Search Documents

By John Richards

MY remarks will be confined to the experience of our company in mining the No. 8 seam of coal in Ohio, although I believe that the relationship existing here between the method of mining and the method of cleaning will hold true in many of the coal seams throughout the country. The increasing demand for a cleaner and better graded product is being felt throughout the entire coal industry, and the methods of mining are playing an important part in the control of various sizes and quality of coal produced. We have found a definite relation between the mechanical loading of coal and its preparation for the market. In the No. 8 coal seam the location of the non-combustible material is regular. The' marketable coal lies in three benches, separated by streaks or bands of impurities. These impurities must be removed from the coal to properly pre pare the product for the market. Where hand-loading methods are employed, the loader removes as much of this non-combustible material as possible at the working face. The impurities that are missed by the loaders are removed as the coal passes through the preparation plant, by means of picking tables. As this method of cleaning cannot improve the quality of the extremely fine sizes, a practice has been established in the company's hand-loading mines, of undercutting the coal about 2 in. above the bottom of the seam, thereby eliminating any possibility of impurities caused by the cutting machines cutting into the rock bottom below the coal seam.

Jan 1, 1934

By Sir Robert Hadfield

LAST year this Institute was good enough to accept some remarks by the writer regarding sound steel, entitled Plant for Hadfield Method of Producing Sound Steel Ingots, being a continuation of a research in which for some time the writer has been engaged, and full particulars of which were submitted in papers entitled A New Method of Revealing Segregation in Steel Ingots, and Method of Producing Sound Ingots, read before the Iron and Steel Institute in October, 1912. These papers gave rise to a very interesting discussion, both in England and America. This question is one of vital importance, as unless sound steel in the form of ingots is first obtained, sound steel in the finished forms of rail billets, rails, bars, sheets, and other forms cannot be expected. The working stresses demanded by modern conditions are so great, each year they probably approach nearer to the limit of safety, that without doubt those who produce steel will be compelled to pay the attention which this subject deserves. Moreover, the problem is not an insuperable one, as shown by the writer in the papers above referred to. In view of the information which has already been presented in these papers, it is not now necessary to go into details of the system advocated by the writer, except to repeat that the ingots and steel now referred to were produced by employing in the first place sound fluid steel, free from blowholes, this being poured into ordinary ingot molds, provided with the necessary feeding heads, the insulating slag medium, also charcoal and air blast or other suitable form of applying heat to the head portion of the ingot. Tile upper or head portion of the ingot is kept fluid by the intense heat generated by the air blast and charcoal, so that such fluid steel passes into the body of the ingot below the head, thus feeding and avoiding the shrinkage or piping which would otherwise occur. The result is the production of a sound steel ingot, free from blowholes, segregation and piping, and in which the waste portion, usually termed the discard, is but little over 7 or 8 per cent.

Jan 4, 1914

Jan 1, 1889

By Heinrich Ries

Jan 1, 1907

By James Lorimer

THE topography at the Stan Trg mine facilitated early exploration by adits; in consequence adit levels were developed at horizons 865, 795, and 760 meters above sea level, and the levels in the mine 'are named according to their elevation. Exploitation started from the 760-m. level . upwards while simultaneously first steps were taken with regard to mining in depth. A deep dewatering adit 2.5 km. long now gives access to the deposit at the 610-m. horizon which also is connected with the 760-m. adit level by a three-compartment main hoisting shaft. Main levels have been developed internally from

