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By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work' on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By E. Amott

A test is described in which the wellubility of porous rock is measured as a function of the displacement properties of the rock-water-oil system. Four displacemet operations are carried out: (I) sponlaneous displaceti?ent of water by oil, (2) forced displacement of water by oil oil in the same system using a centrifuging procetllrre, (3) spontaneous displacement of oil by water. and (4) forced displacment of oil by water. Ratios of the spontaneous displacement volumes to the total displucenlent volumes are used as wettability indicates. Cores having clean mineral surfaces (strongly preferentially water-wet) show displacement-by-waler ratios approaching 1.00 and displacement-by-oil ratios of zero. Cores which ([re. strongly preferentinlly oil-wet give the reverse resu1ts. Neutral wellability cores show zero values for both ratios Fresh cores from different oil reservoirs have shown wettabiltties in tlris te.st covering rrlti~ost 111e conlplrtt, range of thr: te.st. Notvever, nlo.s/ of tlle fresh California cores tested were slightly prcfere111icrlly wclter-\vet. The chrrnge.~ in coro u ('liabilities, as indicated hy this te.st, r~.sril/ing from various CO~P hanrlling procedures tt,ere oh.served. In sonie ca.sc,s /Ire ~,cttahilitio.c. of fresh cores were changell by drxi:~g or 11y e.x/rclct ing with iolcreiii~ or. dioxunc~; in o/h~r cases they were 1101 changed. Co~ltrrc/ of cort,.s ~.ith filtrc~t~c. from water-base rlrilling rilrrrls crlrc.sed littlc change in we/ /ahility ivhile contnct with filtrates frorii oil-hus~ ri1rlcl.s tlecrrascrl the prefcrerlcc, of the, cores for )I.NI Usitig thi,s test to ri.crl~lute n~r~ttubili~y, N .vt~ldy was iilarle of /lie correlmtio~i of wettability with wa/erfloocl nil recovery for orttcrop Ohio sand.stone and for Al~ln-tlunl. Resul/.v indicate thml no single correlatioti between these factors applies to different porous rock syste~n. It is thought that diflerences in pore gen~netry resrrlt in diflrrerrce.~ in this correlurio~z. INTRODUCTTON Most investigators who have reported on the wettahility of porous rock have described such rock as prcferentially water-wet or preferentially oil-wet. In some cases a third classification, neutral wettability. has been used. The efficiency of water floods in each of these wettability groups has been described in numerous publications. Several methods for characterizing porous rock wet tability more precisely have been reported,' " but it appears that because of one weakness or another. none of these has been generally accepted. Early in our studies in this field, it was found that the displacement efficiency of oil by water in a particular porous rock having a strong preference for water was quite different from that in a similar rock having only a moderate preference for water. Thus, there appeared to be a need for a practical, reasonably precise wet tability test. one which could classify porous rocks into 10 to 20 different groups rather than the two or three broad groups listed above. The test developed to meet this need is described in this paper. Also, changes in wettability, as indicated hy this test, resulting from various core handling procedures are discussed. Finally, data showing the corrclation of wettability with waterflood oil recovery for two different types of cores are presented and discussed. Some confusion has resulted from the failure of certain writers to define clearly some of the wettability terms they have used. Accordingly, the following commcnts concerning definitions are offered. The wc t ta-hility of a solid surface is the relative preference of that surface to be covered by one of the fluids under consideration. It is felt that this is the generally accepted definition. The fluids being considered must bc specified (or understood) before the term wettability has any significance. In the work reported here these fluids are water (3 per cent brine) and oil (kerosene). The term preferential wettability is sometimes used, but we think that the word preferential is redundant here and should not be used. Tn line with the definitions of Jennings', a preferentially oil-wet solid surface is regarded as a surface which will show an oil advancing contact angle less than 90" (measured through the oil) in the water-oil-solid system. Oil will spontaneously displace water, if both are at the same pressure, from such a surface. A preferentially water-wet surface is analogous. This is consistent with the wettability definition above. As Jennings has said, frequently the term oil-wet is used to mean the same thing as preferentially oil-wet. However, oil-wet also has been used occasionally referring to an oil-covered surface when the availability of water was limited. To avoid confusion from this source, we do not use the terms oil-wet and water-wet. DESCRIPTION OF WETTABTLITY TEST The following points were considered desirable in a wettability test for our purpose. 1. The test should be a displacement test resembling

