make such a comparison it was necessary to rely upon microscopic analyses made by someone else. It is hoped that some laboratory which is equipped to make both types of analyses will some day make them upon identical samples. During the past 20 years, four Alabama coals have been analyzed petrographically and the results published by the United States Bureau of Mines. They are: 1—Flat Top mine, Mary Lee bed; 2—Empire mine, Black Creek bed; 3—Wylam No. 8 mine, Pratt bed, all in the Warrior field; and 4—Soot Creek mine, Fairview bed, in the Coosa field."-" Of these, only the Flat Top mine is still operating. Because of the closing of these mines, it first appeared necessary to rely upon the indirect and unsatisfactory procedure of sampling the beds in other mines located as near to the closed mines as possible. Upon investigation, however, it was found that the Bureau of Mines still had, in storage, the very same samples which had been used in the published petrographic studies. The Bureau very generously furnished about 2000 g each of the Pratt, Mary Lee, and Fairview bed coals, largely lumps but with some fines. The blocks of coal, when received, still were covered by the paraffin coating which had been placed on the polished surface, in the case of the Mary Lee coal almost twenty years ago. Procedure The procedure for oxidizing the coal sample and removing the alkali-soluble humic acid has been described. In the present study, oxidation periods of 1/6, 1/3, 1/2, 3/4, 1, 2, 3, and 4 hr were used. All oxidations were made in triplicate. After the paraffin had been removed in boiling water and the coal washed carefully with cold benzene, the entire sample of approximately 2000 g, obtained from the Bureau of Mines, was crushed to pass a No. 4 sieve. About 200 g of this material was pulverized to pass

Jan 1, 1954

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound&apos;&apos; twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman&apos; to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350&apos;~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,&apos; and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.&apos; The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,&apos; the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.&apos; Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955