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By L. C. Graton

[CONTENTS PAGE INTRODUCTION AND ACKNOWLEDGMENTS. By George M. Fowler2 Question 1-Is Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions, Especially in Limestone or Other Dense Rock? DISCUSSION by: A. M. Bateman 10 S. F. Kelly 15 C. H. Behre, Jr 8, 13 G. B. Langford 13 T. M. Broderick11 H. E. McKinstry6 R. H. Clarke 13 D. H. McLaughlin8 J. D. Forrester for M. H. Gidel . . . 4 W. H. Newhouse13 G. M. Fowler 2, 6, 11 R. H. Sales 6 L. C. Graton 11 Edward Sampson 12 R. D. Hoffman 10 J. S. Stevenson 7 I. B. Joralemon11 L. B. Wright 2 Question 2-What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? DISCUSSION by: G. W. Bain 17G. M. Fowler 21 C. H. Behre, Jr21L. C. Graton18 J. S. Brown 16G. F. Loughlin18 E. L. Bruce 19R. H. Sales 19 R. H. Clarke 20A. K. Snelgrove 20 Question 3-Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? DISCUSSION by: J. M. Boutwell29G. B. Langford 29 T. M. Broderick28G. F. Loughlin25 E. Y. Dougherty27R. H. Sales 24 G. M. Fowler 22F. A. Thomson 26 I. B. Joralemon 22Edward Wisser 30 General S. F. Kelly35 References36

Jan 1, 1940

By Emil Gathmann

(San Francisco Meeting, September, 1915) THROUGH wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," -i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot: Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe .at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium,

Jan 8, 1915

CONTENTS PAGE BAIN, EDGAR C.-The Nature of Martensite. Discussed by Ancel St. John, Henry S. Rawdon, Jerome Alexander, Howard Scott 1 FEILD, ALEXANDER L.-Effect of Zirconium on Hot-rolling Properties of High-sulfur Steels and the Occurrence of Zirconium Sulfide. Discussed by Beram D. Saklatwalla, Bradley. Stoughton, Andrew M'Cance, George F. Comstock, Alexander L. Feild 12 SAUVEUR, ALBERT and KRIVOBOK, V. N.-Use of Sodium Picrate in Revealing Dendritic Segregation in Iron Alloys. Discussed by George F. Comstock, John H. Hall 17 KINNEY, C. L., JR.-Economic Significance of Metalloids in Basic Pig Iron in Basil Open-hearth Practice. Discussed by V. J. Pazzetti, George B. Waterhouse, C. L. Kinney, Jr 19 NEAD, J. H.-Absorption of Sulfur from Producer Gas in Open-hearth Furnaces.. Discussed by George B. Waterhouse, C. L. Kinney, Jr 26 PRIESTLY, WILLIAM J.-Effect on Steel of Variations in Rate of Cooling in Ingot Molds. Discussed by Emil Gathmann, Paul E. McKinney, George A. Dornin. 27 MONYPENNY, JOHN H. G.-Stainless Steel, with Particular Reference to the Milder Varieties (Stainless Iron). Discussed by P. A. E.-Armstrong, Beram D. Saklatwalla 33 ROYSTER, P. H., and JOSEPH, T. L.-Effect of Coke Combustibility on Stock Descent in Blast Furnaces. Discussed by Ralph H. Sweetser,. Richard Franchot, Sidney Cornell, T. L. Joseph 41 DAVIS, F. W., and BOLE, G. A.-Observations on Requirements of Refractories for Open Hearth. Discussed by C. L. Kinney, Jr., L. F. Reinartz, P. E. McKinney 46

Jan 5, 1924

Jan 1, 1969

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By F. O. Willhofft

The symposium on mine safety held in connection with the annual meeting of the Institute three years ago, it. was pointed out that "at present no convenient, reliable, accurate means for determining the gas content of mine air is available, for use by the ordinary mine man." In a letter addressed to Coal Age and published on Feb. 25, 1925, Thomas T. Read, then Director of the Safety Service of the Bureau of Mines, stated: "It is to be hoped that sometime in the near future some-one will invent a reliable methane indicator that is con-venient to, use and will permit the keeping of all flames of every character out of bituminous mines, through doing away with the safety lamp." The Martienssen methane detector, which has re-cently received the official approval of the Bureau of Mines, is intended to. meet the demand for such an in-strument as expressed at that meeting and on many other occasions. The characteristics which qualify it for the task are the following: (1) simplicity; (2) small bulk and light weight; (3) ruggedness; (4) accuracy sufficient for the requirements; (5) safety; and (6) dependability. The principle on which the working of the instrument is based may best be explained by giving a brief out-line of the various stages of development through which the inventor, Professor Martienssen of the University of Kiel, Germany, advanced to the final solution of the problem which he had undertaken to solve.

