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By James F. Lewis

THE hematite iron ore mines east of the Hudson River are confined to a strip of country ten to fifteen miles wide, commencing on the south, near Fishkill, running northeast through Dutchess County, and striking the southeast corner of Columbia County, extending into Litchfield County, Conn., known there as the Salisbury mines, cropping out again at and near West Stockbridge, Lanesboro, and Cheshire, Mass., also in Bennington County, Vermont. The ores are found in beds or deposits and in veins, with a limestone ledge on one side and slate on the other, from six to thirty feet from the surface. Portions of it are quite solid, called rock ore, but

Jan 1, 1877

By G. R. Belton, R. J. Fruehan

The Knudsen cell-mass spectrometer combimtion has been used to study the Fe-Al and Ag-Al liquid alloys. By application of the recently developed integration technique to the measured ion-current ratios, activities have been derived for the Fe-A1 system at 1600° C and for the Ag-Al system at 1340"C. The results are partially represented by the following equations: Internal consistency between the data on silver-rich and iron-rich alloys is demonstrated by application of the literature measurements on the distribution of aluminum between the nearly immiscible liquids iron and silver. The usual restrictions on the ratio of the mean free path of the escaping atoms to the orifice diameter of the Knudsen cell are shown not to be limiting in this technique. DESPITE the importance of a knowledge of the activity of aluminum in understanding deoxidation equilibria in molten steel, no direct studies have been made of activities in liquid Fe-A1 alloys at steel-making temperatures. Lower-temperature direct studies have, however, been carried out on aluminum-rich liquid alloys by Gross, Levi, Dewing, and Eilson' at 1300°C and by Coskun and Elliott' at 1315°C. Apart from phase diagram calculations by Pehlke, other determinations have been indirect and were made by measurement of the distribution of aluminum between iron and silver475 and combination of these data with extrapolated activities in the Ag-A1 system.~-% ecently, however, Woolley and Elliott have made a significant contribution by directly measuring heats of solution in the Fe-A1 system at 1600°C. The present authorslo have recently employed a Knudsen cell-mass spectrometer technique in a study of activities in iron-based liquid alloys. In this technique activities and heats of solution are determined from a series of measurements of the ratio of ion currents of the components; and since ion-current ratios are used, problems caused by changes in instrument sensitivity or cell geometry are overcome. Results obtained for the Fe-Ni system were found to be in excellent agreement with previous work, thus demonstrating the reliability of the method. The present paper describes a similar study of activities in the liquid Fe-A1 and Ag-A1 systems, this latter system being included in order that a meaningful comparison can be made with the above-mentioned indirect studies. INTEGRATION EQUATIONS A detailed derivation of the equations used to determine the thermodynamic properties from the measured ion current ratios has been given elsewhere;'' however it is useful to summarize them here. By the combination of the Gibbs-Duhem equation with the direct proportionality between ion-current ratios and partial pressure ratios, it was shown that for a binary system at constant temperature and pressure: where al is the activity of component 1 with pure substance as the standard state, N, is the atom fraction of component 2 in the solution, and I; and t'2 are ion currents of given isotopes of the components. The activity coefficient is given by: this latter equation being more suitable for graphical integration. Combination of Eq. [l] with the Gibbs-Helmholtz equation gives an expression for the partial molar heat of mixing: EXPERIMENTAL A Bendix Time-of-Flight mass spectrometer model 12! fitted with a 107 ion source and a M-105-G-6 electron multiplier, was used to analyze the vapor effusing from the Knudsen cell. The arrangement of the Knudsen cell assembly was essentially that of the commercial instrument (Bendix model 1030) but with several modifications. Instead of heating with a single tungsten filament, a cylindrical tantalum-mesh heater was employed. Up to 1400°C simple resistance heating was used but above this temperature electron bombardment between the tantalum mesh and the tantalum cell susceptor was necessary. The temperature was measured by means of a Leeds and Northrup disappear ing-filament type optical pyrometer sighted on an essentially black-body hole in the side of the cell. Details of the temperature control, temperature measurement, and in situ calibration of the optical pyrometer can be found elsewhere.I0 In the investigation of the Fe-A1 system the Knudsen cells were constructed of thoria crucibles with fitted thoria lids (Zircoa). The cells employed in investigating the Ag-A1 alloys were made up of high-purity alumina crucibles (Morganite) with lids of recrystal-lized alumina (Lucalox). The cells were 0.370 in.

