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By A. S. Yue, A. E. Vidoz, F. W. Crossman

Tensile specimens were prepared from a single grain of an epitaxially grown Al-CuAl2 eutectic ingot. The eutectic lanzellae were oriented parallel and perpendicular to the tensile axis of the specimens. Since the composite was of the eutectic composition, the aluminum-rich matrix could dissolve up lo 5. 7 wt pct Cu in solid solution and, therefore, was amenable to strengthening by precipitation hardening. The tensile properties of the eutectic single crystals were determined at room temperature as functions of interlamel-lar spacing, platelet orientation, and thermornechanical trealment. The obserced variations in composite stress and modulus with respect to the level of&apos; composite strain are discussed in terms of premature fracture of CuAlz platelets, a distribution function for the strength of the lamellae, and unequal strains due to localized fracture of&apos; platelets. The discontinuous fiber composite model of Kelly and Tyson is modgied to account for a changing distribution of fiber lengths during composite loading. The tensile properties at elevated temperatures were determined for the direc-tionally solidified eutectic oriented with platelets parallel to the tensile axis. The observed properties are attributed to the onset of plasticity of the CuAL2 phase above 150°C. DURING the investigation of whisker- and fiber-reinforced metallic matrix composites in recent years, two major problem areas have developed: 1) The fabrication of the composite involves tedious handling techniques in order to obtain a unidirection-ally aligned and uniformly spaced set of whiskers in the metal matrix. 2) Due to weak interfacial bond strengths or because of the formation of additional embrittling phases at the metal-fiber interface during long-time exposure or fabrication at elevated temperatures, many composite systems have exhibited considerably lower strengths than those predicted by a law of mixtures analysis.&apos; These problems have been bypassed by the technique of growing whiskers and plates of high-strength materials in a ductile metal matrix by controlled unidirectional eutectic solidification.2 The tensile properties of directionally solidified A1-CuA12 eutectic are presented here. This alloy consists of a ductile aluminum matrix, containing up to 5.7 wt pct Cu in solid solution, which is amenable to precipitation hardening by heat treatment and a reinforcing high modulus CuAlz intermetallic phase. The two phases are present in the form of alternating platelets or lamellae. The microstructural stability of this unidirectionally solidified alloy at elevated temperatures has been studied extensively.3.4 and preliminary tensile and bend tests have been reported. 5-7In the present investigation the tensile properties of the A1-CuA1, eutectic have been studied as a function of several ther-momechanical variables: solidification rate. heat treatment. rolling at elevated temperatures. and lamellar orientation. It was felt that the uniformity of structure and excellent interfacial bonding would give tensile properties concomitant with the metal matrix composite theory of strengthening proposed by Kelly and coson. 8-9 The tensile properties that were obtained point to a wide distribution of strengths for the CuAlZ platelets, which leads to large deviations from the predicted mechanical behavior for this composite. EXPERIMENTAL PROCEDURE Epitaxial Growth of Eutectic Alloy. The A1-CuA1, eutectic alloy was prepared by an epitaxial growth process. Sections of a master alloy ingot (total impurity content <0.008 pct) were placed in an alundum boat, melted. and directionally solidified to obtain a multigrained plate 12 by 2 by 4 in. This plate was tapered at one end to mate with a seed crystal 1; in. long and 4 by $ in. square. Then the seed-plate combination was placed in an alundum boat which sat in a quartz tube passing through the center of a horizontal resistance wound tube furnace. A dried argon atmosphere was maintained. The temperature gradient in the furnace was such that the liquid-solid interface of the eutectic alloy was located near the end of the furnace and could be observed through the quartz tube. Single-crystal plates were formed by melting the material back to the midpoint of the seed crystal of the desired platelet orientation and then epitaxially growing the plate from the seed by withdrawing the alundum boat from the furnace at a constant rate. This technique was used to produce aluminum and CuA12 lamellae parallel and perpendicular to the transverse direction on the plate. Metallographic examination showed that both phases were continuous across the original liquid-solid interface. It was also possible to grow a plate from two seeds placed side by side: and, although the lamellae of one seed were oriented at 90 deg to those of the second seed, the interface between the two grains remained parallel to the growth direction along the entire ingot length. Maintenance of a straight intergranular boundary during the solidification process was possible as long as both seeds were oriented with their original growth direction parallel to the solidification direction of the plate. Eutectic plates were directionally solidified at rates of 0.2, 1.0. and 4.7 cm per hr and sectioned transversely to the solidification direction to determine the apparent inter lamellar spacing of the lamellae. Metallographic examination was also employed