Jan 2, 1928

By Yap Chu-Phay

IN 1923, when the writer began his studies in metallurgy, he came upon an article by Professor Honda on the, Equilibrium Diagram of the Iron-carbon System, 1 which made a profound impression on him. What interested him most was this sentence: "In the recent diagram of the iron-carbon system, the solidus is usually shown as a curve bending considerably downward. But it can be shown by thermodynamics that if the liquidus is straight or slightly curved, the same must also be true for the solidus. Hence, in my constitutional diagram, the lower portion of the solidus is slightly bent upward." Ever since then the writer has been interested in thermodynamics, especially chemical thermodynamics. The applications of thermo-dynamics to the metallic systems have been, in the writer's opinion, sadly neglected, although we continually use the phase rule in our study of equilibria in the liquid and solid states of metallic alloys. Many investigators, among whom may be mentioned Heycock and Neville, and s Honda and his coworkers, have applied the simple Raoult-van't Hoff law of depression of freezing point, mainly to determine the heat of fusion, but no attempt has been made to investigate the applicability of the thermo-dynamic laws of solution (as opposed to the laws of solution derived from other sources) to metallic systems" showing either limited or complete solid solutions. Perhaps the reason for this neglect is that until recently there have been so few reliable data on the solidus, which is much more difficult to determine than the liquidus. The writer has under way at the present time an investigation of a number of systems, the solidi of which have been more or less reliably determined. Recently, the writer has not only shown the valid applicability of the thermodynamic laws of solution as applied to the system antimony-bismuth but has also suggested a method of attacking problems involving complete and incomplete equilibria.2 In the present paper, the same method of approach is employed. For convenience, we shall divide this paper into two parts:

Jan 1, 1931

[Pumps: oil-well: plunger: essential parts, G26, 130; 74, 828 improved type, 74, 846 leakage, 74, 837 operating cycle, 74, 833 Uren design, G26, 145 sucker-rod failures, G26, 136 sucker-rod stress, 74, 835 sucker rods, 74, 830, 832 tubing, 74, 833 tubing difficulties, G25, 138; 74, 836 Olivite, 73, 337 valve and seats, 74, 832 Punching: Monel metal, 78, 86 nickel, 78, 86 Punjab. See Indian Empire. PUPIN, M. L biography, M26, 113 John Fritz medalist, 1931, M81, 499 recipient of Washington Award, M28, 155 PURDY, R.: Discussions: on Relative Efficiencies of Domestic Fuels in Relation to Their Costs and Their Advantages 108, 353 on Uses on Coal in the Ceramic Industry, 108,389,398]

Jan 1, 1936

By N. H. MacMillan, O. C. Dias

Recent work by Westwood et al. (reviewed in Refs. 1-6) has established that many rocks, minerals, ceramics, and glasses exhibit phenomenologically similar chemomechanical (Rebinder) effects when deformed in different liquid environments, apparently as the result of chemisorption-induced variations in their near-surface flow and flow-dependent fracture behavior. In particular, it appears that there exists an empirical, but apparently general, correlation between the near-surface flow stress of an inorganic nonmetal and its surface charge- namely, that such a solid is hardest at its zero point of charge (i.e., when its zeta potential [ ] = 0) and softens as [ ] increases, regardless of the sign of zeta. Moreover, because near-surface flow and fracture phenomena are two of the important determinants of the rates of machining and comminution processes, both Westwood et al. and others7 have been able to use this so-called "[ ]-correlation" to develop cutting fluids and grinding aids that in many instances have given rise to several fold increases in performance. In addition, Westwood et al. have demonstrated that both aqueous and organic environments can give rise to similar improvements in cutting rate for a given combination of tool and workpiece, provided that both impart the same surface charge to the work- piece (i.e., transfer the same number of electrons to or from its surface). This last finding implies that in any application it should always be possible to find some cutting fluid that is at once effective, cheap, nontoxic, and nonpolluting. Thus, reports of apparently similar environmental influences on the mechanical behavior of diamond,8 certain organic crystals and polymers,9-14 and coa1-15-21 suggest that it is pertinent to ask: (a) whether the [ ]-correlation (or any analogous relationship) extends to coal; and (b), if so, whether this relationship can be used to guide the development of superior aids for grinding coal. Accordingly, correlations have been sought between (1) the zeta potentials, (2) the hardnesses, and (3 and 4) the drilling and grinding characteristics of coals of different rank in different aqueous and organic environments. This paper reports the results of that search.