Jan 1, 1970

By M. J. Pool, P. J. Spencer, J. R. Guadagno

THE present work was carried out as part of a general program to study the magnitude and concentration dependence of exothermic heats of solution of various metals in liquid tin. Thermodynamic data for the Te-Sn system are very limited, particularly for dilute alloys. Indeed, apart from the prior heat of solution determinations of Pool,1 the only other published values are those of McAteer and seltz2 who carried out electromotive force measurements on solid alloys of compositions from 75 to 95 at. pct Te at temperatures between 543° and 668° K, of Colin and Dro-wart3 who made mass-spectrometric studies of the vapor in equilibrium with solid SnTe, and of Robinson and Bever4 who determined the heat of formation of SnTe by solution calorimetry. The present work thus provides further thermodynamic information for this system, specifically in a temperature range where the solubility of tellurium is very limited. The liquid metal solution calorimeter used in this investigation has been described previously.' No further discussion of its design or operation will therefore be given here. For each series of measurements a tin bath consisting of approximately 70 g of 99.99 pct pure Sn was carefully weighed out and inserted in the calorimeter which was maintained at the desired temperature to within ± 1/4°c. Tellurium, of 99.999 pct purity, was supplied by Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp. Approximately 0.0006 to 0.001 g-atom specimens of tellurium were used for each experimental run and these were added to the calorimeter from a temperature of 273" K. Heat of solution values were calculated by analysis of a strip-chart recorder plot of the heat effect accompanying the solution of each sample in the tin bath. The heat capacity of the latter was determined at regular intervals during a series of tellurium drops by using pure tin or tungsten calibration samples, the heat contents of which were obtained from the standard compilation of Hultgren et al5 The composition of the bath was calculated after each drop from a knowledge of the weights of tin and tellurium added. Values of the heat of solution of tellurium at 725" and 775° K are listed in Table I together with the corresponding tellurium contents of the alloys. The data are also plotted as a function of tellurium concentration in Fig. 1, which includes the equivalent data obtained by pool' at 750° K. It can be seen that the heat of solution remains

Jan 1, 1969

Pulverized Fuel Combustion The apparatus shown in the illustration is a complete equipment f r supplying coal to boiler and metallurgical furnaces, cement and lime kilns, dryers, and to all furnaces requiring a temperature and quality of fame under prompt and easy control. It is claimed that the Aero Pulverizer makes practicable the highest efficiency obtainable from burning coal. It makes coal burn like a gas, a flame, the physical and chemical character of which is regulable- a flame that may be elongated or shortened, thus placing the zone of highest temperature where needed- a flame that may be made oxidizing, reducing, or neutral, as occasion may require. The coal is burned as pulverized, and there is no storage of the powder with its attendant hazard. Artificial drying before pulverizing is not necessary if the coal supply be sheltered from rain and snow. Where the Aero is used, it is wholly a furnace question whether a dryer should be installed; it is not at all a pulverizing or storage question. Labor is reduced to a minimum. Slack coal at low cost yields its last B.T.U.

Jan 11, 1915

By Paul T. Allsman

Passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of the Federal Government into the problems of mining. Such a law was necessary simply to help re- solve a number of disputes in mining. Now, however, a hundred years later, the extent of government involvement in the mineral industry often comes as a shock to the mining engineer who has reached management level. In fact, he has been poorly prepared for an understanding of the role of government in the industry and he becomes frustrated, even hostile. In our political system, private industry is responsible for producing minerals and the Government sees to it that production will be adequate for a peace-time economy and for any emergency. There have been great social and political changes since World War I1 with the result that the Government's participation in our society has steadily increased. A new dimension in business and government relations has been introduced which should be examined more closely.

Jan 5, 1966

By Conrad E. Hesse

To increase the durability of paint exposed to the weather, it is necessary to protect the oil with a substance that is itself unaffected by the elements. The so-called " metallic " paints, containing ochre,

