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By R. Raring, W. J. Harris, J. A. Rinebolt

G. W. Geil (National Bureau of Standards, Washington, D. C.)—The authors state that the degree of accuracy realized in the experimental determination of a, is likely rather low. This inaccuracy is attributed to the difficulty in reading the load of the tension machine at the instant of fracture of the test bars. I believe there is another factor which may have added considerably to the inaccuracy in the determination of a,, namely, the determination of 8,. Fracture of a cylindrical tensile specimen of a ductile metal tested in tension at room temperature is generally initiated at the axis and rapidly propagates radially to the periphery of the necked section. During the propagation of the fracture, the metal at the rim of the minimum cross-section extends longitudinally and contracts radially. Thus values of 81, based on diameter measurements made after complete fracture of the specimens do not necessarily represent the strain at the initial fracture." Data obtained at the National Bureau of Standards with a 0.3 pct C steel in the condition as-quenched from 1575°F and tempered at 1000°F for 1 hr and tested in tension at room temperature indicated a considerable "rim effect" and as shown in Fig. 13, resulted in an apparent increase in Sf from 0.90 to 0.98. As the fracture strain of this steel is approximately equal to those of the steels reported by the authors, it seems probable that a similar "rim effect" may have added to the inaccuracies in the reported values of Si and accompanying values of El. R. Raring (authors' reply)—The authors are grateful to Mr. Geil for having called attention to a possible source of uncertainty in the determination of fracture stress, and they are in agreement with the principles upon which his discussion is based.

Jan 1, 1952

By N. R. MacMillan

INTRODUCTION The Bullmoose Coal Project is part of a major development in northeastern British Columbia which comprises a new rail line, a new townsite, powerline, highway, the upgrading of the Canadian National Railway's main line, a new coal port at Prince Rupert and two new coal mines, the Bullmoose mine and the Quintette mine. The total investment by all parties is estimated to be in excess of $2.6 billion and made up approximately as follows : [Table No. 1 $ Millions - Quintette Coal Limited 950 Teck-Bullmoose Coal Inc. 275 Canadian National Railway Company 800 6 British Columbia Railway Company Port at Prince Rupert 280 Townsite, Roads 6- Power ] The new infrastructure is intended to serve not only the Bullmoose and Quintette coal projects but also eventually a number of other coal properties in northeastern British Columbia. The Bullmoose project is structured on a joint venture basis as follows : [Table No. 2 Teck Corporation 51% Lornex Mining Corporation Ltd. 39% Nissho Iwai Coal Development 1 0% (Canada) Ltd. -- 100% ] The mine has a capacity of 2.3 million tonnes of clean coal per year. In the initial years 1.7 million tonnes will be metallurgical coal and 0.6 million tonnes thermal coal. After the first three years of operations the annual production of metallurgical coal will increase to an average of approximately 2.1 million tonnes and the production of thermal coal will decrease to an average of approximately 0.2 million tonnes. At this level of 2.3 million tonnes annual production, the Bullmoose mine has sufficient reserves for at least 26 years of production. History Brameda Resources Ltd. commenced coal exploration in the Bullmoose-Sukunka area in 1969. Teck obtained an option on the Bullmoose coal licences in 1970 and started surface exploration and diamond drilling in 1971. Teck earned a 50% interest in the property, and thereafter expenses were jointly financed by Teck and Brameda. In 1981 Brameda merged with Teck making Teck the sole owner. The initial phase of the exploration program, which was completed in 1975, included 7,200 meters of diamond drilling in 35 holes. During 1976 and 1977, detailed exploration and test work were carried out on the South Fork and West Fork areas where multiple seams close to surfaces indicated the potential for large tonnages of strippable coal. In those two years, work included road construction, detailed mapping and trenching to outline the coal seam traces at the surface, 6,300 meters of diamond drilling in 80 holes, and 300 meters of underground bulk sampling from seven adits. Washability tests and analysis work were carried out on the drill cores and adit samples, and pilot plant washability studies were undertaken. In 1978 and 1979 Teck engineers prepared open pit mining plans and production schedules and Kaiser Engineering was retained to prepare a layout of the plant preparation facility. A feasibility study prepared by Teck's engineering group in January 1982 was the base document used by the Lenders in assessing the technical and economic viability of the project. Property Location The property lies some 650 kilometers northeast of Vancouver, and 87 kilometers south by road from the village of Chetwynd. The Sukunka property (British Petroleum) adjoins to the north, the Mount Spieker property (Ranger Oil Option) adjoins to the east, and the Quintette property is located to the southeast.