Jan 1, 1936

By C. R. Boyd

THE region to which I have the pleasure of calling your attention, though limited in area, is remarkable for the quantity and purity of its mineral deposits, and in these respects it would be difficult to find its equal anywhere. IRON ORES. The red and brown hematites, pipe ore, and semi-magnetites, from which is made in charcoal furnaces the highest quality of iron for car-wheels, extend through the counties of Giles, Montgomery, Pulaski, Wythe, Smyth, Washington, Bland, Tazewell, Russell, Scott, Lee, Floyd, Carroll, and Grayson, Virginia, and run over into Ashe County, North Carolina. One locality of semi-magnetite, in the centre of the great Giles County basin, has in sight, by actual measurement, 50,000 tons of ore, which, according to Prof. Fesquet, contains 69.74 per cent. of iron and no phosphorus. In the great brown-ore belt, which passes through the counties of Montgomery, Pulaski, Wythe, Smyth, and Washington, there is an extraordinary deposit of more than a million tons. A small section of this very long vein, on Cripple Creek, in the County of Wythe, yields an ore which, analyzed by Mr. James Aumann, gave the following results: Metallic iron, - 58.15 Water, - 12 96 Alumina, - 2.32 Silica, - 1.09 Phosphorus, - none. At one point towards the western end of Red Land Mountain, in Pulaski County, New River section, I measured a body of ore in this belt which will yield, to a depth of 150 feet, over 8,000,000 tons, and the deposit extends far below the 150 feet measured at the upper part. Again, at Rich Hill, near the mouth of Reed Island Creek, these veins show extraordinary surface development, giving an ore of very great purity. At numerous places, also, in the counties of Giles, Bland, Tazewell, Russell, Scott, Wise, and Lee, these brown and red iron ores are exposed in such vast quantities as to baffle both description and measurement. That of Chestnut Flat, in Giles County, back or west of the Angel's Rest Mountain, is an easily reducible ore, blood-red when crushed, of which there are fully 300,000 tons in sight. Its analysis is as follows

Jan 1, 1880

By Gifford E. White

Explanations of the basic procedure for making earth-conductivity studies by the Eltran method have already appeared in several placeS. 1,2,3 In its essentials, this method consists of applying step functions of voltage to one pair of earth grounds and measuring the transient potential resulting at a separate pair of ground points. As previously pointed out,' the transient potential resulting from a suddenly applied steady voltage is the indicia1 transfer function of Carson1 6 which has been extensively studied in network theory. The discussion here, with one special exception, will ignore the problem of how the physical configuration of the earth affects the transient response voltage; it appears that this phase of the problem has been solved in only a few special cases having any direct bearing on the prospecting problem. Entirely distinct from the potential-theory aspect of the conductivity problem is the interesting material that can be had from studying the well-known network relations between cause and effect in linear circuits, and thus deducing criteria for the application of the several experimental methods available. To do this, only one assumption need be made about the nature of the earth. The earth is to be considered a linear conductor within the tolerance of ordinary measurements. The discussion will be restricted to collinear electrode configuration like that of Fig. I, since this is the only type of spread practical for use with driving currents that vary with time. Here one pair of grounds carries the driving current, and in line with these and external to them is a RECORDING Fair of potential probes. The problem will be to consider the relation between the different voltages appearing between the potential circuit terminals when various types of driving voltage sources are inserted in the current circuit. Suppose that the grounding points G, and G2 make good contact with the earth, and that a battery of sufficient voltage to produce one ampere of direct current is introduced into the current circuit by the closing of a switch. The potential transient response to such a voltage can be measured by taking an oscillogram at the potential Directors terminals, giving the time function that has been called A(l).4 This time function has been solved for analytically in the case of a homogeneous earth,"' and the

Jan 1, 1946

By Gifford E. White

Explanations of the basic procedure for making earth-conductivity studies by the Eltran method have already appeared in several placeS. 1,2,3 In its essentials, this method consists of applying step functions of voltage to one pair of earth grounds and measuring the transient potential resulting at a separate pair of ground points. As previously pointed out,' the transient potential resulting from a suddenly applied steady voltage is the indicia1 transfer function of Carson1 6 which has been extensively studied in network theory. The discussion here, with one special exception, will ignore the problem of how the physical configuration of the earth affects the transient response voltage; it appears that this phase of the problem has been solved in only a few special cases having any direct bearing on the prospecting problem. Entirely distinct from the potential-theory aspect of the conductivity problem is the interesting material that can be had from studying the well-known network relations between cause and effect in linear circuits, and thus deducing criteria for the application of the several experimental methods available. To do this, only one assumption need be made about the nature of the earth. The earth is to be considered a linear conductor within the tolerance of ordinary measurements. The discussion will be restricted to collinear electrode configuration like that of Fig. I, since this is the only type of spread practical for use with driving currents that vary with time. Here one pair of grounds carries the driving current, and in line with these and external to them is a RECORDING Fair of potential probes. The problem will be to consider the relation between the different voltages appearing between the potential circuit terminals when various types of driving voltage sources are inserted in the current circuit. Suppose that the grounding points G, and G2 make good contact with the earth, and that a battery of sufficient voltage to produce one ampere of direct current is introduced into the current circuit by the closing of a switch. The potential transient response to such a voltage can be measured by taking an oscillogram at the potential Directors terminals, giving the time function that has been called A(l).4 This time function has been solved for analytically in the case of a homogeneous earth,"' and the

