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By R. W. Stahl

Burning coal-mine refuse banks were surveyed in 15 States. The following characteristics were tabulated for 495 hanks: County; name, population, and distance of nearest town; size and status of bank; status and stage of fire; and topography. Ways of controlling fires were reviewed, the compacting and sealing method proving most satisfactory. Means for preventing refuse-bank fires by proper construction of banks are described.

Jan 1, 1964

By Danforth R. Hale

The pressure of military use of quartz resonators led to efforts to Grow high, grade quartz crystals in Germany and in Great Britain during 19)3-25, and was responsible for a series of U.S.A. Signal Corps contracts beginning in 1946 with the Clevite Corporation (as the former Brush Development Company), Bell Telephone Laboratories, Antich College, and others. The technique of growing crystals from the melt, such as KI, NaBr, was already commercially inuse Quartz could not be so grown, since its utility depends on the form stable below 573°C, and, even if it could be grown from an extraordinarily viscous melt, the higher form passing through this transition becomes twinned. Again, several crystals were being grown commercially from water solutions; quartz, however, is listed in the common literature as being insoluble in water. Fused quartz, or vitreous silica, was chosen as raw mater¬ial by the European experimenters because of its thermodynamically lesser stability than quartz, and various alkaline solutions were tried for the purpose of enhancing the solubility.

Jan 1, 1964

COMPARED with the equipment used in most industrial processes, the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. This discussion of the physics and chemistry of the individual refractory materials will keep uppermost the question "Why, how, and where does it fail?" CAUSES OF FAILURE The principal causes of failure of open-hearth refractories are, in their order of importance : 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spalling. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. Reaction with iron oxides and slag is by far the most important cause of failure. Liquid iron oxide comes near to being the "universal solvent" sought for by the alchemists. Among the materials commonly used in the open-hearth furnace, magnesia has the greatest resistance to this liquid and fireclay the least. The relations of iron and oxygen at high temperatures are illustrated in Fig 14-18. The liquid iron oxide that forms wherever iron is in contact with air or combustion gases cannot be given a definite formula. The percentage of oxygen at steelmaking temperatures may range from 21 to 28 (iron 79 to 72), depending upon the temperature and the oxygen pressure and also upon whether or not the liquid is in equilibrium with metallic iron. Oxide mixtures exist not only in the solid and liquid phases but also in the vapor phase, for metallic iron and its oxides have

Jan 1, 1964

By John Bley

White Pine Copper Company operates a mine in the Upper Peninsula of Michigan using a modified room-and-pillar system for extracting ore.1 Mine production averages 15, 500 tons per day. The terrain is predominantly level and the depth of cover varies from 500 to 800 feet over the present workings with depth increasing as mining progresses down the dip. The deposit is situated on a low angle plunging, anticlinal structure composed of sedimentary beds. Local terminology for the stratigraphic units which contain the ore horizons, named in ascending order, is as follows: lower sandstone, parting shale, upper sandstone and upper shale. The ore zones of copper enrichment are, contained in the parting and upper shales. The parting shale will vary; from 6. 5 to 9.0 feet thick; the upper sandstone from 2 to 10 feet; and the upper shale from 1. 5 to 6. 5 feet. Two variation of the room-and-pillar system are used to extract the ore depending on grade and local ground conditions. One system is called the parting shale method and recovers the parting shale only. This system requires a mining height of 8 1/2 feet to accommodate large-scale, high-capacity equipment and this working height is obtained by removing approximately 1 to 2 feet of the barren lower sandstone with the ore. Under the second system, locally termed full column, the mining height is about 14-1/2 feet and this system removes the parting shale, the upper sandstone and the lower mineralized zone, approximately 1-1/2 feet, of the upper shale at which point it is possible to maintain a competent back (Fig. 1).1

Jan 1, 1964

By Benjamin C. Allen

The surface tensions of liquid chromium and manganese were determined by a modification of the dynamic drop-weight method and found to be, respectively, 1700 * 50 and 1100 * 50 dynes per cm at their melting points. Molten drops were formed LITTLE is known about the surface tension of liquid chromium and manganese, even though they are technologically important metals and widely used in steelmaking. In the past, direct determinations have been hampered by their high reactivity on the lower end of a vertically held rod inductively heated under argon. The technique essentially reproduced surface tensions reported for liquid nickel and zirconium using static drop-shape methods. and vapor pressure. In this work, surface tensions were measured by the drop-weight method, using induction heating under argon. EXPERIMENTAL WORK Chemical analyses of rods used are given in Table I. Chromium rods were prepared from iodide-process crystals which had been are-melted, hot-extruded, warm-swaged, and centerless-ground.'