Jan 1, 1985

By Stephen Krickovic

AS it is commonly understood in the bituminous coal mining industry, pillaring means removal, as completely as is practical, of all pillars formed in the development of headings and rooms on first mining. The degree to which this can be accomplished, termed percent of recovery, is of course dependent generally upon the physical conditions of the bottom and the overburden, the system of min-

Jan 1, 1956

By Daniel M. MacNeil, Carle R. Hayward, Raymond L. Presbrey

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By Daniel M. MacNeil, Raymond L. Presbrey, Carle R. Hayward

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By A. L. Slaughter

The Homestake mine, located in western South Dakota, was discovered in 1876. The first reported production was in I 878. Total production through 1965 is 6,554,249 troy ounces of silver and 27,961,276 troy ounces of gold, worth $987,000,000 at present prices. Precambrian sedimentary formations at Lead total 20,000 feet. The Poorman Formation, the oldest, is chiefly ankerite carbonate. The Homestake Formation is iron-magnesium carbonate. The younger formations are argillaceous with some quartzites. The Cambrian Deadwood Formation unconformably overlies the Precambrian. All are cut by Tertiary intrusives. Sideroplesite schist of the Homestake Formation was converted to cummingtonite schist in the zones of higher-grade metamorphism. The Precambrian rocks show the effects of extreme isoclinal folding. A second stage of folding ( cross folds) may have been caused by the Tertiary intrusives. All folds plunge to the southeast. The Homestake ore bodies are pipe-like replacements of the Homestake Formation in zones of cross folding. It is believed that dilatation of the schists has increased permeability in these zones. Chloritization of the schists is the most widespread effect of the mineralization which is divided into four stages. Principal minerals of the first stage are quartz, chlorite, and arsenopyrite; in the second stage, quartz, ankerite, and pyrrhotite. In the third stage only pyrrhotite was deposited. The fourth stage followed the intrusions of Tertiary dikes and deposited mostly pyrite and calcite. Gold accompanies all stages and is always the last mineral to be deposited. It is most closely associated with arsenopyrite of the first stage but can be interpreted as having been deposited during the fourth stage and superimposed on the products of the earlier stages.

Jan 1, 1968

By C. A. Wert

THE solid solubility of cementite in a-iron has been investigated a number of times and there is now general agreement on the solubility of about 0.018 wt pct at the eutectoid temperature, 720°C. With decreasing temperature, the solubility falls off so rapidly and to such a low value that no data obtained by standard metallurgical methods are available below 500°C. Using a new technique, however, Dijkstral has obtained apparently accurate solubilities down to 400°C; which data agree well with previously measured solubilities in the 600" to 700°C temperature range.' The present paper has in part the purpose of extending his work to still lower temperatures. Earlier work of Low and Gensamer3 on iron has established that the presence of a relatively small amount of carbon can play a tremendous role in affecting the mechanical properties. In particular they found that the yield point remained high as they reduced the amount of carbon in the iron; the yield point dropped only after the carbon content had fallen to something less than 0.003 wt pct, the point where their carbon analysis failed. It seemed desirable to the present author to see if some means could not be found to extend this part of their work. This investigation has then the additional purpose to determine the range of carbon concentration in which the major change occurs. Solubility The method used in the present work to measure small percentages of carbon in a-iron utilizes internal friction. Since this method may not be fa-miliar to the reader, the following explanation will be given (a part of this procedure is from unpublished results of Dijkstra): It is known that the internal friction associated with the diffusion of