By N. Malakouti, R. H. Whipp, O. A. Kuby, R. M. Smailer

A detailed description of the development of the FIOR process (Brown, Campbell, and Saxon, 1966) and, subsequently, other technical papers related to the operation and start up of the FIOR plant (Violetta, 1975; Whipp, 1980) are available in the technical literature. The Fluidized Iron Ore Reduction (FIOR) process plant constructed in the Matanzas region of Venezuela represents the first commercial application of this technology. The FIOR process was developed by Exxon Co. during the 1950s and 1960s. The facility in Venezuela was designed and constructed by Davy McKee, with plant start-up in 1976. While there is a minority government ownership in the company, FIOR de Venezuela operates as a private sector company with the majority of ownership being private capital. The FIOR process is well suited to utilize the naturally occurring iron ore fines of the Cerro Bolivar and San Isidro iron ore deposits located less than 100 km (62 miles) south of the plant site. Availability of natural gas within 150 km (93 miles) to the north, and a location bordering on the confluence of the Caroni and the Orinoco Rivers makes for an ideal geographic site. Feed stock to the FIOR plant consists of naturally occurring iron ore fines from these ore bodies, which are screened to -6mm (-0.2 in.) prior to drying in the ore preparation plant. A simplified flow plan is shown in [Fig. 1]. The dried ore is then transferred to the top of a structure containing four fluid-bed reactors located above one another so the mineral may flow from one reactor to the next by gravity. A reducing gas containing 90% hydrogen is made by steam reforming of natural gas, a CO shift

Jan 1, 1983

By John M. Kelly

New Mexico produced 38,882,342 bbl. of oil in 1943, and regained seventh place among the oil-producing states. This production was an increase of 6,968,526 bbl., or 21.8 per cent, over the figure for 1942. The maximum per-well allowable on Jan. I, 1943, was 38 bbl. daily and at the end of the year this figure had been increased to 48 bbl. Allocations as set by the New Mexico Oil Conservation Commission closely followed recommendations by the Petroleum Administrator for War and the average daily pipe-line runs were 106,476 bbl., being within 2.2 per cent of these allocations. Production for Lea County was 33,043,925 bbl.; Eddy County, 5,405,-967 bbl.; northwestern New Mexico, 432,070 bbl., and Chaves County, 380 barrels. Drilling activity for New Mexico in 1943 was only 75 per cent of that in 1942, with 255 completions. Of these completions 180 were oil wells, 10 gas wells and 65 dry holes. The ratio of dry holes to producers, more than I to 3, was the greatest in recent years. Of these dry holes, 46 were drilled within the boundaries of proven . areas while 19 were wildcats. Wildcat drilling during 1943 was responsible for the discovery of four new oil fields and one new gas field, as well as three extensions to existing proration areas. At the close of the year the New Mexico Oil Conservation Commission had designated 64 areas as proven for oil and/or gas. The Monument area was again New Mexico's largest producing oil field, with an annual production of 7,228,855 bbl. Next was Eunice, with 6,461,044 bbl., followed by Vacuum with 4,946,110 bbl. IIobbs, ranking fourth, with 3,799,114 bbl., was the leader in total recovery with an accumulated production of 104,180,53I bbl., or more than 10,000 bbl. per acre to date. Drilling activity in Lea County accounted for completion of 67 oil wells, 2 gas wells and 24 dry holes. One of these oil wells was the discovery well of a new area and three extended proven areas. The most active drilling campaign in the county was again in the Maljamar area, where 18 oil wells were completed. The Maljamar Cooperative Repressuring Agreement affected 141 producing wells, and operations were a decided success, more than 85 per cent of the gas produced being returned to formation. The new oil field for Lea County was designated as the San Simon area although boundaries have not been established to date. Discovery well for this area was the Skelly Oil Company's State U. No. I, in theNE. NE. K of sec. 5, T.22 S.,R.ssE. This well was drilled to a total depth of 4183 ft. and plugged back to 4138 ft. after encountering bottom-hole water. Initial production was 124 bbl. per day on the pump. This oil is 37.4' gravity and has a sulphur content of I per cent. Productian is from Yates sand of Permian age. The Lynn area of southern Lea cbunty was extended 145 miles to the northwest