Jan 1, 1970

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000&apos; and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,&apos; and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"&apos;" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,&apos;&apos; and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick&apos;s law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert&apos;s law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick&apos;s Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By P. Gordon, A. S. Iyer

IN a paper on the mechanical behavior of heat-treated steel, N. H. Polakowski&apos; put forward arguments to the effect that the stored energy resulting from the deformation of metals should be reduced during the inital stages of subsequent deformation carried out under conditions which produce work softening. At the time (1957) the only energy measurements available as indirect evidence on this point were the results of M. M. Degtyarev,2 some of which Polakowski reproduced in his Fig. 6, and which are again reproduced here in Fig. 1. The solid lines in the upper part of Fig. 1 are Degtyarev&apos;s, the dashed Lines Polakowski&apos;s prediction of the true trend of the stored energy in copper samples pre-strained in tension and then given various amounts of subsequent compression. The accuracy of this prediction has been borne out by some experiments carried out on American Smelting and Refining Co. copper (99.999&apos; percent Cu) by the present authors. Bars of this copper about 0.4 in. in diam and 12 in. long were prepared by vacuum melting and casting, followed by cold forging and swaging in several stages of about 40 pct reduction in area with intermediate recrystallization anneals. After the final anneal one bar was deformed in tension to 30 pct elongation; the gage length was then cut into several samples which were given axial compressions of various amounts. The hardness of

Jan 1, 1960

By Sergio G. Jarpa

A mining project is, at one and the same time, capital intensive and highly risky. Besides, because of its usual long projected life, the operating cost is more difficult to predict and offtentimes exceed, during the life of the project, the first investment manifold. The objective of this study was to evaluate the applicability of cost-capacity relationships as used in the chemical industry to mining operations and, when necessary, to develop new ones. With the aid of a computer library program available at the Computation Center of the Pennsylvania State University, the total investment in mining equipment was determined to vary exponentially with production capacity, and the scaling exponents for each class of equipment, i.e., drills, shovels, trucks and earth moving equipment, as well as for the total operation were calculated. Since the scaling exponent for the whole mining operation happened to be equal to 0.94, it was concluded that more significant economies of scale are achievable in processing plants than in mining operations. From the operating cost point of view, unit material cost was found to decrease more rapidly than unit labor for the same increases in production capacity. The analysis of cost centers revealed that drilling and blasting, which are materials-intensive operational stages, were the most favorable in achieving significant economies of scale. Hauling unit cost, on the other hand, decreased only slightly when production capacity increased.

Jan 1, 1977

By Fred Chappell

Pyrophyllite, a hydrous aluminum silicate, physically similar to talc, receives its name from the Greek word Pyr, for fire and phyllite, a rock or stone. Firestone refers to its first recorded use as firestones or hearthstones. Composition and Properties Pyrophyllite is an aluminum silicate A12O34SiO2H2O (alumina 28.3 pct, silica 66.7 [ ] pct, water 5.0 pct) (Table 1). Vanderbilt1 gives pH value of pyrophyllite as 5.6 to 8.4. Pyrophyllite is usually white or cream, though it may be found in shades of pale green, pale yellow, buff or light gray, and in darker shades and other colors principally due to oxidation of contained iron minerals. It is opaque to translucent in thin sections. Its hardness is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. Its luster is pearly to dull; it is recognized chiefly by its micaceous structure and cleavage, and its soft greasy feel. Two other varieties occur, one in which there are radiated needles in the crystalline form, and there is also a massive homogeneous structure found. Fine grinding reduces pyrophyllite to fiat plates or scales but aggregates of minute foliated plates may be formed.1 Distribution of Deposits Pyrophyllite is found in metamorphic rocks throughout the world but it is only in comparatively recent years that it has assumed much commercial importance. The principal

