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By William H. Morris

At the Glen Summit meeting, the question of controlling the silicon in pig-iron WAS raised; and as this has been deemed by most furnace-men for years past a matter of special difficulty, an account of our experience in the matter may be of interest. When running on mill-iron, some years ago, we aimed to keep

Jan 1, 1893

By NEWTON C. MARSHALL

AS every school boy knows, the Andes mountain range forms the backbone of South America, extending the full length of the continent along its western edge and fairly close to the Pacific coast. But in Colombia these mountains are divided into three distinct ranges known as the Western, Central and Eastern ranges of the Andes. United at the southern end, they spread out like three fingers in a northerly direction across the Republic of Colombia. These great natural barriers have only in recent years been tarried by railroads or wagon roads, and they have had their effect upon the history of the country, both political and ethnological. Each of the three ranges dies out and dwindles away before reaching the boundary of Colombia on the Caribbean Sea. When I studied my geography as a youngster 1 used to think that the

Jan 1, 1935

SEVERAL distinctions can rightfully be accorded the Bagdad enterprise. For one thing, it has the most romantic name among the Porphyry Coppers and this is said with all due deference to Copper Queen and Inspiration! Bagdad was one of the richest and most magnificent cities of the glamorous world of the Arabian Nights. The record does not say who was responsible for applying the name Bagdad to the company that in 191 1 took over the property of the Arizona-Nevada Copper Company; but whoever it was must have had visions (or at least hopes) of a fabulously profitable mine. So far as I know, Bagdad is the only Porphyry whose owners, or officials, ran afoul of the law because of alleged sins of omission or commission in vending shares of the company's stock. E. B. Bronson, of New York, had been interested in Bagdad since 1909; and, during the lean period of the 1930's he had, as president of the corporation, endeavored to raise needed funds by the sale of 140,000 shares of treasury stock. Some legal questions arose as to the need for registration under the Securities and Exchange Act; but, when Mr. Bronson finally filed a registration statement, the New York office of the Securities and Exchange Commission found 155 "deficiencies" in the document. According to the judge who later heard the criminal case against Bronson, no evidence was introduced to show that he had personally benefited "to the extent of one dollar." However, it was charged that the setup was such that he was in position to profit if he had wanted to! A somewhat quixotic position, it would seem. In any event, he was convicted, on highly technical

Jan 1, 1957

The mining fraternity of North America was grieved and shocked to learn of the death of Dr. Willet G. Miller on Feb. 10, 1925. Doctor Miller was for many years the Provincial Geologist of Ontario and the one who more than any other had contributed by his personal work and the reports of his subordinates to the recent extraordinary mineral development of the Province. Doctor Miller was fifty-eight at the time of his decease. A man of unusually stalwart physique, he seemed destined to many years of useful service. His friends in both the American and Canadian Mining Institutes can with difficulty reconcile themselves to his loss. Doctor Miller was born in 1867 in Port Rowan, Ont., on the shores of Lake Erie. After preparation in the high school of his native town, he entered the University of Toronto and took his bachelor's degree in 1890. He pursued graduate studies in geology at Chicago, Harvard, and Heidelberg Universities. In 1893, he was first appointed lecturer and soon thereafter Professor of Geology in Queens University, Kingston, Ont., a chair which he held until 1902. He was then appointed Provincial Geologist of Ontario and was placed at the head of the Survey which was attached to the Department of Mines. Within the next year, 1903, he performed the service that made him famous. In the summer of 1903, in connection with the building of the Ontario Government Railway toward an objective on James Bay, veins had been noticed by construction parties just north of what is Cobalt Lake today, and in the rocky pass that is now traversed by the main line of the Canadian National Railway en route to Vancouver. The pink stain of cobalt bloom on the vein, known later as La Rose, caught the eye of a workman; in November, Doctor Miller recognized the silver in it, and brought the possibilities of the district to general attention. In December, he published an article in the Engineering and Mining Journal, stating that the veins could be worked at a handsome profit. During the winter and spring, the mining interest awoke, which resulted in the astonishingly productive silver district of Cobalt; but in which, Doctor Miller, because a government official, scrupulously refrained from having any financial interest whatever. Seldom has so high a sense of honor been manifested; and as the result, Doctor Miller commanded confidence and respect to an extraordinary degree. Hard on the discoveries at Cobalt came, in the next few years, those at the other famous camps in Northern Ontario; and step by step with them, reports issued from