Jan 1, 1946

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

THE CHAIRMAN (E. G. SPILSBURY, New York, N. Y.).-The relation of the character of manganese ore to the surrounding rocks was called to my attention very strikingly in a recent investigation in Costa Rica. In the foothills of the main coastal range there is a large deposit of manganese which extends for over 150 miles along the coast. This is in a porphyry district and the occurrences are almost exclusively along the lines of contact between a recent diorite intrusion through the porphyries. Wherever that intrusion appears to have exerted great force, the line of contact is very clear between the porphyries and the diorites. Where the action has been slower and the lifting force of the intrusion more gradual, there has been a zone of fracture of very considerable width. Those ores which occur where the fractured zone has not been very extensive carry a, lower percentage of manganese than where it has been deposited along a wider zone of fracture. In the so-called narrow veins, which are really the predominant ones, the solution carrying the manganese has evidently attacked the silica in the intrusive rock, and the resulting ore is practically a combination of manganese and silica, running froth 20 to 30 per cent. of manganese and from 20 to 40 per cent. of silica: hence those ores are not likely for a long time to become a factor in our manganese supply :for this country. On the other hand, where the disturbance to the porphyritic schist has been more intense; the manganese deposits are not so extensive, but the ore is richer, running from 45 to 51 and 52 per cent. manganese, with a silica content of from 4 to 5 per cent. There seems to be some resemblance in these deposits to those of the Cuyuna range. EDMUND NEWTON, Minneapolis, Minn.-The State Bureau of Mines has been working on the problem of concentrating manganiferous iron ore for two years or more. I should consider hand sorting as the best form of treatment, because it is practised at all of the mines which ship ore for making alloys, but not, however, oil the ore that is being used for pig iron. Hand sorting, assisted by selective mining, is readily applicable to some of this ore because the gangue is practically the original rock and is easily separated. However, it is only in rather limited zones that we find clean patches of rock. Generally the silica exists as a skeleton of the original rock structure, in which the manganese has been precipitated; some of the silica may have been dissolved, but if any of the original rock remains, the silica must be eliminated by ore-dressing processes.