Jan 1, 1964

By J. M. W. Mackenzie

The rheological properties of aqueous solutions of several commercial flocculants were investigated using a rotating coaxial cylinder viscometer. Similarities between the pH-apparent viscosity relationship and the flocculating properties of the reagents are discussed here. Synthetic neutral polymers and polyelectrolytes are used extensively as flocculants in mining and chemical engineering operations. The action of these reagents has been interpreted as adsorption of the polymer flocculant to the mineral surface, followed by the formation of physical polymer bridges between the particles.4,5 A consequence of the bridging model is that the efficiency of a polymer flocculant depends on the degree with which the polymer is adsorbed to the mineral surface, and the extent to which the polymer molecule forms a bridge between colliding particles. The length of the polymer molecule and its orientation at the mineral surface are important in the bridging mechanism since the further the polymer segments can protrude from the mineral surface the greater the probability may be of these segments contacting another mineral particle. Linke and Booth7 have shown that, for a silica suspension, both the settling rate at a given polymer addition and the maximum settling rate obtainable increase with increasing molecular weight. The analysis of silberbergl0 has

Jan 1, 1964

By Martin Weinstein

A technique is described for preparing finegrained lead telluride by ultrasonic agitation of a solidifying melt. Material prepared by this technique is dense and chemically homogeneous. N-type PbTe, containing 0.03 mole pct PbIz, has been made and its thermoelecCric Properties have been measured as a function of temperature. For comparison, the properties of similarly doped PbTe made by cold pressing and sintering, and by extrusion, have also been measured. The ultrasonically prepared material compares favorably with the others in its thermoelectric-efficiency factor. Comparison of compressive-flow curves for the three kinds of PbTe show that the ulhasonically prepared material has much superior ductility. The cleavage strength of the ultrasonic material is related to the grain size, D, by the Petch relation:Extrapolation to infinite grain diameter yields a fracture strength of 5000 psi for single-crystal PbTe. WHEN metals and semiconductors solidify in a mold they normally assume one of three cast structures illustrated in Fig. 1.' Solidification in a casting starts at the mold walls where a large number of fine crystals of random orientation can be nucleated to form the chill zone. Because of the anisot-ropy of the growth rate, those crystals whose direction of maximum linear growth is parallel to that of the heat flow grow faster and crowd out the crystals of less favorable orientation. A second zone, having a preferred orientation, called the columnar zone, thus forms adjacent to the chill zone. The speed of growth of the columnar grains will depend, in the case of limited undercooling of the melt, on the rate at which heat can be abstracted. The columnar zone can extend to the center of the casting, Fig. l(a), but it is frequently followed, in solid-solution alloys, by another zone of equiaxed randomly oriented grains in the central portion of the casting, Fig. l(b). The equiaxed structure in Fig. l(c) represents the completely grain-refined case where the equiaxed grain size is small. The third type of structure is the most desirable because it imparts a somewhat higher strength for all except high-temperature applications, it reduces segregation of the doping constituent, and it reduces the possibility of hot tearing (the separation of grains due to the melting of a low-melting point constituent in the grain boundaries). In order to obtain fine-grained castings, the nu-cleation frequency must be increased and grain growth must be restricted. Various techniques have been employed for obtaining this end, namely: rapid cooling, vibration, and inoculation of the melt. The success of these techniques depends upon the characteristics of the metal species and on factors controlled by heat transfer through the crucible walls. Recent studies2" have shown that the application of ultrasonic energy to the solidifying ingot is an extremely powerful tool in the improvement of the crystalline structure of metallic castings. Both the mechanical properties and homogeneity of the ingots are improved. Ultrasonic oscillations may affect the crystallization process by 1) permitting subcritical nuclei to agglomerate and thus form nuclei of sufficient size to cause crystallization, 2) changing the state of surface adsorption of various catalysts found in the liquid melt, 3) breaking pieces of solid from the solidified surface near the supercooled region thereby increasing the number of possible nuclei, 4) causing temperature fluctuations to occur in certain parts of the melt thereby increasing the supercooling at specific points in the liquid, and 5) decreasing the critical nucleus size by increasing the pressure at specific points in the melt.' Various investigators have concluded that the effectiveness of the ultrasonic oscillations results from cavitation which disrupts the growing solid-liquid interface The present paper describes the application of ultrasonic oscillations to the crystallization of the semiconductor N-type PbTe. The purpose of this study is to prepare crystalline