Jan 1, 1980

By AIME

WE got our chance to talk with Arthur J. Blair at the Annual Meeting at the Pennsylvania Hotel. By two o'clock Wednesday afternoon things had quieted down enough so we had our interview in the foyer to the Ball Room. There were the usual questions. Where were you born? In La Salle County, Ill., on March 26, 1885. Where did you go to school? Northwestern University, B.S. degree in 1906. Where did you start work? For E. J. Longyear right after leaving school. One's ability as a geologist was measured by one's ability to wield a brush hook and ax. He stayed on the job as geologist for three years and then got to thinking about the advantages of a warmer climate. The advantages stacked up favorably, so off he went to Birmingham, Ala., just about the time U.S. Steel took over the Tennessee Coal, Iron and Railroad Co.

Jan 1, 1948

By A. W. Fahrenwald

Flotation practice in Idaho is now about 13 years old. The advance has been steady during these 113 years. The operators have been alert to take advantage of the newest developments and they have themselves made a constant effort to improve their work. The metallurgical improvements are due to the development of (1) better equipment, (2) better reagents, and (3) better understanding and control of the process. During the eight years the writer has been in this district, there has been continuous experimentation by several companies to improve the ore dressing by flotation methods. Gravity concentration has fought hard to hold its place, and although it is true that gravity processes have been improved during this period, nevertheless, in several of the important mills of the district the few tables that managed to hang on have finally given way. On the straight-lead ores, tables and jigs are still used; and, due to better classification, their hold on this job has been strengthened. Ores of the District The ores of the district are of two general classes: (1) clean lead ores, such as those from the Bunker Hill and Hecla mines, and (2) complex lead-zinc ores. The general impression prevails that the clean lead ores, class 1, are simple and that it is easy to obtain high recoveries and good grade products. This, in a way, is a false impression; there is quite a high percentage of locked middling in these ores at 100 and' 150-mesh sizes. Improved classification preparatory to table treatment of this type of ore has made it possible to segregate effectively a high-grade middling which is further comminuted and floated. The complex lead-zinc ores of the district, of which the ore from the Morning mine of the Federal Mining & Smelting Co. is a typical example, always have presented a difficult problem. It always has been comparatively easy to make a clean lead concentrate, but it never has been possible to concentrate sphalerite with a specific gravity of 4.10 from siderite of gravity 3.88. Also, a large percentage of the galena and sphalerite of this class of ore refuses to separate out until the crushing has been carried

Jan 1, 1928

By A. G. Weber, R. L. Ledbetter, A. L. Hicks

A procedure which makes use of both analog and digital computers has been developed for predicting the pressure-production behavior. of water-drive reservoirs. The electric analyzer is used for matching the past pressure and production history of the reservoir and inferring the physical characteristies of the aquifer. When the history has been matched, a .set of base curves called influence functionce" are derived and the future behavior of the reservoir is calculated from these curves. INTRODUCTION Electric analog methods are particularly well-suited for complex water-drive problems. Like all other methods of analyzing water-drive reservoirs, however, analog methods are subject to certain limitations. One of the more obvious and serious of these results from inaccurate or insufficient knowledge about physical characteristics of the reservoir and aquifer. However, it is not insurmountable because the unknown characteristics can usually be inferred from the reservoir's previous behavior. Simons and Spain have shown that even with scant reservoir data and limited production history, electric analyzer studies can provide useful and reliable results. Aside from this limitation on analyzer predictions, the main disadvantage has been lack of a technique for keeping predictions abreast of latest production forecasts. Pressure behavior of a reservoir depends on the rate at which fluid is withdrawn; it is therefore necessary to specify the future withdrawal schedule before the future pressure behavior can be calculated. Conventionally, the electric analyzer predicts pressure behavior for a specific production schedule. If this schedule is abandoned in favor of some new one, as is frequently the case, either the study must be rerun or results adjusted in some manner. The usual procedure is to predict pressures for several different forecasts covering a wide range of production rates. Pressures for specific rates other than those studied can then be approximated by interpolating between the analyzer predicted curves. However, reliability of this type of prediction is doubtful. This paper describes a technique for predicting future behavior of water-drive reservoirs that retains all advantages of electric analyzer analysis and eliminates the main disadvantage. That is, the analyzer is used conventionally to infer unknown reservoir parameters from the pressure history, but not to predict the future behavior directly. Instead, a derived set of base curves, called influence l'unctions, can be used to calculate future behavior for any production schedule.