Jan 1, 1918

By A. E. Back, S. F. Ravitz

When manganese ores are leached with sulphur dioxide, a large part of any zinc in the ore usually is extracted with the manganese.1 In the dithionate process,2,3 in which the manganese ore is leached with dilute sulphur dioxide gas and the manganese is subsequently precipitated by adding lime to the pregnant solution, the zinc is precipitated with the manganese. These facts suggested the possibility of applying the dithionate process to the recovery of zinc from oxidized ores or calcined sulphide concentrates. Accordingly, an investigation was begun, and preliminary tests were made on several ores and concentrates. The results were encouraging, but the need to devote available funds and personnel to other projects made it necessary to drop the work before the various factors involved in the process could be studied in detail. A brief mention of the process,4 however, elicited a number of inquiries, so that it appeared desirable to report the results of the preliminary work. The dithionate process as applied to zinc may be summarized briefly as follows: The ore or calcined concentrate is leached with dilute SO2 gas to dissolve the zinc, largely as zinc sulphate, in accordance with the following equation in which [ZnO] represents the "oxide zinc" in the ore or calcine: [ZnO] + SO2(g) + 1/2 O2 = Zn++SO4— [1] If, in the leaching step, the ore or calcine is suspended in calcium dithionate solution, the sulphate ion, as it is formed, is precipitated immediately as calcium sulphate, which is subsequently filtered off with the insoluble ore residue: Zn++SO4— + Ca++S2O6— = CaSO4(s) + Zn++S2O6- [2] An alternative procedure is to suspend the ore in water, filter off the insoluble ore residue after leaching, add calcium dithionate to the resulting zinc sulphate solution, and then filter off the calcium sulphate precipitate. In either event the zinc is obtained in the form of a pregnant solution of zinc dithionate, from which it can be precipitated as relatively pure zinc hydroxide by adding milk of lime: Zn++S2O6— + Ca(OH), = Zn(OH)2(s) + Ca++S2O6- [3] The zinc hydroxide precipitate is calcined to form the final zinc oxide product: Zn(OH)2 = ZnO(s) + H2O(g) [4] Theoretically the process is completely cyclic with respect to dithionate ion, the calcium dithionate required for reaction 2 being replaced by that formed in reaction 3. In practice, of course, small amounts of dithionate would be lost in the various filter cakes, depending on the economic washing limits. In the leaching step, however, some of the SO2 is oxidized to dithionale instead of sulphate, accord- ing to the following overall reaction: ZnO + 2SO2(g) + 1/2 O2(g) = Zn++S2O6-, [5] so that the dithionate losses are made up, at least in part. Ores and Concentrates Tested The analyses of the ores and concentrates tested are summarized in Table 1, which also includes the analyses of the calcines produced from the concentrates. The concentrates were roasted in a laboratory muffle furnace at the temperatures indicated until evolution of SO2 could no longer be detected; shallow clay dishes ordinarily were used; but calcines 2a and 2c were prepared in iron dishes, with the result that these two calcines were badly contaminated with iron scale. The "complex" concentrate, sample 1, consisted essentially of sphalerite grains containing inclusions of pyrite and other sulphide minerals too minute to be liberated by grinding within economic limits. In the " marmatitic" concentrate, sample 2, the iron was present largely as marmatite (that is, as iron sulphide in solid solution in zinc sulphide) rather than as pyrite inclusions. The zinc was present largely as the carbonate in the two "oxidized" ores, samples 3 and 4, and as the silicate in the "willemite" ore, sample 5. Leaching Tests The leaching cell was a 3-liter glass beaker placed in an electrically heated water bath manually controlled to maintain a temperature of 35°C in the leach slurry. The slurry was agitated by means of a flat paddle-type stirrer

Jan 1, 1950

By Gifford E. White

EXPLANATIONS of the basic procedure for making earth-conductivity studies by the Eltran method have already appeared in several places.1,2,3 In its essentials, this method consists of applying step functions of voltage to one pair of earth grounds and measuring the transient potential resulting at a separate pair of ground points. As previously pointed out,4 the transient potential resulting from a suddenly applied steady voltage is the indicial transfer function of Carson,5 which has been extensively studied in network theory. [ ] The discussion here, with one special exception, will ignore the problem of how the physical configuration of the earth affects the transient response voltage; it appears that this phase of the problem has been solved in only a few special cases having any direct bearing on the prospecting problem. Entirely distinct from the potential theory aspect of the conductivity problem is the interesting material that can be had from studying the well-known network relations between cause and effect in linear circuits, and thus deducing criteria for the application of the several experimental methods available. To do this, only one assumption need be made about the nature of the earth. The earth is to be considered a linear conductor within the tolerance of ordinary measurements. The discussion will be restricted to collinear electrode configuration like that of Fig. I, since this is the only type of spread practical for use with driving currents that vary with time. Here one pair of grounds carries the driving current, and in line with these and external to them is a [ ] pair of potential probes. The problem will be to consider the relation between the different voltages appearing between the potential circuit terminals when various types of driving voltage sources are inserted in the current circuit. Suppose that the grounding points G1 and G2 make good contact with the earth, and that a battery of sufficient voltage to produce one ampere of direct current is introduced into the current circuit by the closing of a switch. The potential transient response to such a voltage can be measured by taking an oscillogram at the potential circuit terminals, giving the time function that has been called A(t).4 This time function has been solved for analytically in the case of a homogeneous earth,6,7 and the