Jan 1, 1951

By A. Gatti

Studies were made on the system iron plus alumina. Various methods of dispersing and various amounts of alumina were used. Powder metallurgy techniques were used to produce the final product. Microstructures and some mechanical properties are presented. Alloys containing up to 16 pct alumina by weight are ductile at all temperatures tested. The ivon-alumina materials have a higher yield stress and improved creep resistance over that of pure iron. SINCE the development of SAP' an A1- Al2O3 powder metallurgy product, great interest has been shown in the development of a SAP-like structure in metals and alloys other than aluminum. The outstanding properties of this class of materials are: 1) Good creep resistance at high temperature. 2) High yield strengths and high hardness at high temperatures. 3) High recrystallization temperature. However, the lack of ductility and formability has thus far limited the applications of SAP-like materials. The following report deals with methods of dispersing A12O3 in Fe, processing of powders into rod, structures produced after processing, and mechanical properties of the iron-alumina material produced. Methods of dispersing the alumina and also the volume fraction of alumina added were varied. MATERIAL Powder Processing— Four methods of obtaining dispersions of alumina in iron were studied. 1) Oxidation-reduction of a Fe + 8 pct Al alloy. .2) Coprecipitation of Fe(OH)3 + Al(OH)3 from aqueous solution. 3) Colloidal mixing of Fe,O3 and Al2O3. 4) Colloidal mixing of Fe powder and A1,O3. Fig. 1 is a processing flowsheet which outlines the processing steps taken to produce a final extruded bar 1/4 in. in diameter and about 30 in. long. The - 100 mesh iron-aluminum alloy was oxidized by placing a thin layer of powder on an alumina plaque. The reduction step was modified to include 1/2 hr at 1000°C since the powders tended to become pyro-phoric unless sintered slightly after low-temperature reduction. Compacting was done in a 1-1/8-in.-diam pressing die. The slugs produced averaged 1 in. in length. The billets were encased in low-carbon steel cans shown schematically in Fig. 2. The blank is included for structure and property comparison purposes. TESTING PROCEDURE All tests were made on as-extruded material.

Jan 1, 1960

By Robert S. Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultirnatc cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of .the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development. The alloys or processes to be used in the production of aluminum castings are to be considered from the standpoint of their effects on both the utility and the cost of the finished casting. Specific gravity and mechanical properties come under the first head, while the properties

Jan 1, 1927

For the year ending February, 1920 PRESIDENT HORACE V. WINCHELL MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. LOUIS, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON. . . . ' NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1919

By Norman D. Fitzgerald

The purpose of this paper is to analyze the behavior of oil securities during the six-year period January 1932 through December 1937. This period was selected because of its varied character. It includes the depths of the depression, the broad and spasmodic recovery, and the recession collapse. The first part of the analysis is devoted to the correlation of a number of economic factors with an index of 13 oil stocks. The second part is a comparison of the different,ial behavior of 6 oil stocks. The relationships developed here are only a few of many that might be considered in a complete analysis. The stock market is regarded as a barometer of business confidence and as such exerts an important influence upon corporate policies, particularly upon industrial expansion. The complex and continuously changing nature of its price structure, the ebb and flow of influences and the effects of impacts require dynamic rather than static analysis. When treated in this way, many of the important fluctuations in market prices and changes in the relationships between securities appear quite logical. The market for oil securities has varied widely in recent years. The Standard Statistics index of 13 oil stocks made a bull market peak of 166.7 in September 1929. The collapse of the boom and the ensuing bear market finally carried the index down to a low of 36.4 in June 1932. From this point oil stocks made an irregular recovery; they reached a top at 139.7 in March 1937, and after maintaining this approximate level through August, declined precipitously to 93.3 in December 1937. The prices of these 13 oil stocks have gone up and down under the influence of numberless variables. These variables are of two kinds, those external to the industry, and those that are solely due to its internal condition. The external factors are political, social, and economic, both domestic and foreign. These are the influences that induce the ebb and flow of all prices in general and security prices in particular. Among the internal factors are the regulation of industry, the development of new reserves and processes, and the disequilibrium due to lack of balance between supply and demand. Some of the simpler relationships are examined in this paper.