Jan 1, 1964

Despite the large areas of sedimentary basins in Western Australia, the coal resources are very meagre., This is a serious problem for the State, which-at present-lacks any other alternate source of fuel-for power production.. Located coal deposits are all poor in quality and mostly brown coals of little importance. The best..coal suitable for extraction is at Collie, where a black=sub- bituminous non-coking coal is mined. Most other coals recorded are low grade or lignite, with high ash'and moisture content and a low calorific value. Coal was first discovered in Western Australia in the bed of the Irwin River, 50-miles south-east of Geraldton, by the Gregory brothers, explorers, in the year 18+6,. but although investigated, it has never been developed. The most noteworthy discovery of coal was in the Collie River, 26 miles east of Bunbury, by Arthur Perrin in 1883. Production commenced in 1898 and ever since, Collie has continued to be the State's sole producing coalfield.

Jan 1, 1964

Unrelieved residual strains can influence the states of stress in rock masses. If cheap, stable structures are to be constructed in Tock in which large pressures are exterted by unrelieved residual strains, the pressures must be either utilized or neutralized. A photoelastic technique has been used to show that the release of residual strains in rocks is influenced by the mechanical properties of anisotropic rock fabrics. The relationships between directions of residual strain release and the attitudes of minor geological structures have been determined. For engineering design purposes it is possible to estimate the principal stress directions in rock containing unrelieved residual strains if the attitudes of such minor geological structures as foliation planes, lineations, and joints are known.INTRODUCTIONQuarry workers have long been aware that near-surface rocks may be highly stressed. In many cases the stresses are too large to be the result of gravitational loads. Dale (1923, pp. 34-35) gives many instances of deformation produced by the violent release of residual strains in quarry rocks. Coates (1963) has described powerful rock bursts and cases of rock deformation underground implying the existence of much larger stresses than are likely to result from present-day gravitational loads. The only explanation is that pressures of up to several thousands of pounds per square inch may be caused by unrelieved residual strains in rock.Instruments have been developed for measuring states of stress in rock masses. Most stress determinations in rock have been made on the assumption that rock behaves as a simple elastic material. It is now known that rock is a...

Jan 1, 1964

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By Erle C. Donaldson

A study of subsurface waste disposal in the United States shows that in eight States a wide variety of industrial wastes are being injected into formations ranging in age from Precambrian to Recent. More than 30 wells ranging in depth from 300 to 12,000 feet are used for waste disposal into subsurface formations which include unconsolidated sand, sandstone, vugular limestone, and fractured gneiss.