Jan 1, 1941

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By Leonard Larson

BEFORE direct or wet smelting of copper concentrate was adopted at the McGill smelter, in November 1932, actual furnace smelting tests had indicated the possibility of smelting between 400 and 500 dry tons of wet concentrate per furnace day. Under calcine smelting practice, solid charge up to 1165 tons per furnace day had been smelted. It was realized that in order to smelt wet tonnage in equivalent amount per furnace day, a higher combustion rate and higher temperatures would be neces-sary within the furnace. The reverberatory furnace considered in the following history of wet-smelting de-velopments is a unit 127 ft. long and 28 ft. 8 in. wide, inside dimensions (Fig. r). This furnace was in operation through all the years from 1934 to date. During 1933, the first complete year of direct or wet smelting, the plant was on a curtailed copper-production basis and the available concentrate tonnage to be smelted was limited. The average coal-firing rate in the reverberatory for that year was 124 tons per furnace day. This rate was lower than the average for years immediately preced-ing under calcine smelting practice. With this coal-firing rate, an average of 391 tons of new metal-bearing material (N.M.B.M.) was smelted per furnace day. The following year, 1934, the coal-firing rate was in-creased to 139 tons and the smelting rate increased to 448 tons N.M.B.M. per fur-nace day. In succeeding years production required that either more tonnage be smelted in the one furnace or an additional furnace be placed in operation. With this situation confronting the smelting depart-ment, it was determined to continue the program of increasing the coal-firing rate and also to intensify the temperature in the smelting zone of the furnace. In order to accomplish this, various improvements were made to aid combustion within the furnace. The burners were enlarged, in-creased primary air was supplied to the burners, and changes were made in the furnace to enlarge and streamline the out-let, thus increasing the furnace draft.

Jan 1, 1940

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By S. Shapiro, G. Krauss

We will reply to Dr. Pitsch's discussion by 1) presenting in greater detail the single surface trace analysis which we performed on the reversed austenite plates in a single parent plate of martensite of known orientation, 2) relating the results of our analysis to the conclusions which Dr. Pitsch makes on the basis of our data, and 3) examining the validity of our selection of twenty-nine individual traces from the over 200 austenite plates which were observed in a surface of this single martensite plate. Fig. 7 shows a standard (001) projection of the martensite plate from which the austenite-martensite interface traces were taken. The traces are plotted on the projection as the small solid circles, and the great circles corresponding to the loci of plane normals which could contain each trace or could intersect the surface plane along the measured directions are also plotted. It can be seen that these great circles intersect at a point which corresponds to the normal of the surface plane on which the traces were observed. Also rate which occurred only at particularly low heating rates, see Figs. 1 and 3 in the paper.2 Since in this case the interpretation of Jana and Wayman is plausible and since we have no alternative to this interpretation, we would like to state only that the existence of a diffusion-controlled reversal at low temperatures seems to be not yet proved beyond any doubt. The author wishes to thank Professor G. Krauss for making available his manuscript prior to publication. It is also a pleasure to acknowledge the lively written discussions, which the author has had with Professors G. Krauss and C. M. Wayman prior to this communication. The financial support of the Deutsche For-schungsgemeinschaft for the work on which this communication is based is also gratefully acknowledged. plotted within small dotted circles which represent a i3 deg scatter in each of the twenty-four unit stereo-graphic triangles are our A and B poles7 and the pole P determined by Kessler and itsch.' The data presented in Fig. 7 permit a direct association of the measured traces and the various proposed habit plane poles for the reversed austenite plates in the martensite crystal. If the sample measurements do in fact

Jan 1, 1969

Discussion of the paper of Edward Keller, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 2093 to 2115. GEORGE L. HEATH, Hubbell, Mich.:-In the admirable paper quoted, is mentioned the date when the 5-g. assay was first proposed is a standard for refined metal. The author omitted, however, to mention a later paper,1 which contains a proposal for the use of a single " stock solution " of mixed acids, which has been adopted by the American Brass Co. and others. The suggestion is made that such a scheme would save time and manipulation with converter metal. Unless the low current of 0.5 ampere and the large excess of nitric acid, recommended by Mr. Keller, have been proved necessary to hold up antimony-and selenium, the use of the mixed solution which we have adopted will permit the use of 1 ampere of current per square decimeter of cathode surface, until the solutions have become colorless. At this point, we wash the covers and reduce to 0.5 ampere to prevent oxidation or contamination. The ordinary split electrodes have been used. With strong current, at least, the use of an excess of nitric acid tends to the neutralization of the solution before the end of the period, from the formation of too much ammonia., and this is detrimental. Antimony deposits more easily than arsenic, and tends to drag the latter dorm with it. There must, be some such explanation for the fact. that we have made hundreds of deposits of pure cathodes from Lake material containing no antimony, but as. high as 0.5 per cent. of arsenic. By placing an assay beaker in the Frary solenoid, or rotary device, a cathode deposit with less than 0.01 per cent. of impurity is easily obtained in one operation from 3 g. of whitneyite, carrying from 7 to 10 per cent. of arsenic. In such a case, it is necessary to test several times for end point and remove the plate as soon as no brown tint appears (at once) when hydrogen sulphide water is added to the test portion on the spot plate. Edward Keller's proportion,, of solvent figure out as 14 cc. of strong nitric to 11.4 cc. of sulphuric acid (1.84).