Jan 1, 1944

By John M. Kelly

New Mexico produced 38,882,342 bbl. of oil in 1943, and regained seventh place among the oil-producing states. This production was an increase of 6,968,526 bbl., or 21.8 per cent, over the figure for 1942. The maximum per-well allowable on Jan. I, 1943, was 38 bbl. daily and at the end of the year this figure had been increased to 48 bbl. Allocations as set by the New Mexico Oil Conservation Commission closely followed recommendations by the Petroleum Administrator for War and the average daily pipe-line runs were 106,476 bbl., being within 2.2 per cent of these allocations. Production for Lea County was 33,043,925 bbl.; Eddy County, 5,405,-967 bbl.; northwestern New Mexico, 432,070 bbl., and Chaves County, 380 barrels. Drilling activity for New Mexico in 1943 was only 75 per cent of that in 1942, with 255 completions. Of these completions 180 were oil wells, 10 gas wells and 65 dry holes. The ratio of dry holes to producers, more than I to 3, was the greatest in recent years. Of these dry holes, 46 were drilled within the boundaries of proven . areas while 19 were wildcats. Wildcat drilling during 1943 was responsible for the discovery of four new oil fields and one new gas field, as well as three extensions to existing proration areas. At the close of the year the New Mexico Oil Conservation Commission had designated 64 areas as proven for oil and/or gas. The Monument area was again New Mexico's largest producing oil field, with an annual production of 7,228,855 bbl. Next was Eunice, with 6,461,044 bbl., followed by Vacuum with 4,946,110 bbl. IIobbs, ranking fourth, with 3,799,114 bbl., was the leader in total recovery with an accumulated production of 104,180,53I bbl., or more than 10,000 bbl. per acre to date. Drilling activity in Lea County accounted for completion of 67 oil wells, 2 gas wells and 24 dry holes. One of these oil wells was the discovery well of a new area and three extended proven areas. The most active drilling campaign in the county was again in the Maljamar area, where 18 oil wells were completed. The Maljamar Cooperative Repressuring Agreement affected 141 producing wells, and operations were a decided success, more than 85 per cent of the gas produced being returned to formation. The new oil field for Lea County was designated as the San Simon area although boundaries have not been established to date. Discovery well for this area was the Skelly Oil Company's State U. No. I, in theNE. NE. K of sec. 5, T.22 S.,R.ssE. This well was drilled to a total depth of 4183 ft. and plugged back to 4138 ft. after encountering bottom-hole water. Initial production was 124 bbl. per day on the pump. This oil is 37.4' gravity and has a sulphur content of I per cent. Productian is from Yates sand of Permian age. The Lynn area of southern Lea cbunty was extended 145 miles to the northwest

Jan 1, 1944

By AIME AIME

THE non-ferrous alloys have been placed in the same class with steel by metallurgical research on hardening, and hardenable alloys of all metals except zinc are now manufactured. The hardening of the non-ferrous alloys is accomplished by a process of heating, quenching and ageing. R. S. Dean, head of the research department of the Western Electric Co., told of the results of this research in 'a lecture on "Recent Advances in the Art and Science of Fabricating Metals," given before the Missouri Mining and Metallurgical Association on Jan. 24, 1929.

Jan 1, 1929

By Albert Arents

This test is based upon the fact that metallic copper will precipitate gold and silver upoil its surface from acid solutions. Of course, the fact is not new, but its application is probably so. I have used the method with success; it recommends itself by the rapidity and ease with which it may be carried on. An auriferous cyanide solution, if made acid with sulphuric acid and boiled with finely divided, pulverulent, metallic copper, will, within a short time, deposit its gold-content on the copper. Any silver in the solution is also precipitated. If this mixture is now filtered, the filter and contents may at once be subjected to a crucible assay treatment, and its lead buttons cupelled and determined. If, instead of taking cement-copper, or any metallic copperpowder, a solution of bluestone is used after acidification, and a few small pieces of sheet aluminum are added, and the solution boiled until all the copper has come down, the result as to the precipitation of gold and silver is the same. This modification takes more time and attention in boiling. If aluminum has been used, it should go into the crucible with the filter and