Jan 1, 1964

By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

The effect of such variables as feed size, particle shape, cleavage, and hardness on the relative proportion of impact, abrasion, and chipping events in a tumbling mill is demonstrated. The concept of an average event, which is a combination of the three comminution mechanisms, is introduced. It is postulated that the average event in a particular mill determines not only the size distribution but also the energy-size reduction relationship for the comminution process. Fragmentation of particles in tumbling mills appears to result from a combination of impact, abrasion, and chipping grinding.' The relative rates of size reduction attributable to any of the basic grinding mechanisms must depend upon a number of variables, such as feed size, particle shape, hardness, and the number and kind of particles in the mill. The purpose of this paper is to show experimentally how these variables in the properties of materials affect the size distributions obtained by grinding the material's in a laboratory tumbling mill. The resulting size distributions will be intetpreted in terms of a combination of three comminution mechanisms. METHODS AND MATERIALS In this study, minerals of widely differing properties were ground either separately or as mixtures in laboratory mills using rods or balls for grinding media. The materials used include quartz, Tuolomne, limestone (99.8% CaCO3), barite, corundum, galena, pyrite, glass beads, and crushed glass. The mill used was 8 in. in diam. and 9-1/4 in. long. For the ball milling tests, 17.6 kg of steel balls (36: 7/8 in. balls, 178: 1 in. balls, and 44: 1-1/8 to 1-1/4 in. balls) were used. For the rod milling experiments, 17.6 kg of steel rods 9-1/16 in. long (25: 5/8 in., 10: 3/4 in., and 5: 7/8 in. in diam.) were used. In each test, 1 kg of solids were ground wet at 60% solids at 77 rpm. In all cases except where otherwise specified, the feed to the mill was 4 x 8 mesh material. Size distributions of the ground products were determined by a wet-dry sieving procedure with Tyler series sieves. Size distributions of mixed products containing limestone were determined by dissolving the limestone with acid and sizing the residue. EXPERIMENTAL RESULTS AND DISCUSSION If the size distribution of the product from a tumbling mill depends upon the relative proportion of impact and attrition (abrasion and chipping) events, altering the grinding conditions may change these proportions and consequently alter the size distribution of the product. Data to illustrate this point can be taken from Gaudin's classic 1926 paper.2 In one series of experiments, Gaudin ground quartz of different initial sizes for four hours in a laboratory ball mill with 7/8-in. balls. In Fig. 1, his data are reproduced as the cumulative fraction finer than the stated size for the following initial feed sizes: 13.3 x 9.4 mm, 6.7 x 4.7 mm, 2.6 x 1.6 mm, and 0.83 x 0.59 mm. As the feed size was decreased, a dramatic change in the shape of the size distribution curves took place, even though the amount of minus 100-mesh

Jan 1, 1964

By Phillip A. Stoll, Young Ku Yoon

ThE deterioration of the magnetic properties of silicon-steel core materials during service (magnetic aging) is quite undesirable. Although some information about the effects of impurity elements on magnetic properties is available, 1,2 magnetic aging that occurs at low temperatures has not been extensively studied. Moreover, the microscopic techniques used by earlier workers were not suitable for study of fine metastable phases that are precipitated at relatively low temperatures. Recently, several investigators3,4 successfully used transmission electron microscopy in the study of low-temperature precipitation in Fe-C, Fe-N, and Fe-Mn-C alloys. To investigate metallurgical factors that affect magnetic properties after aging, the microstruc-tures of steels having different magnetic-aging

Jan 1, 1964

By N. Arbiter, J. Steininger, C. C. Harris

Power consumption and operating variables in air-liquid systems for a wide range of operating conditions in the turbulent region have been correlated by two dimensionless groups involving the power ratio and the flow number. The form of the correlation was developed by considering flow balances related to the air-liquid composite density in the impeller zone. Data for two phase air-liquid systems, both from literature and from the present investigation, has been correlated with high statistical significance. Two phase solid-liquid and three phase gas-liquid-solid systems have also been correlated. The quantification of power requirements in the agitation of liquids is well established.1 Rushton, Costich and Everett have shown that, for mixers operating in the fully turbulent region with no vortex, the power number

