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By W. Rostoker

LAVES and Wallbaum1 and more recently Duwez and Taylor' have reported on the occurrence of a family of intermediate phases having the composition Ti2X, where X may be Cu, Ni, Co, Fe, or Mn.

Jan 1, 1953

By Chikao Nishiwaki

INTRODUCTION The Japanese dependency for mineral raw materials from foreign sources increased rapidly within the 20 years since the Korean war. During this 20 year period Japan has attempted to industrialize and develop her economy while depending mostly on heavy import of nearly all kinds of mineral raw materials. She has fabricated them using energy generated mostly by mineral fuel that are also imported. Fabricated goods are either used domestically to accelerate more fabrication industry or exported after adding more refinement or fabrication. In this paper iron ore as a major raw material for the Iron and Steel industry, three major base metals, copper, zinc and lead, and petroleum as a major energy source have been selected as examples to represent the general features of various kinds of mineral raw materials that are imported. Among other important mineral commodities for which Japan dependa upon foreign sources are: Aluminium, nickel and cobalt, potash and phosphorous 100 percent dependent and tin, tungusten, chromium and molybdenum over 95 percent dependent. IRON ORE Statistics for the important iron and steel raw materials, namely iron ore, coal and scrap iron are shown in Tables 1, 2 and Fig. 1. Iron ore is by far the most important and basic among these three commodities. There has been practically no steel or iron imported as a metal into Japan during this period. Iron ore, including aggregate such as pellets, and metallurgical coal are mostly transported in large ore cargo boats to the port where very efficient port facilities unload them directly at the steel mill site. As a result

Jan 1, 1976

By E. I. Larsen, E. F. Swazy, F. R. Hensel

High strength, high-conductivity copper-base alloys have found considerable use in the resistance welding and electrical industry in the form of castings, forgings, or wrought products. There are a number of parts utilized by these industries which would lend themselves to manufacture by powder metallurgical methods provided the required physical and electrical properties are obtainable with such methods. The present paper describes the results of a study of certain copper-base powder metallurgical products susceptible to precipitation hardening. Copper Powders The general types of commercially available copper powders are flake, spherical and electrolytic. Micrographs of these three types are shown in Figs. I, 2 and 3. The difference in particle shape is pronounced and obvious. The type of powder used is determined, or at least indicated, by the final properties desired in the finished article. The type of powder employed during the present investigation was electrolytic powder shown in Fig. 3, and was chosen because of its particular adaptability to the work described in this Paper. The screen and chemical analyses of this powder are shown in Table I. In the preparation of compacts of high electrical conductivity, the purity of the copper powder is of importance in addition to other factors, such as density and the state of internal stresses. These variables were studied briefly by pressing a number of compacts to various pressed densities, sintering them for one hour in hydrogen at 975OC and repressing. The size of the finished compacts was 1/4, by % by 8 in. The time interval from the application to the termination of pressure was approximately 20 sec. Some of the compacts were annealed before testing. The results are listed in Figs. 4 to 8, inclusive. In Fig. 4 the curves of pressed density vs. compacting pressure, and sintered density versus compacting pressure show the typical direct relationship of pressure and density. Compacting pressures exceeding about 30 tons per sq. in. result fiequently in expansion during sintering for the type of powder used. Fig. 5 indicates that variations in the initial pressed density within the range of about 5 to 6 grams per c, c., affect only slightly the pressure required to obtain a