Jan 1, 1891

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By G. R. Wilms

A study has been made of the structural changes in polycrystalline high purity aluminum during the tertiary stage of creep under conditions of constant tensile load. It appears that there is no basic modification in the particular mechanism of deformation that characterized the preceding secondary stage of creep, but that the changes in crystalline structure produced during the tertiary stage are only a consequence and not a cause of the accelerated strain. Intercrystalline fissures were observed on entry into the tertiary stage, and these might supplement the accelerated rate of strain owing to local stress concentrations. There is evidence that the formation of these fissures may be associated with the presence of surface imperfections, and it is suggested that a more generalized treatment of the results may explain certain creep characteristics of commercial alloys. IN previous work'-4 a study was made of the changes produced when specimens of annealed aluminum were deformed at various temperatures and rates of strain, especially under conditions leading to creep under constant tensile load. It was shown that, as the temperature was increased or as the rate of strain was decreased, elements of the substructure produced within the grains became coarser, and with the strain rate constant at a given temperature, their size tended to an equilibrium value. The preliminary process of the breaking down of the grains into a substructure was identified with primary creep.' The subsequent equilibrium, condition was associated with secondary creep. The question then arose whether the tertiary stage corresponded to any further significant change in the substructure. The question is also of interest in view of the opinion, expressed for instance by Andrade,5 that the tertiary stage is merely an accelerated rate of strain due to the reduced area of section of a specimen under continuous tensile load, and the other opinion, as suggested by the observation by Sully, Cale, and Willoughby6 of a tertiary stage in com-pressive loading, that this third stage is a real effect in its own right. The object of this paper is to record some observations on the tertiary stage of high purity aluminum. Experimental Procedure The material was aluminum of 99.98 pct purity as previously used. The specimens had a rectangular section of l/8 x l/2 in., and extensions were measured over a 1 in. gage length. After machining to shape, the specimens were annealed to give a standard grain size of 0.2 mm and then electropolished. The general procedure involved metallographic and X-ray diffraction examination at progressive stages of elongation (marked by arrows on the curves shown in Figs. 1 and 2), the specimen being extended to fracture under constant load at a given temperature. The X-ray tests were made by the back-reflection method from a stationary specimen, using CoK radiation. The longer edge of the micrographs in the paper corresponds to the direction of applied stress. Results The previous work showed that, in the secondary stage of creep in aluminum, three basic types of structure could be developed according to the temperature and rate of strain. These were: 1—slip, which predominated at the lower temperatures and higher rates of strain and produced the finest and least perfect substructure; 2—cell structure, which superseded slip as the temperature was raised and the rate of strain decreased and which was characterized by a coarser and more perfect structure and an absence of slip lines; and 3—a stage termed "boundary microflow," which predominated at still higher temperatures and lower rates of strain when the cell size had increased and become comparable

Jan 1, 1955

By R. W. Leonard

A method of accurately determining the value of gold-bearing ores and gravels with a compact field-outfit is much desired by prospectors, especially when the work lies in a district far removed from railways or good wagon-roads. We are all familiar with the fire-assay of gold-ores, and fully recognize its accuracy and value; but only those who have tried to determine the value of a gold-bearing vein as a commercial venture, from fire-assays of selected samples, know how misleading is the information thus obtained, however carefully and honestly the samples may be selected. The reasons are that, for the fire-assay a very small portion of ore is treated (rarely more than six assay-tons, or a little over one-third of a pound), and a minute particle of the precious

Jan 1, 1896

By E. P. Klier

THE work of Klier and Lyman1 on the bainite reaction has led to the full description of this reaction for medium-carbon low-alloy steels. Certain experimental data reported by Klier and Lyman appear, however, to be improbable of obtaining in very high-carbon steels. The study herein reported consists of an analysis of the transformation characteristics of a 3 per cent chromium, 1 per cent carbon steel by means of X-ray and metallographic methods. From the results obtained it is concluded that the bainite reaction in this steel is more complicated than that reported by Klier and Lyman for the low-carbon low-alloy steels. However, the mechanism of bainite formation in this steel appears to be essentially the same as proposed for the low-carbon low-alloy steels with the modification that the first volumes to transform are carbon-rich rather than carbon-poor. EXPERIMENTAL PROCEDURE The analysis of the steel studied was: Cr, 2.89; C, 1.02; Mn, 0.33; Si, 0.35; S, 0.012; P, 0.020. The stock was received from the Carpenter Steel Co. in rolled bars. Specimen Preparation Specimens were austenitized at 1200°C. (2192°F.) for 25 min. in purified nitrogen. The resultant A.S.T.M. austenite grain size was 0-1. Isothermal transformation was allowed by quenching the specimens into liquid metal baths controlled to ±5°C. at 540°C. (1004°°F.) and above, and to ±2°C. at 490°C. (914°°F.) and below. Following the desired degree of transformation all specimens were water quenched. Metallographic Examination Specimens 1/4 in. round by 1/4 in. were used for metallographic examination. Etchants used were Vilella's reagent (1 gram picric acid, 10 ml. hydrochloric acid to make l00 ml. ethyl alcohol solution) and alkaline sodium picrate (electrolytic). Vilella's reagent was effective in revealing all microconstituents, while the alkaline sodium picrate developed the carbon-rich structures or carbides only. X-ray Examination Two X-ray techniques were used-the Debye-Scherrer method and a back-reflection method. The small specimens necessary for the Debye-Scherrer method were austenitized and then allowed to transform, or were cut from the larger metallographic specimens. The metallographic specimens were used for the back-reflection X-ray analysis. When it was desirable to determine the structure of the carbide present, sliver specimens were electrolytically etched to develop a carbide coating, then were exposed in the cameras. This technique was frequently necessary to allow positive identification of the carbide.