Jan 1, 1964

By A. P. Pipilen, M. Weintraub, W. F. Hosford, A. A. 230-000-000-006 Orning

In a study of the principal factors affecting the transport of coal-water mixtures through a centrifugal pump and a pipeline, the interrelation between solids concentration, velocity, and pressure drop was established for a minus 2-in. bituminous lump coal in concentrations up to 48% by weight. Optimum concentrations were found to exist for maximum capacity of a given pipeline and for minimum energy requirements per ton of coal. Coal size degradation by particle fracture took place in the pump; abrasion and attrition to form fines took place in both pump and line. A novel system of studying flow of solid-liquid mixtures in pipelines by the determination of relative sound intensities was developed. The hydraulic transport of minerals is in part an established art and in part a relatively new field of industrial technology. The established art developed especially where the mineral was under water, where water was used in hydraulic mining, or where large quantities of water had to be pumped from the mining site to expose the mineral. Power requirements and limited life of pumps and pipelines, under such conditions, were relatively unimportant. Examples may be found in dredging, and in hydraulic mining and transportation of phosphate rock.' In the design of a coal pipeline the most needed information relates to flow characteristics, power requirements, pressure drop, size degradation, and size segregation as a function of solids-water ratio and size distribution of the mineral. A considerable amount of information has become available concerning pressure drop and energy requirements.2'3 These topics were therefore not studied intensively. Coal degradation, however, has not been clearly delineated. Lammers and coworkers4 showed that coal may be severely degraded in size but did not distinguish between degradation produced in the pump and in the line. It is the primary purpose of this paper to outline techniques used to acquire some of the much needed design data. A full report of the investigation is to be published by the Bureau of Mines at a later date. APPARATUS AND PROCEDURE The apparatus for circulation tests (hereafter referred to as Type III tests) consisted essentially of a loop and a centrifugal solids handling pump, with attendant instrumentation, and coal weighing and feeding equipment. It also included an adequate water supply, as shown in Fig. 1. The selection of 6-in., schedule 40, carbon steel pipe was based on the top size of coal to be used. Assuming that the top size of coal should not exceed 1/3 the inside diameter of the pipe, a 6-in. pipe would accommodate 2-in. coal, a realistic size for transport from the mine face. An 872-ft loop was constructed first. Later a few tests were made with a lengthened circuit of 1361 ft by superimposing an additional loop on the original one. All bends used were of 3-ft radius. A noisemeter microphone, taped to the pipe at various points, but generally about 50 ft downstream of the pump, was used to sense segregation of the coal and the length of slugs of coal in water. To measure the stream velocity, radioactive sources were encapsulated in plastic cubes. The specific gravity of the blocks was adjusted to 1.3 and 1.8 to simulate low ash and high ash coal particles. Their passage through the pipeline was detected by a Geiger counter. Because the repeated circuits of the Type III tests did not permit coal degradation in the line to be distinguished from that produced by the pump, the two

Jan 1, 1964

By H. M. Thorne

Oil shale, a potential source of products presently obtained from petroleum, is found in many countries. The most extensive known deposits from the standpoint of potential shale oil in place are those in Brazil and the United States of America. Mining methods used for oil shale range from open-pit operations for shallow deposits to room-and-pillar and longwall techniques for deposits with thick overburdens. Oil shales from different sources vary greatly in the amounts and types of organic and inorganic constituents. By retorting, the organic material is converted to oil, gas, and coke. The largest percentages of oil are obtained from materials having the highest hydrogen content. Over 2,000 retorting systems have been patented, but only a few have been used industrially, and no single process seems best for all types of shales or economic conditions. Shale oils have different characteristics, depending on the source rock and method of retorting. They contain large quantities of olefinic hydrocarbons and more oxygen, nitrogen, and sulfur derivatives of hydrocarbons than most petroleums. Consequently, petroleum refining methods usually must be modified for shale oil. This is particularly true in catalytic processing. Hydrogenation, even under mild conditions, improves shale-oil refinability. Several byproducts may be obtained from both the retorting and refining steps.