Jan 1, 1946

By E. I. Larsen, E. F. Swazy, F. R. Hensel

High strength, high-conductivity copper-base alloys have found considerable use in the resistance welding and electrical industry in the form of castings, forgings, or wrought products. There are a number of parts utilized by these industries which would lend themselves to manufacture by powder metallurgical methods provided the required physical and electrical properties are obtainable with such methods. The present paper describes the results of a study of certain copper-base powder metallurgical products susceptible to precipitation hardening. Copper Powders The general types of commercially available copper powders are flake, spherical and electrolytic. Micrographs of these three types are shown in Figs. I, 2 and 3. The difference in particle shape is pronounced and obvious. The type of powder used is determined, or at least indicated, by the final properties desired in the finished article. The type of powder employed during the present investigation was electrolytic powder shown in Fig. 3, and was chosen because of its particular adaptability to the work described in this Paper. The screen and chemical analyses of this powder are shown in Table I. In the preparation of compacts of high electrical conductivity, the purity of the copper powder is of importance in addition to other factors, such as density and the state of internal stresses. These variables were studied briefly by pressing a number of compacts to various pressed densities, sintering them for one hour in hydrogen at 975OC and repressing. The size of the finished compacts was 1/4, by % by 8 in. The time interval from the application to the termination of pressure was approximately 20 sec. Some of the compacts were annealed before testing. The results are listed in Figs. 4 to 8, inclusive. In Fig. 4 the curves of pressed density vs. compacting pressure, and sintered density versus compacting pressure show the typical direct relationship of pressure and density. Compacting pressures exceeding about 30 tons per sq. in. result fiequently in expansion during sintering for the type of powder used. Fig. 5 indicates that variations in the initial pressed density within the range of about 5 to 6 grams per c, c., affect only slightly the pressure required to obtain a

Jan 1, 1946

By Culver, Richard S.

In spite of the widespread interest in rock bolt research, relatively little is known about the critical region surrounding the bolt anchor. In analyzing the stress distribution around an opening resulting from rock bolt support, it is commonly assumed that the bolt is fixed at a point far enough from the surface so that the anchor does not influence the performance of the bolt. Furthermore, a bolt anchor is assumed to per- form satisfactorily if it will hold the design load with a minimum amount of load relaxation, commonly called bleedoff. From the standpoint of the design engineer both of these assumptions are reasonable, but they ignore the fact that the extremely high stresses in the region of the anchor are capable of generating fractures in the rock. Lang estimated the bearing stresses for a slot and wedge anchor on a one-inch-diameter bolt to be as high as 125,000 psi. This paper describes a more thorough analysis of the magnitude of the stresses around the anchor and the nature of the potential fractures that might result.

Jan 1, 1968

By S. G. Dixit, A. K. Biswas

The flotation and adsorption behavior of ilmenite, monazite and zircon have been studied with sodium oleate as the collector and pH as the principal variable. The maxima in the flotation and adsorption properties of any of the above minerals fall within similar pH ranges. The bell shaped pH versus adsorption magnitude (r) curve is explained on the basis of collector concentration (Co and the concentration of hydroxyl ion (COH-) acting as the depressant. An equation of the type: 1 =KiCor~K2 Coh-/Coi-is proposed to account for the experimental data. The beach sand deposits along the sea coast in Southern India contain ilmenite, monazite, zircon, rutile and sillimanite as valuable minerals while quartz, garnet, shells and traces of hornblende form the gangue. A typical composition of the deposits is reported to be as follows:' Ilmenite 75%, Zircon 4-6%, Rutile 3-4%, Monazite 2 - 4%, Garnet 2 - 5% and the rest 8 -10%. Selective flotation of beach sand constituents has been reported by many workers.2-4 The fatty acid soaps have been invariably used as collectors. It is seen that all the valuable constituents of the beach sand are efficiently floated by soap collectors such as sodium oleate. In order to selectively float the beach sand constituents, it is necessary to use some depressants such as sodium silicate.3 The physicochemical parameters that govern the flotation of these minerals are yet to be studied in detail. In the present article, the findings on the parallel studies on the flotation and adsorption of the systems — ilmenite-sodium oleate, monazite-sodium oleate and zircon-sodium oleate — are being reported. In these correlative studies on adsorption and flotation of beach sand minerals, ilmenite (FeTiO3), monazite (Ce, Dy, Nd) PO4 and zircon (ZrSiO,) have been selected because they represent three important