Jan 1, 1960

By C. M. St. John

INTRODUCTION The stress redistribution accompanying the excavation of a deep tunnel may induce failure of the rock. The role of the support system is to control the extent of the failed region and hence to limit closure of the tunnel within an allowable amount. In such circumstances, the design of the support system is generally based on the Ground Reaction Curve (GRC). The GRC is the relationship between the support pressure and the induced displacement at the tunnel wall for a circular tunnel under hydrostatic loading. In the calculation of the GRC (see Brown et al. (1983) for an exhaustive list of reference), the rock is generally treated as an elastoplastic material characterized by cohesive-frictional yield strength and by dilatancy during plastic deformation. A recent analytical development (Detournay, 1983) has allowed the generalization of the GRC concept for some cases of non-hydrostatic in-situ stress fields (Detournay and Fairhurst, 1982). As an application of that development, this paper describes design charts that provide powerful means of performing parametric analysis for tunnels subject to non-hydrostatic loading. BACKGROUND The in-situ stress in a plane perpendicular to the tunnel axis can be decomposed into mean and deviatoric components, Po and So (see Fig. 1). Since it is assumed that the rock is characterized by a Mohr-Coulomb yield strength, the deviatoric invariant So must be less than the limiting value Sl0 given by

Jan 1, 1984

By Dol Duwez, R. H. Willens

A technique is described by which metastable alloy phases can be obtained by very rapid cooling from the liquid state. The results obtained so far have lead to; 1) extension of solubility limits beyond their equilibrium values, 2) new phases not found under equilibrium conditions, and 3) amorphous alloys. MANY new nonequilibrium phases have been found in alloys rapidly cooled from the liquid state. The technique used in these investigations essentially consisted of propelling a small molten globule of an alloy against the inside surface of a rotating copper cylinder. Since these original experiments were performed, the technique has been greatly improved. The purpose of this paper is to describe in detail, for the first time, a simple and efficient apparatus for producing foils of alloys which are rapidly cooled from the melt and to summarize some of the observations made on these alloys. I) FAST COOLING APPARATUS In the original fast cooling apparatus used by Duwez, Willens, and Klement,&apos; the alloy was melted in a graphite container having the shape shown schematically in Fig. 1. A shock tube was attached to one end of the graphite part to supply the pressure for ejecting the molten globule. The globule was received on the inside of a rotating cylinder located about 0.5 in. from the exit of the graphite container. The globule trajectory made an angle of about 15 to 25 deg with the tangent to the cylinder at the point of

Jan 1, 1963

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells&apos; effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer&apos;s Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding&apos; showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,&apos; the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By J. Nagy, D. W. Mitchell, E. M. Murphy

In 1957 research was initiated in the U.S. Bureau of Mines experimental coal mine near Pittsburgh, Pa., to study factors affecting foam generation and transport, to evaluate the effectiveness of high-expansion foam for controlling mine fires, and to develop techniques for applying the method under U.S. mining conditions. These investigations showed that high-expansion foam containing at least 0.2 oz of water per cu ft of foam is effective in controlling experimental underground fires burning coal, wood, and oil. Sometimes the fire was completely extinguished, but more often, it was brought under sufficient control to permit either a direct attack on the fire with a stream of water or loading of the hot material into cars. A progress report&apos; prepared in July 1958 summarized the initial achievements of the USBM experiments. Since then other phases of the foam-plug method for attacking fires have been studied in the laboratory and in the mine. Previous studies by British engineers&apos; of the foam-plug method for fighting mine fires indicated that high-expansion foam was effective in controlling experimental timber fires in an underground passageway. Their subsequent workx-1 pertained to the practical aspects of fighting large fires within a mining area with a foam-plug. CONTROLLING EXPERIMENTAL FIRES In the USBM tests foam was formed by spraying a dilute solution of a foaming agent on a metal or cotton net of 1/8 to 1/4-in. mesh. Air passing through the continuously wetted net forms bubbles of 1/2 to 11/2-in. diam and produces a honeycomb of foam that fills the passageway. Under the ventilating-air pressure, this light-weight plug moves forward through the passageways, around sharp corners, and over obstacles. as illustrated in Fig. 1. High-expansion foam was transported to a wood fire, an oil fire, and 13 coal fires. Figs. 3 and 4 show a typical coal fire before and after attack with foam. In 12 of the 15 experiments the fire was brought under control when the water content of foam was 0.2 oz or more per cu ft. A fire was considered controlled when the flames were quenched and observers could cross the area without wearing breathing apparatus or protective clothing. In the other three experiments, conducted when the water content was less than 0.2 oz per cu ft of foam, the flames were retarded but the fire was not controlled. Coal fires have been attacked successfully by foam introduced at points varying from 155 to 1010 ft from the fire. The time of burning in coal beds 10 in. thick ranged from 11/2 to 5 hrs or more. Most of the experimental fire beds were 15 ft in length. However, in one experiment a floor fire 25 ft long and 5 ft wide was constructed $5 upwind from another fire 15 ft in length; in another instance, the fire was 100 ft long and 5 ft wide. Foam was applied to the fires for periods ranging from 7 to 36 min. The time required for foam application depends on the extent of the fire, time of burning, water content of foam, foam velocity, and degree of fire control desired. In addition to the coal fires, foam was transported to a fire covering 45 sq ft, produced by 15 gal of oil burning in metal trays on the floor. The foam extinguished the oil fire in about 1 min. In one other test, the burning of 1100 lb of dry sawmill slabs stacked in open cribs 4 ft high and 16 ft long was brought under control by foam in 2 min. Composition of Gases in Return Air: In several of the experiments samples of the return air from fire zones were collected; composition of the atmosphere before, during, and after foam application was then determined. Because of condensation in the relatively cool sampling tube, the amount of water vapor was not determined. Analyses showed that concentration of carbon dioxide and combustible gases increased as the foam began passing over the fire. This resulted from the decrease in the volume of air when foam generation started and from the formation of gases when water reached the fire.* The quantity of gases generated would not be greater than that from an equivalent amount of water applied directly to the fire. The highest total concentration of combustibles (CO, CH1, and H2 mixture) obtained during the experiment was about 2 pct; this occurred 6 min after foam reached the fire. This atmosphere was nonex-plosive, but calculations show that if the air flow were reduced to about 5 fpm and if the rate of gas liberation from the fire remained constant, the mixture would be explosive. The use of foam on a fire in all probability would affect the normal ventilation of a mine. If the mine is gassy, this factor must be carefully considered before the foam is applied. APPLICATION OF THE FOAM-PLUG TECHNIQUE IN MINES Equipment and procedures for applying the foam-plug methods must be adapted to the prevailing conditions at a particular mine. Some factors to be considered in developing equipment are: size or extent of the mine, dimensions and number of entries, ventilation system, mining methods, haulage facilities, availability of water, amount of methane liberated, and existing fire-control apparatus. • In most experiments the initial air velocity of 200 fpm decreased to 50 to 100 fpm as the foam plug increased In length.