Jan 1, 1964

By P. G. Winchell, J. K. Jackson

The strtcture of body-centered Fe-Ni-C alloys (0 to 16.5 wt pct Ni) containing less than 0.015 wt pct C was investigated by measuring the carbon-diffusion peak at low frequencies with a torsion pendulurrr. By determining the Snoek damping in ferrite and in quenched alloys of identical composition, the effects of nickel content and heat treatment were separated, and the existence of a structure in which Snoek damping is greatly reduced was revealed in the quenched ternary alloys. The relative amount of this structure increases with increased nickel content and cooling rate. It is proposed that this structure may be highly imperfect or tetragonal. In Fe-Ni-C alloys containing only ferrite the addition of nickel (0 to 5.1 wt pet) decreases tke area of the carbon-diffusion peak and shifts its position to lower temperatures but broadens the peak only slightljl. The decrease in peak area with increasing nickel implies that short-range interactions with the nickel atoms prevent some of the carbon atoms from participating in the relaxation process. The shift in the peak position indicates a long-range effect of nickel on the movement of carbon atoms so that at 300°K the diffisivity of carbon in -ferrite is increased by about 35 pct by the addition of 5.1 tut pct Ni. The results are presented as distributions of relaxation strength 072 the activation energy under the assumption that the frequency factor is invariant. BODY-CENTERED iron-base solid solutions dissolve carbon interstitially in the octahedral sites. The occupation of an octahedral site produces a tetragonal distortion of the surrounding lattice. These sites fall into three sets according to the orientation of the tegragonal distortion associated with each and may be identified by their lattice coordinates as: type 1/2 0 0, type 0 1/2 0, type 0 0 1/2. At low carbon levels in cubic ferrite the carbon atoms are distributed at random1 among these sites. In high-carbon body-centered iron-base solid solutions, which are unstable with respect to several two-phase mixtures, a tetragonal structure occurs as the product of the diffusionless transformation of austenite. This transformation is commonly accompanied by appreciable microstrain and its product is called martensite. The tetragonality of martensite, a supersaturated solution of carbon in a iron, is maintained prior to decomposition even though local diffusion of carbon occurs as evidenced by carbide precipitation. The tetragonality is taken as evidence that one set of octahedral sites is preferentially occupied by carbon. (This preferential occupation is called ordering below.) Support for this view is presented by the absence of strain-induced carbon-atom diffusion in high-carbon solid solutions (martensite). Such diffusion occurs in ferrite and produces the 40°C internal-friction peak observed at 1 cps frequencies.' Thus, there appears to be qualitative evidence favoring the view that at sufficiently high carbon levels tetragonality arises spontaneously as a result of the ordering of the carbon atoms; however, no experimental evidence exists concerning an equilibrium between cubic and tetragonal body-centered solid solutions. Moreover, attempts to estimate the energy of ordering7-' predict a value too low to maintain the tetragonality observed at medium carbon levels, 0.3 to 0.6 wt pct C. In the present work an attempt using internal-friction measurements is made to establish the presence or absence of tetragonality in low-carbon body-centered solid solutions formed by quenching austenite. Fe-Ni alloys containing about 0.01 wt pct and 0 to 15 wt pct Ni were selected for the study. While the work was in progress Gilbert and Owen10 reported that the transformation which occurs in these alloys during quenching at rates up to 5000°C per sec is not martensitic but is more properly categorized as massive. Thus, the solid solution

Jan 1, 1964

By J. B. Newkirk, R. W. Hendricks, R. Baro

STUDIES of the kinetics of precipitation in binary alkali halide systems are of interest from a theoretical point of view, because of the possibility of controlling diffusion rates by additions of aliovalent impurities. This note reports some preliminary results of a study of the kinetics of precipitation of AgCl from supersaturated solid solutions of AgCl in NaCl containing trace amounts of divalent cation impurities. In their study of the system NaC1- AgC1, Stokes and Li1 derived the phase diagram containing a mis-cibility gap with a broad maximum at approximately 170°C. They found that single crystals quenched from above the miscibility gap and aged at various temperatures within the two-phase region gradually turned light blue, then cloudy white, and finally opaque. The rate of transformation depended markedly on the aging temperature. The light-blue color in the early stages of aging was interpreted to be the result of Rayleigh scattering from precipitated particles less than 0.1 µ in diameter. These qualitative observations have been confirmed by us. However, a more precise tool was needed in order to quantitatively follow the growth kinetics of the precipitate particles. Because of the suspected small size of the precipitate particles and for other reasons, small-angle X-ray scattering was thought to be a suitable technique for this study. Small-angle X-ray intensities scattered from powder specimens were recorded on a General Electric XRD-5 diffractometer using the four-slit geometry described by Neynaber, Brammer, and Beeman.2 The slits were 0.08 mm wide by 10.00 mm high. It was found that, with very careful alignment, meaningful data could be obtained to within 3 min from the middle of the direct beam. Chromium radiation (?Ka = 2.29Å) was used in order to spread the scattered intensity to a relatively high angle, as indicated by Eq. [1]. A specimen containing 21.0 at. pet AgCl was prepared by melting analytic reagent-grade AgCl and NaCl under a chlorine atmosphere in a vycor cap-