Jan 1, 1904

By F. M. F. Cazin

Some twenty years ago the author of a book,* by which, for the first time, molecular action was made to account for nearly all phenomena in hydrodynamics, began his preface as follows: " It is contrary to all experience, that any branch of science should suddenly cut short its own line of reasoning, and drop all connection with its past, and yet as quickly re-establish itself on an entirely new basis. It is, therefore, not without justification that this book should be met with caution and even distrust." When the newly-discovered natural facts and laws presented in this paper were, in 1891, first laid before the officers of the American Institute of Mining Engineers, they might have been preceded by a preface to the same effect; and the expression would have found its justification by the actual experience these facts and laws met with. Since then, as the result of their publication in one of the most prominent

Jan 1, 1895

By Henry Phelps Howland

During the last decade no topic has created more interest or received more thought among blast-furnace men than coke. One reason for this is, undoubtedly, the remarkable increase in the use of byproduct coke. Formerly our coke was made at a distance from the furnaces and by a distinct organization. There was little cooperation or development possible under these conditions. Today the situation is greatly changed. Much of our coke is made by the organization operating the furnaces and the coke oven is operated with the primary object of obtaining the best results in the blast furnace. The effect of changing the method of coke manufacture, even in some minor detail, is often felt almost immediately at the blast furnace. There naturally results one of the most valuable assets of the byproduct coke oven, i.e., the possibility of increased blast-furnace efficiency due to close observance and correct operation of the ovens. The results are evident, but often it is difficult correctly to account for them. In attacking the solution of a problem of as much importance as why one coke is better than another, there are facts which should be kept clearly in mind. The author hopes, in this paper, to bring out some points relative to the use of carbon in the blast furnace which will be of value in solving this question. GeÜner's Ideal Working Years ago GrÜner made a statement regarding the use of carbon in the blast furnace, which has been very generally accepted by metallurgical and blast-furnace men. I quote this theory as given by Prof. Richards on p. 248 of Metallurgical Calculations: "From the standpoint of the generation of the maximum quantity of heat in the furnace, GrÜner was right in formulating his dietum of the ideal working of a blast furnace, vie.: All the carbon burnt in the furnaee should be first oxidized at the tuyères to CO and all reduction of oxides above the tuyères should be caused by CO, which thus beeomes Co2."

Jan 1, 1917

By William Campbell

FiRst I must express my deep appreciation for the honor of being privileged to give the Howe Memorial Lecture this year and at the same time my feeling of inadequacy to do justice to the subject. The first Howe lecturer was most fittingly, Professor Sauveur, his contemporary and friend, and the subject was beta iron. Last year the second Howe lecture was delivered by Dr. Mathews, one of his most distinguished pupils, who spoke on austenite. This year, the Howe Professor of Metallurgy was chosen to deliver the third annual lecture, and the subject ought to be martensite. No one but Professor Sauveur could have brought to life what was considered by many to have been dead and buried, and he so persuasively and convincingly proved to us by his experiments the existence of something that the followers of that new cult "X-Ray and Crystal Structure " would have us believe is simply alpha iron. And Dr. Mathews from his wide practical experience was so easily able to convince us that austenite was not only the most wonderful of the iron-carbon series, but that it was the wonder alloy of the future. If I were to follow in the footsteps of my distinguished predecessors, I would talk to you about martensite. But when I had planned this lecture, I found that I was writing about Professor Howe and his work and his influence on the science of metals of today, and that martensite had become the secondary theme. And when finally I was obliged to choose a title, I remembered that it was in 1901 I came from Roberts-Austen with a letter of introduction to his very dear friend, Henry Marion Howe, at the Columbia School of Mines, to continue my work at the next bench to Dr. Mathews. Since then a quarter of a century has gone by, and during that time all branches of science seem to have been remade, so great has been our advancement in knowledge and discovery. And now that Metallography has finally established its place as an important branch of science, with its own textbooks and literature, I would like to review what seem to me to be the most important advances we have made in the last 25 years. To do this, I would start with Howe's "Iron, Steel and Other Alloys," and end with Jeffries and Archer's " Science of Metals." In the preface of the former, Professor Howe wrote: My warmest thanks are due to the friends who have aided me with their counsel and knowledge. In particular, let me thank most sincerely Prof. Margaret E. Maltby