Jan 1, 1961

W. Morton Webb, Germiston, Transvaal, South Africa (communication to the Secretary*):—The experience of Mr. Boeh-mer in the Leadville district and his reputation as an engineer assure the interest of anything he may write on the ore-bodies of that district; and all engineers who have operated in Leadville will agree that the theory of the origin of the Leadville deposits, as given by Mr. Emmons in his famous monograph, does not adequately explain the genesis of all the deposits. The solutiou of the problem does not, however, appear to be quite so simple as Mr. Boehmer would make it; and the advance pamphlet issued by the U. S. Geological Survey, pending the completion of the main report, shows that there is still much ground for controversy. No doubt the later eruptive0 had a greater influence on the deposition of the ore-bodies than was thought at the time of the first investigation by the Survey; but it has always appeared to me that the influence exerted by these dikes mas more in the nature of a physical than a chemical one. The weight of evidence in recent years is mostly in the direction of ascension rather than lateral secretion; and one of the strongest evidences is the fact that most of the ore-bodies lie under one of the comparatively impervious layers which help to make up the structure of these hills.

Jan 1, 1911

WALTER N. CRAFTS,* Toronto, Canada (written discussion?).-During the forging of 9.2-in. shells -for the United States Army, it was noticed that better results were obtained in certain instances when test bars had been held sometime before pulling. An investigation, therefore, was made by our metallographer, Mr. F. M. Arnold, to determine the effect of seasoning. The forging consists of a single operation, piercing a solid cast blank. The test sections were cut from the walls by an oxyacetylene flame, one piece from the nose end and one from the base on the opposite side. The test pieces were not heat treated in any way and the tests and seasonings were carried on at normal atmospheric temperatures. The specifica-tions were as follows: Standard 2-in. test bar, 0.505 in. in diameter; elastic limit, over 19 long tons, or 42,500 lb.; ultimate stress, 39.6 to 49.1 long tons, or 87,500 to 110,000 lb. per sq. in.; elongation, over 13 per cent. As a preliminary test two heats were selected; BP555, which was tested and reported failed on elongation on Aug. 20; and B01771, which was tested and reported failed on Aug. 24. On Aug. 29, retests were cut and machined from the same shells and held till Sept. 3 (5 days) when they were pulled. Both sets of results are given below.