Jan 1, 1938

For the year ending February, 1920 PRESIDENT HORACE V. WINCHELL MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 12, 1919

By W. C. Spence, Burt C. Mariacher

Methods employed to beneficiate ores utilize relatively few fundamental principles to effect size reduction and concentration. In crushing and grinding only impact and compressive forces with a minor amount of shear are employed. In concentration, gravity, magnetic, electrostatic and flotation constitute the major methods of concentration with minor use of sizing, hand picking and adhesion. This industry, as all others, can expect in the near future to see the development of new techniques for improved efficiency, cost reduction, and exploitation of raw materials hitherto considered unmanageable. NATURAL AND INDUCED RADIOACTIVITY At the Canadian Department of Mines in Ottawa in 1946, C. M. Lapointe developed a picker belt system whereby radioactive ores could be concentrated by electromechanical means. This invention ultimately led to development of what is now refer- red to as the Lapointe Picker and which has been used commercially at Port Radium and Port Hope for the upgrading of jig concentrates. Basically, the system consisted of conveying sized uranium ore on a belt under a radioactivity detection device which in turn electronically operated a kicker or plunger that separated the ore from the gangue constituents. Thus, a new principle for mineral concentration, radioactivity, was introduced commercially.

Jan 7, 1962

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members who registered at Institute headquarters during September: William B. Phillips, Austin, Texas. Will L. Clark, Jerome, Ariz. Olof Wenstrom, Boston, Mass. Robert H. Richards, Boston, Mass. Anthony F. Lucas, Washington, D. C. Hennen Jennings, Washington, D. C. P. H. Griffin, New York, N. Y. Waldemar Lindgren, Boston, Mass. H. N. Lawrie, Portland, Ore. C. Snelling Robinson, Youngstown, 0. Clarence P. Linville, Everett, Pa. E. P. Ross, Johnson, Tenn. Members of the XII International Geological Congress who made the Institute Office their headquarters while in New York A. Bigot, Caen, France. E. Gentil, Paris, France. J. Caillebotte, Paris, France. H. Saint-Clivier, Paris, France. John Ashworth, Manchester, England. Tadasu Hiki, Kioto, Japan. T. Dahlblom, Falun, Sweden. L. Milch, Greifswald, Germany.

Jan 10, 1913

By R. W. Smith

It is well known that certain silicates such as the feldspars and beryl can be readily floated from quartz at a low pH value using a long chain cationic collector in the presence of a fluoride.1-3 However, the mechanism whereby the fluoride activates feldspars and beryl is not known. Indeed, only a few authors have even speculated about possible mechanisms.1,3,4 As a first approach to the problem, it is perhaps best to look closely at the interesting character of hydrofluoric acid and how it dissolves silica and silicic acid. Hydrofluoric acid, unlike hydrochloric acid, is a weak acid with a dissociation constant of about 3.53 x 10-4 at 25°C.5 The reason for the weak acidic character of HF lies in the very small size of the fluoride ion.6 The pKa value is 3.45 which means that at pH 3.45 half the HF is present in molecular form and half in ionic form. The anion present is probably HF2.-6 At pH values below the pKa value, molecular concentration increases rapidly at the expense of the HF2- anion. It is known that HF readily attacks glass, silicates, quartz and silicic acid. The equation usually cited pertaining to the first step in HF attack of silica is6-'

Jan 1, 1965

By Sydney H. Ball

I. INTRODUCTION. DURING the past 50 years the attention of mining-men has been turned to Africa, and within the past decade prospecting-expeditions sent into Central Africa have resulted in the opening-up of several mines. Having recently spent two years in the Belgian Congo for the Société Internationale Forestiere et Miniere du Congo, it is our purpose to outline briefly the mining-conditions in that part of Central Africa. Before it became, in 1908, a Belgian colony, this region was known as the Congo Free State. II. LOCATION AND AREA. The Belgian Congo lies in southwestern Central Africa, west of the continental divide, is illustrated in Fig. 1. It has a coastline of but 20 miles on the Atlantic, but widens rapidly eastward to points 5° north and 14° south of the equator. Its area is 908,000 sq. miles, which is almost one-quarter that of the United States and Alaska, or more than one and one-half times that of Alaska. Stated in other terms, its area is nearly one-third that of the United States, exclusive of Alaska and the insular possessions, or more than that of all the United States east of the Mississippi river. III. TOPOGRAPHY AND DRAINAGE. From north to south, Africa is made up of three topographic elements: 1, the Atlas mountains, a highly-accentuated region