Jan 1, 1926

By Anson Hayes

FOR the purpose of the following discussion the word "research" is interpreted as including all phases of development work on methods of manufacture, metallurgical characteristics, and uses of iron and steel. Research in the iron and steel industry then includes both plant re- search and laboratory research. Since iron and steel came into being, the steel consumer's plant and the steel producer's plant have been important factors in the development of the steel industry. Good minds have always been associated with both consumer and producer plants, so marked progress was made in the industry even when these were the only types of research and development groups in action.

Jan 1, 1937

By Alden H. Emery, J. J. Forbes

The data contained in this paper were collected during the course of an investigation which covered 15 representative coal mines in six coalmining states. The purpose of the investigation was to determine by atmospheric sampling how much dust was raised into the air during the various operations of coal mining, such as undercutting with machines, loading coal by hand and transporting it from the working face to the surface. The data thus obtained were considered from two angles; namely, the possible physiological effect of inhalation and the explosion hazard of the dust. No attempt will be made to discuss the former factor in this paper. ConDitions of Mining The mines in which this investigation was conducted were considered representative, and it is believed that the results obtained will suffice for the average dustiness encountered in most coal mines. All of the coal mined was bituminous, from beds 30 to 120 in. thick. Only the ordinary room-and-pillar system of mining was employed. Daily production ranged from approximately 700 to 1500 tons and the men employed from 150 to 450. Coal was undercut by shortwall mining machines in all mines, with the exception of one in which pick mining was employed. Loading at the face wets done by miners; none of the mines used mechanical loaders. Electric drills, both for brushing roof and for shooting coal were commonly used, although some roof work was done with jack-hammers and a little of both with augers. Coal was hauled by motor, mule, or rope power in end-gate cars with capacities ranging from 1800 to 3600lb. With few exceptions, coal was won at the face by dry methods, that is to say, no water was employed for wetting down the dust either during undercutting, loading or transportation. Observations of Sources of Dust The common sources of coal dust as observed, arranged by decreasing amounts, were as follows: (1) Undercutting with mining machines; (2)

Jan 1, 1927

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By William P. Blake

THE phenomena of concentric arrangement of minerals in rock-masses, generally known as "orbicular structure," have of late received much attention from investigators. Lawson, of the University of California, has described the orbicular gabbro at Dehesa, San Diego county, Cal. Kessler and Hamilton, of Stanford University, working independently upon the same subject, published their descriptions,2 giving also a list of many other localities in Europe and America where orbicular rocks are found, adding copious references to the literature of the subject. The orbicular diorite of the type locality in Corsica., familiar to mineralogists and petrologists under the name "Napoleonite," was described by Vogelslang in 1862.3 Chrustschoff, of St. Petersburg, has also given much atten¬tion to the subject, and is the author of a classification of the various known forms of orbicular structure.4 No complete and satisfactory explanation of the origin of or¬bicular aggregations in rocks has yet been offered. The patent fact is generally recognized that the constituent minerals have crystallized from a more or less molten or plastic magma, but why these minerals should be arranged in concentric spheres or crusts has not been clearly shown. Vogelslang, for example,

Jul 1, 1905

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

[ZAY JEFFRRIES, Vice-chairman PAUL D, MERICA, Chairman W, M, CORSE, Secretary Executive Committee J. It, FREEMAN, JR., Local Section S. SKOWRONSKI, Papers Committee R. S, ARCHER, Non-ferrous Data Sheets H, C, JENNISON, Membership Committee E, C, BAIN, Journal Committee L, W. SPRING Local Section Committee J. R, FREEMAN, JR,, Chairman R. J, ANDERSON, Cincinnati R. L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G, H, CLAMER, Philadelphia W. A. SCHEUCH, Chicago R, F, WOOD, New York]

Jan 1, 1928

Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953