Jan 1, 1945

By J. B. Newkirk, A. H. Geisler

Certain of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some perrnanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems oA&apos;er for study over the usual in which an intermetallic compound is formed are many: 1. Since the precipitate has the same crystal strutture as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be ex. petted to have the same orientation. 3, Small &,registry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from 0 to 100 pet* thus permitting wide freedom for the study of the effect of cornposition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1&apos;2 The two have the same <Jo parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for CU-Ni-CO alloys because of the similarity in constitution but this had not been demonstrated. The Present investigation was conducted on a CU-Ni-CO alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established, however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system Was chosen for a comprehensive investiga-

Jan 1, 1949

By J. Redstone, A. R. Laplante

Sidbec-Normines operates six large iron ore concentrate regrinding mills in parallel and open circuit at its Port-Cartier pelletizing plant. Grinding kinetics in these mills were characterized for slurry densities varying between 70 and 89% solids, using a lumped parameter size discrete model. Optimum grinding conditions were encountered at 83.5 to 84% solids. Higher densities decreased the normalized selection function and increased slurry short-circuiting, yielding a sharply coarser mill discharge. At lower slurry densities, the normalized selection function decreased and the mill discharge coarsened slightly. The grinding kinetic model predicted particle size distributions within the mill. These were found to vary significantly from the feed to the discharge end. This is likely to cause nonlinear breakage kinetics.

Jan 1, 1985

By D. W. Philips

The problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized rescarch began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board&apos;s publications.&apos; - Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the chief Mining Engineer of the Research Board, and was coordinated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: 1. To provide. by supports, means to prevent falls of fractured ground. 2. TO develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the properties of supports and their correct application. The second aspect is perhaps more fundamental, and involves also the properties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient frequency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1947

By D. W. Philips

The problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized rescarch began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board&apos;s publications.&apos; - Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the chief Mining Engineer of the Research Board, and was coordinated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: 1. To provide. by supports, means to prevent falls of fractured ground. 2. TO develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the properties of supports and their correct application. The second aspect is perhaps more fundamental, and involves also the properties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient frequency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1947

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10&apos; cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.&apos; This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.&apos;-= At the same time, the material shows considerable ductility.3&apos;4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin&apos;s relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1&apos; presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.&apos;3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella&apos;s reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With&apos; elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

By AIME AIME

COUNCIL PRESIDENT OF THE COUNCIL. CHARLES KIRCHHOFF NEW YORK, N. Y. (Term expires February, 1912.) VICE-PRESIDENTS OF THE COUNCIL. BENJAMIN B. LAWRENCE NEW YORK, N. Y. JOSEPH W. RICHARDS SOUTH BETHLEHEM, PA. ALBERT SAUVEUR CAMBRIDGE, MASS. (Term expires February, 1912.) S. B. CHRISTY BERKELEY, CAL. W. A. LATHROP PHILADELPHIA, PA. GARDNER F. WILLIAMS WASHINGTON, D. C. (Term expires February, 1913.)

Oct 1, 1911

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N&apos;,N&apos;-tetraacetic acid and N&apos;-(2-hydroxyethyl)ethylenediarnine-N,N,N &apos;-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1&apos;9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH&apos;s in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH&apos;s. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By Alfred E. Hunt

Tars paper is suggested by the appointment on the part of the American Societies of Mechanical and of Civil Engineers of committees upon the subjects of " Standard Tests and Methods of Testing," and " Uniform Methods of Tests of Material used in Metallic Structures," respectively, and by a study of the report of one of these committees, and other papers. Moreover, the writer has had frequent occasion to hear the complahts of tnanufacturers who furnish structural material subject to specifications, that in the tests prescribed, the number of tests required, and the methods of making

Jan 1, 1892

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10&apos;a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann&apos; in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5&apos;6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1&apos;-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1&apos; ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968