Jan 12, 1919

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n&apos;ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.&apos; recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author&apos;s laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.&apos; The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.&apos; The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-&apos; M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"&apos;" due to a

Jan 1, 1971

By Billy L. Crowder, John M. Fairfield

The implantation of B+ , P+, and As&apos; into silicon has been studied with the purpose of making shallow p-n junctions. The influence of such parameters as 1) ion energy, 2) target orientation and temperature, 3) total dose, and 4) annealing schedule was investigated. An energy range of 70 to 300 kev was used for boron and phosphorus implants and up to 500 kev for arsenic. It is found that the experimental projected range agrees well with theory and that shallow junction depths can be made reproducibly. ION implantation has received much attention recently as a technique for doping semiconductors. Specifically, it has the potential of supplementing or replacing the diffusion process as a method for making p-n junctions. In a few specific cases it has been used successfully to make semiconductor junction devices. Potential advantages of ion implantation doping over diffusion techniques are: 1) It affords greater control of shallow junction depths (< 0.2 µ) while maintaining high peak concentrations. This is particularly important for high-speed switching devices, since lower junction capacitances and resistances can be achieved. 2) More precise registration of small planar structures can be realized if proper masking procedures are employed. This advantage is especially useful in the design of high-density integrated circuits. It has been used to advantage in FET fabrication since the edge of the source or drain can be aligned precisely at the edge of the gate electrode.&apos; 3) Ion implanatation permits lower temperatures than diffusion techniques. This factor alleviates the problem of compatibility of diffusivities often encountered when designing multiple-junction structures. Also, the lower temperatures create fewer thermal defects and dislocations, which may account for the high efficiency of some ion-implanted solar cells.2 4) Impurity profiles can be more easily tailored to resemble ideal distributions. Successful exploitation of the potential advantages of ion implantation techniques will depend on increased knowledge and understanding of the subject. The factors likely to be influential in determining impurity distribution profiles in ion-implanted single-crystal targets have been reviewed by J. F. Gibbons.3 In addition to the mass and energy of the implanted ion, the total dose, target orientation, and target temperature are important parameters. The annealing temperature required for removing lattice damage and incorporating the implanted species on an electrically active site is very important. This paper describes an investigation of some of these factors. Implants of boron, phosphorus, and arsenic into silicon have been studied. Energy ranges of 50 to 300 kev were used for boron and phosphorus and up to 500 kev for arsenic. In addition to the implantation energy, the effects of total dose, target temperature, and post implant anneal have been investigated. EXPERIMENTAL PROCEDURE The implantation targets were silicon wafers cut from Czochralski-grown crystals, lapped, and chemically polished. The orientations were (111), (110). and (100) with misorientations of up to 7 deg from the principal axis. For this study, accurate target alignment (i.e., within 0.1 deg) was not available and quoted misorientation values should be regarded as approximate . The implantation equipment consisted of an ion source, a 300-kev linear accelerator tube, an electromagnetic separator, and the associated target supporting and beam focusing assemblies. The ion source was a simple oscillating electron type source,4 which has been described elsewhere.5 The gaseous compounds BF3, PF5, and AsH3 were used as ion sources for B+, P+, As+, and AS+&apos;. Analyzed current levels of up to 20 pamp could be obtained; however, for this investigation target current levels of 1-3 µ amp were usually employed. The analyzed ion beam was collimated through a double slit (1.4 x 0.4 cm) and swept perpendicularly to the long axis of the slit such that an area of about 2 sq cm on each target was covered. Dosages of around 1015 cm-2 were normally employed, but smaller amounts were also used for comparison. A uniform flux density over the bombarded area was assured by the continuous use of profile monitors similar to those described by Wegner and Feigenbaum.6 Post-implant annealing was accomplished in an argon atmosphere in a temperature range of 600" to 950°C. It was not part of the purpose of this investigation to study the annealing kinetics; however, some isochronal and isothermal anneal experiments were conducted to determine the time and temperature necessary to render a reasonably high portion of the implanted ions electrically active (i.e., higher than 50 pct). Post-implant anneal temperatures of around 900° and 600°C were required for boron, and arsenic and phosphorus implants, respectively. Arsenic and phosphorus implants increased in conductivity rather abruptly at the proper anneal temperature of the isochronal curve, but boron increased more gradually over a wider range. Isothermal anneal curves were reasonably flat after 10 min, so an anneal time of 1/2 hr was used for the experimental results described below. The profiling techniques were: 1) neutron activation analysis, 2) differential sheet resistance,7 and 3) junction staining.8 The differential sheet resistance technique is commonly employed in this type of study. Its principal disadvantage is the uncertainty of the ef-