Apr 1, 1910

By J. D. Grace

Screening by centrifugal force is a unique subject, for all vibrating screens, with but one exception, depend on gravity alone to pass material through a sizing mesh or screen cloth. Centrifugal screening is one of the greatest advancements made in screening since the development of vibrating screens. It makes possible sizing in a range previously im-practical by mechanical methods. The centrifugal screen is specially designed for fine sizing from No. 4 separations to finer than No. 100 separations. Centrifugal force provides a positive control of factors that make fine particle separation practical and effective as opposed to gravity which is a fixed force acting only in a fixed direction, The centrifugal screen provides a control of the force of material against the screening surface, and also controls the distance of departure of the material from the surface and its rate of return. The centrifugal screen has a rotating drum that becomes a natural fan blowing air outward through the material being screened and carrying float dust and fines through the apertures with it. Screening by centrifugal force is an unique subject, for with the exception of only one vibrating screen presently on the market, all vibrating screens depend upon gravity to pass material through a sizing mesh or screen cloth. This one screen that sizes by centrifugal force and utilizes gravity only to convey material along the screen, is the Symons V-Screen. The requirements of the industrial minerals industry to meet ever-increasing stringent fine sizing specifications by a practical mechanical method accentuates the weakness of gravity, a fixed force acting in a fixed direction, as a prime force for fine sizing. It was apparent a force other than gravity was needed. This led to the development of a centrifugal screen to meet modern demands for practical fine sizing operations. Gyratory-type screens in use today were originally designed in a day when a 1/4-in. separation was normally considered fine sizing and 1/8-in. separations were extremely fine sizing. Although gyratory-type screens are sometimes used for separating below 1/8-in., they are not practical screens for this purpose. They were not designed to do this type of work. A growing demand for a practical means of making positive mechanical separations in a range of from 1/8 in. downward led to the development of the vibrating screen. These screens utilize higher speeds and lower amplitudes of vibration than

Jan 1, 1967

By Harry W. Antes

The density changes that occurred on annealing cold-worked poly crystalline molybdenum, over the temperature range of 870" to 1630 SC, were determined. Increases in density were observed for recovery and the beginning of recrystallization. An initial decrease in density was observed during re-crystallization. A second decrease in density was observed after recrystallization was completed, as the microstructure changed from columnar grains to equiaxed gvains Both decreases in density were associated with an increase in gain boundary area to volume ratio. The second decrease in density was observed in the annealing range that immediately precedes secondary recrystallization as reported in the literature VARIOUS techniques have been used to identify the recovery, recrystallization, and grain growth processes that occur when cold-worked metals are annealed. As early as 1928 work was conducted that indicated measurable density changes occur when cold-worked single crystals of brass are annealed.' More recently, work by Murphy exhibited a corre- lation of density with microstructural changes observed on annealing cold-worked polycrystalline a brass.2 Other investigators have performed similar work on a brass and copper.324 In reviewing the literature, it was apparent that density work had been limited to fcc materials. Therefore, it was the purpose of this investigation to determine the density changes that accompany annealing the cold-worked bcc material, molybdenum. Two degrees of cold work, 30 and 90 pct reduction of cross-sectional area by rolling, were selected for this study. EXPERIMENTAL PROCEDURE High-purity vacuum arc-cast molybdenum was used in this study, the principal impurity being carbon in the amount of 80 ppm. The final rolling reductions were made at 1200°C in grooved rolls to provide 5/8-in.-diam rod. Density specimens 0.500 in. diam by 1.5 in. long were machined from the bar stock. The specimens were ground to the final dimensions to provide a smooth surface. Density measurements were made using a hydrostatic technique similar to that used by ~urphy.' This type of equipment permitted weighing in liquid immediately after the air weighing. During each weighing the temperature of the air and liquid was controlled to within 0.0l°C. This was accomplished by sealing the analytical balance in an air-tight brass chamber and surrounding it by an insulated wooden case. Preheated air was circulated in the air space between the brass chamber and wooden case by means of a blower. The temperature of the

Jan 1, 1964

For the -year ending February, 1920 PRESIDENT HORACE V. WINCHELL MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 5, 1919

By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick's first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)'/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.' , ' Regarding mass transport through dense solid oxide layers, Wagner' has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.' Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work', 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-'" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956