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Cananea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geo- logic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline.

Jan 6, 1954

An index covering the papers presented at the 19 Open Hearth Conferences from the first meeting at Pittsburgh, April 15 and 16, 1925, through the most recent meeting in Detroit, April 16 and 17, 1936, the reports of the meetings and the discussions that took place has been published, accompanied by a list of the papers presented, grouped by subject matter and a list of books of interest to open hearth men The list below gives the Open Hearth Conference meetings in chronological order and the symbols used to designate them in the index SYMBOL MEETINGS P25 Pittsburgh, April 15 and 16, 1925 C125 Cleveland, Oct 13 to 15, 1925 Ch26 Chicago, April 12 and 13, 1926 P26 Pittsburgh, October, 1926 B27 Buffalo, May 3 to 5, 1927 D27 Detroit, Nov 2 and 3, 1927 Y28 Youngstown, May 3 and 4, 1928 P28 Pittsburgh, Nov 15 and 16, 1928 C129 Cleveland, May 16 and 17, 1929 Ch29 Chicago, Nov 5 and 6, 1929 B30 Buffalo, May 20 and 21, 1930 C130 Cleveland, Nov 20 and 21, 1930 Ch31 Chicago, May 12 and 13, 1931- D31 Detroit, Nov 24 and 25, 1931 P32 Pittsburgh, May 24 and 25, 1932 Ch33 Chicago, June 29 and 30, 1933 P34 Pittsburgh, June 28 and 29, 1934 C135 Cincinnati, April 11 and 12, 1935 D36 Detroit, April 16 and 17, 1936 The list of papers mentioned in the first paragraph above is reprinted on pages 428 to 431 The Index of the Open Hearth Proceedings may be purchased at A I M E headquarters, 29 W 39th St, New York

Jan 1, 1936

By AIME AIME

THE following paragraphs comprise such information as the Secretary has been able to obtain concerning the members and associates whose deaths have been reported. Further particulars or corrections of errors, and biographical data concerning deceased members or associates not already noticed in this way, are solicited. Pat Doyle was born in 1849. At the age of fifteen he entered the Civil Engineering College of Madras, India, and left it at seventeen, having achieved special distinction in mathematics, chemistry,. and geology. Before be was eighteen years old he was in charge of two of the most important Sub-Divisions in the Madras Presidency, where he had ample opportunities for acquiring a preliminary knowledge of his profession, which was his chief object in joining the Public Works Department. In 1867, his energetic measures saved the island of Seringham from disastrous inundation. At this period he began contributing to the press ; and after a varied practical experience he came into public notice again in 1876, with an article in the Colliery Guardian on Indian Mines and Mining. In 1877 he became a Fellow of the Statistical Society of London. He was a founder of the Straits Branch of the Royal Asiatic Society and a life member of the parent Society of Great- Britain and- Ireland, as well as a member of the Independent Asiatic Society of Bengal. In 1878-9 he was Chief Superintendent of the Public Works of Perak; was active in having the Associate Member Class added to the Institution of Civil Engineers; and became a member of the Society of Engineers of London and of the North of England Institute of Mining and Mechanical Engineers. In 1880 he went to the Southern Colonies and held several appointments in Australia, where he became a member of the Johnsonian Club, Brisbane, and the Queensland Philo-

Jan 5, 1908

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962