Jan 1, 1970

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By P. W. Gilles, B. D. Pollock

THE pioneering work of Steinitz1 and Steinitz, Binder, and Moskowitz2 has shown conclusively the existence at high temperature of two additional phases in the molybdenum-boron system and thus brings to a total of six the number of structures appearing in this system. To the structures Mo2B, MOB, and Mo2B5 they have added MO3B2, a new -MOB form, and have shown that MOB,, which has the same range of composition as Mo2B5, is only a high temperature structure of the latter. This solid solution, interestingly enough, includes neither of the compositions corresponding to the stoichiomet-ric compounds, MOB, or Mo2B5, but rather at all temperatures has intermediate values of composition. These workers have also, in the course of their work, measured melting points, transition temperatures, eutectic and peritectic points in the system and have shown that Mo3B2, because of its dispro-portionation at low temperature to Mo2B and MOB, is stable only in a limited high temperature range. During the course of the present work on the vaporization properties of the molybdenum-boron compounds, a few transition temperatures were observed. When the report of the other workers appeared, it was decided to repeat, in part, their study of the system. As a result, considerable evidence has been obtained that substantiates the specific kinds of melting processes they report as well as the general features of their diagram. However, a marked difference was found between the temperatures they report and the ones observed in this study, with the latter being higher. The purposes of this paper are to present the evidence obtained in this laboratory that verifies their diagram of the system, to give some important temperatures in the system, to compare them with those previously published, and to seek an explanation of the difference. Samples The metal starting material was 400 mesh molybdenum powder with a purity stated by the manufacturer to be 99.9 pct. The initial treatment, designed to remove volatile contamination, consisted of heating in a vacuum for 10 min to a temperature of from 800" to 1000°C during which a loss of 0.3 to 0.4 pct occurred. An assay following this treatment showed it to be 99.4 pct pure, with the principal impurity probably being oxygen. The boron starting material was obtained from the Cooper Metallurgical Laboratories and the Fair-mount Chemical Co. as 325 mesh powder with manufacturers&apos; analyses of 99 pct or better. Initial treatment consisted of heating in molybdenum in a vacuum at about 1700°C for 10 min. During this time a loss of 3.5 pct occurred. An assay following this treatment showed the different samples to have purities ranging from 95.5 to 99.0 pct with iron and carbon as the principal impurities. Following the initial treatment, the elements were combined to form stocks of Mo2B and MOB by heating pressed mixtures in a vacuum to 1100" to 1200°C to accomplish reaction and to 1500" to 1900°C for a few minutes to evaporate the more volatile impurities. Analysis of the two compounds for boron by a modification of the method of Blumenthal3 and for molybdenum by the lead-molybdate method indicated them to have purities greater than 99 pct. The individual samples to be studied had compositions in the Mo2B-MOB range and consisted of mixtures of the stock compounds. Procedure As is usually the case in high temperature work the selection of containers for the samples posed some problems. For vapor pressure studies tantalum crucibles, allowing little contact with the pressed samples, were used and some of the observations made during these experiments are pertinent to the study of the phase diagram. Most of the experiments, however, were performed in graphite containers, as were those of the previous authors. Two kinds of spectroscopic grade graphite crucibles were used. One was a % in. cylinder, 3/4 in. high, containing seven 3/16 in. holes drilled 1/2 in. deep into which were packed samples of the different mixtures weighing 250 to 500 milligrams. The other, consisting of separate crucibles, was prepared by drilling 3/16 in. holes, 1/2 in. deep into 1/4 in. graphite rods % in. long. The 7/8 in. cylinder was heated directly by induction while the small crucibles were packed in a tantalum heating element for induction heating. All heating was done in a high vacuum system in which the pressure was generally less than 1x10-5mm and never rose above 2x10-5mm when the samples were hot. The general pattern of the heating in graphite was to heat rapidly to a temperature somewhat below the desired one, then to raise the temperature slowly. The samples were held for 2 to 5 min at the maximum temperature, which in all cases was far higher than that needed to produce reaction. The short time was employed to reduce possible contamination by the crucible material and to reduce composition changes that would occur because of vaporization. After examination following the heating, the samples were reheated to a higher temperature. Temperatures were measured with a Leeds and Northrup disappearing filament optical pyrometer, certified by the National Bureau of Standards, by sighting through a window at the top of the vacuum

Jan 1, 1954

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965