Jan 1, 1925

By Arthur Clark, Terrill

THE Tri-State field is now believed to be the largest zinc district in the world. It has a potential production sufficient to supply the entire zinc demands of the country. It is estimated that a train 70 miles long would be required to haul the district's 1919 output of 60 per cent. zinc concentrates. For many years,, including 1917, Missouri surpassed Oklahoma in zinc production. In 1918, however, Oklahoma led by a wide margin and, in 1919, Missouri produced less than one-sixth of the total for the three states, when Kansas replaced Missouri in second place in the production. The district is now producing one-third of the zinc of the world and twice as much as ever before at the present price.

Jan 1, 1920

By Frederick Görannsen

McDuffie county, once a part of Columbia county, lies in the eastern part of central Georgia, about 20 miles west of the Savannah river, and bounded on the northtwest by Little river. Wrightsboro, now almost forgotten, was one of the principal towns of Georgia before the Revolutionary war, and much of the land hereafter described as belonging to one of the principal gold-bearing sections of the South had been taken up by the early agricultural settlers, and was already under cultivation. Indeed, some of the present mining companies can trace their chain of title back to the original grant of King George III., made in 1771. The first discovery of gold in Georgia, however, was not made until 1823, when two English miners, who had emigrated to this country and were traveling as peddlers through this section, discovered quartz, rich in gold, on what is now known as " the 40-acre lot," and owned by the Columbia Mining Go. These men had no money to buy the lands, and not being able to stake off a claim and begin work, as is the custom in other places, they were forced to seek the aid of the native farmers. In this we are told that they were for a long time unsuccessful; the farmers and land-owners not knowing or caring anything about gold mining. In 1826, Jeremiah Griffin, a wealthy farmer, became interested with them, and they did some prospecting and located several rich veins. Mr. Griffin soon became enthusiastic, and bought about three thousand acres of supposed gold-lands, lying along Little river.. This purchase was unfortunate for the mining industry, as it effectually shut out all other prospectors, and confined entirely to Mr. Griffin and his associates the mining development of the whole region. As a consequence, the ground was never covered, arid there are virgin lands in this section now, which offer to the prospector as

Jan 1, 1903

By AIME AIME

FORMATION of a new company through the union of two familiar names in the mining and metallurgical world has just been announced. J. V. N. Dorr and E. L. Oliver have united the businesses and assets of The Dorr Company and Oliver United Filters, Inc., of which they are the respective heads, by the formation of the Dorr-Oliver Corporation under their joint management, and stockholders have approved the merger.

Jan 1, 1931

By C. W. MacGregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the intersection of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow,2 Elam,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By J. D. Meakin