Jan 11, 1913

[NORTH AMERICA UNITED STATES ALABAMA America.-Dyar, 0. C. Anniston.-Klugh, B. 0. Ashland.-Pallister, H. D. Auburn.-*Poor, R. S. Bessemer.-Creveling, J. 0. Lindstrom, W. A. McKenzie, W. 0. Mitchell, F. R. Birmingham.-Abbott, C. E. Aldrich, T. H., Jr. Armstrong, 0. R. Beard, A. H. Benjamin, F. S. Blackburn, E. 0. Blair, A. J. Blair, 0. S. Blair. H. W.]

Jan 1, 1946

By V. A. Phillips, M. Safdar Ali

The tensile properties of Cu-0.20 pct Al, Cu-0.45 pct Mg, Cu-0.27 pct Cr, and Cu-0.22 pct Be solid-solution alloys were studied at -196°, 18°, 2509 and 500°C on wires internally oxidized at 900°and 1000°C. Internal oxidation produced marked increases in yield strength relative to pure copper, particularly at low temperature. The yield strength decreased with increase in temperature to a much greater extent than predicted by current theories of dispersion hardening. The strengthening effect of internal oxidation persisted throughout the entire stress-strain curve, but since a marked loss of ductility occurred at all test temperatures, only modest increases in tensile strength were realized. INTERNAL oxidation involves the preferential oxidation of a baser solute in a relatively noble solvent by diffusion of oxygen into the solid. Since the process is diffusion controlled, it is expedient to carry it out at a high temperature often approaching the melting point. The amount of solute is limited and the oxidation conditions adjusted so that oxygen diffuses inwards to meet the solute causing reaction to progress inwards and form subscale instead of only sur face scale. The reaction can be made to occur throughout the thickness of thin material producing a fine dispersion of oxide inside the metal. C. S. Smith1"3 appears to have been the first to recognize the true nature of the process of internal oxidation. Although extensive kinetic and metal-lographic studies followed by Rhines and coworkers,4-5 Chaston7 andMeijering and Druyvesteyn8 working independently were the first to report hardening effects due to internal oxidation. These results prompted detailed studies of the effects of internal oxidation on the hardness, tensile, creep, and fatigue properties of a number of alloys by G. C. Smith and coworkers9-12 in England, on hardness by Gottardi13 in Italy, and on hardness and tensile properties by wood14 in the U.S.A. Publications dealing with other aspects of internal oxidation will not be reviewed here. Internal oxidation of solutes having a high affinity for oxygen provides a means of obtaining very fine dispersions stable in a suitable atmosphere at temperatures well above those at which most age harden ing precipitates coalesce. The process therefore offers a method of producing thin sheet and wire of possibly outstanding creep resistance. The size limitation might be overcome by internally oxidizing porous powder compacts made from alloy powder before final sintering. PREPARATION OF ALLOYS The alloy ingots, which were approximately 5 1/2 in. long by 1 in. diam, were made up in a high-frequency furnace, using as raw materials OFHC copper, 99.99 + pct Al, high-purity magnesium, and master alloys of Cu-4.19 pct Be and Cu-10 pct Cr. The alloys containing aluminum and magnesium were melted ii closed high-purity graphite crucibles and solidified in the crucible which was lowered partly Out of the coil to give a hot-top effect. The alloys containing beryllium and chromium were made by melting in vacuo in alumina-lined sillimanite crucibles. The magnesium, chromium, and beryllium

Jan 1, 1960

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968