Jan 1, 1964

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By R. A. Wolfe, H. W. Paxton

Self-diffilsion coefficients for cr51 and Fe55 in 12 pct Cr-Fe and 17 pct Cr-Fe for Fe55 in chromium, and for Cr51 in vanadium have been measured. The results are compared with other values for the Fe-Cr system, and with the various theories of diffusion in hcc metals. Some empirical correlations are discussed between Do and Q in hcc systems, or, expressed differently, the constancy of ?G*/T solidus for seveval bcc metals and alloys is noted. It appears very probable that a vacancy mechanism is operative in bcc metals, hut this cannot he stated with certainty. THE great bulk of work on diffusion in metals, both experimental and theoretical, was for many years concentrated on those with close-packed and, in particular, fcc lattices.1,2 There appears to be little doubt that the mechanism of diffusion in these solids is vacancy migration, leading to mass transfer and in substitutional solid solutions to a Kirken-dall effect.3,4 For bcc metals, the picture is much less clear. The Kirkendall effect certainly occurs in several alloys.5-10 However, attempts to understand the factors contributing to the pre-exponential in the usual expression for the diffusion coefficient D =D, exp {-Q/RT) by extension of ideas useful in close-packed lattices have not always been successful. Zener,11 Leclaire,12 and Pound, Paxton, and Bitlerl3 have suggested that various forms of ring diffusion may be important in some bcc metals. For close-packed metals, Do is usually about 1 sq cm per sec and Q - 35Tm kcal per mole (Tm = melting temperature in OK). The theory of Pound et al. suggests for ring diffusion that Do may be about 10-4 and Q, although difficult to calculate with any precision, would be significantly less than 35 T,. The experimental results on self and solute diffusion in ? uranium14,15 and ß zirconium,10 and for solutes in 0 titanium,17 and possibly for self-diffu- sion in chromium below about 0.75 T,," gave some credence to this theory. However, not all bcc materials display low values of DO and Q, and the exceptions were not predicted by any theory. Furthermore, it has recently become apparent that, in bcc materials, log D is not always linear with T-l if a sufficiently wide range of temperature is studied.16,18 This variation may be such that Q may increase18,19 or decrease20 with increasing temperature. The present work was undertaken in an attempt to provide further diffusion data on bcc metals, and to try to understand the factors which contribute to differences in behavior between the various elements. For part of this work, the Fe-Cr system was chosen since it is of considerable technological importance, and data on 12 pct Cr and 17 pct Cr alloys appeared well worthwhile to supplement that existing for the remainder of the stern.18,22 The diffusion of Fe55 in chromium was studied as an example of a more or less "normal" tracer element in a possibly abnormal host lattice. Finally, no data were available for vanadium, the neighbor of chromium in the periodic table, because of lack of a suitable isotope so cr55 was used as a tracer in a few preliminary experiments. For convenience, we shall refer to elements whose Do and Q are low compared to those predicted by Zener's theory as "anomalous". PROCEDURE This investigation determined self-diffusion rates by means of radioactive tracers and the integral-activity method first utilized by Gruzin.23 In this method a thin layer of radioisotope of the diffusing element is plated or coated onto a planar surface of the diffusion sample, which is then given an isothermal-diffusion annealing treatment. The determination of an activity-penetration curve involves measuring the residual activity of the specimen after each successive layer or section has been removed parallel to the original planar surface. The method used here is essentially the same as that used by Gondolf18 and Kunitake.21 Two radioactive tracers, cr51 and Fe55, were used in this investigation. Diffusion coefficients were determined for the diffusion of one or both of these tracers in four different materials, viz., Fe-12 wt pct Cr alloy, Fe-17 wt pct Cr alloy, chromium, and vanadium. The diffusion samples had nominal dimensions of 1.5 cm diameter and 0.5 cm thickness. The grain size was several millimeters for the Fe-Cr alloys and at least 1 mm for the chromium and vanadium samples. Accurately planar surfaces

Jan 1, 1964