J. D. Meakin (The Franklin Institute Laboratories)— In a recent paper Garofalo12 has shown that a number of experimental creep results can be represented by the empirical relation In this expression ? is the steady creep rate, s is the applied stress, and A is a constant at a given temperature; a and n are adjustable parameters. Garofalo has shown that Expression [6] approximates to a power function at low stresses and a simple exponential function at high stresses. Among the data used by Garofalo are the results we published for creep of copper." For these results we found that the best correlation was an exponential law with different parameters in the low-and high-stress region, respectively. That is, i = A exp qs where A and q have different values above and below a critical stress a,. In Ref. 13 are listed a variety of observations which support the proposal that different mechanisms are operative at stresses above and below a,, and it is not felt appropriate to repeat those observations here. The purpose of this note is to demonstrate that, although the representation used by Garofalo does fit the experimental data very well, this fit cannot be used to conclude that only one mechanism is rate-controlling. The argument is best made graphically and is illustrated in Fig. 9. The continuous curves 2 and 3 represent pairs of simple exponential functions which intersect at i = 10-5. The curve 2 closely resembles the copper results in that a change of slope of 2:1 occurs at i = 10-5; the two functions shown are in fact: e = 10-7 exp (1.150) and ? = 10-6&apos; exp (0.576s) For purposes of comparison, curve 3 represents two exponential functions with a change of exponent of 3:1 and curve 1 has the exponent 1.150 throughout. It is quite clear that a satisfactory straight-line fit is obtained on a Garofalo plot for all three curves. The curves represent processes which have either a single stress exponent or two ex- ponents in a ratio as high as 3:l. It must, therefore, be concluded that the ability to obtain a linear dependence between log i and log (sinh cyo) cannot be taken as evidence for a single activated process. In fact, to some extent the way the experimental points quoted by Garofalo lie about a best fit straight line on the log (sinh as) plot indicates that two processes are indeed occurring. This is seen in Figs. 7(c) and 8(c) of Ref. 12 where it is particularly evident that the experimental points deviate from the straight line in a manner similar to curves 2 and 3 of Fig. 9. It is, of course, recognized that the generally used exponential form is an approximation to the hyperbolic sine function which is not valid for exponents of less than 1.2, e.g., qs < 1.2. The only curve in Ref. 12 which is affected by this restriction is Fig. 6(b) where the deviation from a In ? vs s

Jan 1, 1964

Jan 1, 1900

By R. W. Culbertson, S. Kasper

During the 1920&apos;s, approximately 11,000 small gasifiers were in operation in the United States. They converted about 15 million tons (13.6 Mt) of coal per year into low Btu gas. In some cases, hot raw gas was used for applications such as firing open hearth furnaces or brick kilns. In other cases the gases produced in the gasifiers were cooled, cleaned and desulfurized for various utility and industrial purposes. The steel industry was by far the largest user. The most important fact was that the conversion of coal to a usable fuel gas was demonstrated to be commercial. During the late 1940&apos;s and early 1950&apos;s, this form of energy was largely replaced by natural gas as the pipeline net work was expanded. Producer gas was no longer economically competitive. Over the past 25 years, government controls on the interstate price of natural gas have maintained this situation. At present only three commercial small coal gasifier plants are still in operation in the United States. These facilities are operated

Jan 1, 1980

H. W. MussEn, Collingwood, Ontario, Can. (communication to the Secretary*):—Doubtless all engineers who have paid more than a casual visit to Russia have come into contact with that formidable document, the " smieta," or estimate of the Russian manager. It is an institution which seems to be inseparable from Russian mining-methods. As Mr. Shockley points out, the year&apos;s costs a agree very closely" with the figures of the smieta made at the beginning of the year. In cases which have come under my notice, I have been satisfied that there had been a good deal of " rigging" of accounts to this end. The sum spent by the manager was carefully kept down to the total of the estimate, because it was well known that no more money would be forthcoming, and when this is done it is not a difficult matter to see that the right amounts come under the right heads in the final accounts. I do not say that this is always the case, but I have come across notable instances. Looking at it from the Russian owner&apos;s point of view, I think that the balance of the argument is usually in favor of the smieta as limiting " impulsive indiscretion" on the part of managers. The Russian Mining Code of to-day leaves much to be desired, but this is thoroughly appreciated by the official world there, and great changes are spoken of for the future. In many, if not in most, cases the laws are interpreted liberally, and a great deal is left to the discretion of the district mining engineer or inspector, with whom it is necessary to keep in close touch. As Mr. Shockley points out, the officials of a mine, who are always Russians, are held personally responsible for accidents resulting to employees, quite independently of any compensation which may be made to the sufferer. This seems startling enough, but I have always found that a penalty is imposed only

Jan 1, 1909

Jan 1, 1901

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K&apos;l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 &apos; at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K&apos;1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken&apos;s10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- &apos;, and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By J. G. Thompson

PROJECT 8411 of the U. S. Bureau of Standards, sponsored by the Iron and Steel Division of the A.I.M.E., is an attempt to define more concisely than has been possible heretofore the accuracy and the Limits &apos; of usefulness of the &apos; various methods now in use for the determination of oxygen as it exists in ferrous materials. It originated in correspondence between John Johnston and other metallurgists, and was brought to the attention of the Iron and Steel Division of the Institute at the Annual Meeting in February, 1933. As reported in MINING AND MET,ALLURGY, Vol. 14, page 152, March, 1933, "Dr. Johnston introduced, and those present adopted, a resolution that the Iron and Steel Division of the A.I.M.E., believing that a careful comparison of the several methods now in use for the analysis of steel for nonmetallic elements such as oxygen is highly desirable, heartily endorses the proposal that the U. S. Bureau of Standards act as a clearing house " in this matter, undertaking the final preparation and allocation of identical samples to those laboratories willing to collaborate in this important question, and collate the results re- ported back to the Bureau.&apos;"

Jan 1, 1934

By H. W. Seamon

The data here given were obtained by 1500 tests made by the United Verde Copper Co. to determine the most economical air pressure for the operation of hammer drills under the varying conditions of use, and to investigate the variation in drilling speed at different air pressures. Twelve models of drills were used at gage pressures ranging from 40 to 130 Ib. No effort was made to harmonize theory and practice; but rather to formulate empiric rules that would cover the average variation of the results obtained. These rules on the performance of hammer drills, based on the air pressure as the main variable, however, are not necessarily of universal application, but they apparently satisfy the results obtained in this series of tests. The drilling conditions at this property vary widely; an average of twenty-one machine shifts to a 3-ft. (0.9-m.) round has been found necessary in some of the development work, while an advance of 56 ft. has been made in seven shifts in the "oxide" ground. This range precludes the adoption of one type of drill as a standard; consequently almost every kind of hammer drill sold in this country has been tested. At present, sixteen models are in use, of which two types of the heavy (150 to 160 lb.) mounted drills, one of the light mounted drill, one stoper, and two hand plugging drills are considered as standard. Method of Conducting Tests All machines were of the wet type, and were selected as being representative of the several types in use at this property; all had been in use from two to four months except the Waugh 66 and the Sullivan DX61, which were new. All machines were thoroughly overhauled before they were sent to the testing ground. Tests were made on the following machines: Ingersoll-Rand, No. 248 Leyner-Ingersoll, No. 18 Leyner-Ingersoll, No. 26 Baby Leyner, BCRW430 Jackhamer, and CCW11

Jan 1, 1922

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1&apos; that the "{0,1,13)" habit reported for the Fe-Ni-C alloys&apos;&apos; is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By F. F. Aplan

Pollution control will be of utmost importance in the 1970&apos;s. In this area, the mineral process engineer has a special competence to understand and remedy many pollution situations. There is an old adage that goes, "Build a better mouse- trap and the world will beat a path to your door." Would that it were so, but the reality of the situation is such that, just as a supplier must sell his machine, a professional man must sell his competence. It is a sad but true fact that mineral processing engineers have not done a very good job in selling their extensive competence in the control of a broad range of pollution problems. Recently one of our students visited a paper pulp mill where he was shown a foam fractionator used to remove paper pulp fibers from plant discharge waters. "Foam fractionator hell, that&apos;s a flotation cell!&apos;&apos; was his comment. Ah so, it would appear that large numbers of technical people consider themselves experts on "foam fractionation" Or is it that we have been very remiss in demonstrating the usefulness of our equipment and processes and our professional competence to solve, these pollution problems?

Jan 1, 1970

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.&apos; on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-&apos; (g S per sq cm)&apos; corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.&apos; The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175&apos;C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini&apos; mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970