Jan 1, 1970

By Davis Baker

The direct-metal cars or ladles of the Maryland Steel Company have a capacity of 18 tons when filled within 12 inches of the top. On account of this large capacity, the formation of skulls in these ladles is by no means as rapid as in smaller ladles; but a skull once formed is a very unwieldy piece of metal to handle, and especially to remove from the ladle. We have found it cheaper to clean ladles often rather than make very heavy skulls. We aim to keep the ring of chilled metal that forms on the surface of the iron chipped off, so that the skull shall form principally at the bottom until it becomes so thick as to render the ladle unfit for service. Sometimes it happens that a ladle may be held for several hours filled with molten metal. This invariably leaves a large amount of chilled metal in the ladle. Frequently the skull will weigh several tons, and will be of the full size of the ladle inside, with a top crust, having perhaps a hole 12 inches square, through which the molten metal was poured. In order to remove skulls that cannot be easily chipped out with a bar, we use what may be called a skull-extractor, consisting of a hydraulic cylinder mounted in the center of a heavy cast-iron plate, standing vertically on a suitable foundation. Figs. 1 and 2 show the construction and operation of this apparatus, Fig. 1 being a view of the extractor with pistons extended to full stroke, and Fig. 2 a view with ladle in position and pistons about to commence the stroke. in both figures, A is the hydraulic cylinder, B the vertical cast-iron plate, and C the foundation. The water-pressure, admitted through the pipe, P, is 750 pounds per square inch, and the inside diameter of A is 14 inches. There are two pistons: D, fitting the bore of the cylinder, and E, 84 inches in diameter, moving inside of D. Both pistons move together when

Jan 1, 1893

By E. Breinan, M. Salkind

Al3Ni whiskers were chemically extracted from unidirectionally solidified Al-A13Ni eutectic ingots, bent into loops, and heated for 0.1 to 10 hr at 320°, 415", and 510°C. The initial strains ranged from 0.003 to 0.055. In all cases, permanent plastic deformation was noted after heat treatment. The deformation consisted of relatively uniform bending at low stresses and temperatures and short times and kinking followed by fracture at high stresses and temperatures and long times. After kinking, the whisker segments adjacent to the kinks were found to have straightened, which is evidence of a dislocation condensation mechanism. The range of temperatures and strains at which time dependent plastic deformation was found indicates that creep of whiskers probably plays a role in the creep of A13Ni whisker-reinforced aluminum. WHISKERS may be defined as nearly perfect single crystals which exhibit high strength. Because they can support high stresses at relatively low strains, they have been successfully employed in reinforcing metals at both ambient and elevated temperatures. In studying the creep behavior of A13Ni whisker-reinforced aluminum at elevated temperatures,1,2 it was noted that the composites exhibited measurable creep deformation. This investigation of the creep relaxation of individual A13Ni whiskel, extracted chemically from the composite was initiated to determine if creep of whiskers could con. "bute to the overall creep of the composite material. Many observations of plastic deformation of metal and halide whiskers have been made. Brenner3-8 noted that copper, silver, and iron whiskers exhibited heterogeneous plastic deformation at room temperature when strained beyond their yield points. Gyulai9 and Gordon10 observed plastic deformation of relatively large (>3 µ) NaCl and KC1 whiskers, although the smallest, most perfect whiskers were completely elastic. Eisner" noted plastic deformation and microcreep of iron and silicon whiskers at room temperature after straining beyond the yield point. Whiskers reported to exhibit creep at stresses below the yield point were zinc1'-" and Silicon.15 Cabrera and price" observed some zinc whiskers which crept at room temperature after a short incubation period but then stopped creeping after a short time. Because some of their specimens exhibited no creep, they concluded that those whiskers that crept were relatively imperfect. Pearson, Reed, and Feldman15 observed similar creep behavior of silicon whiskers at 800°C. They also concluded that creep of the whiskers was a result of imperfections in their crystals. Brenner16 observed delayed failure of A12O3 whiskers at elevated temperatures but found no evidence of plastic deformation up to 2030°C (99 pct of E.EREINAN and M.SALKIND,JuniorMembers AIME,are Research Scientist and Chief, respectively, Advanced Metallurgy Section, United Aircraft Research Laboratories, East Hartford, Conn. Maunscript submitted April 5, 1968. IMD the melting temperature). Brenner also noted7 that some copper and iron whiskers exhibited delayed kinking above 350°C while others did not. One can conclude from these observations that small relatively perfect whiskers could exhibit completely elastic behavior during sustained elevated-temperature loading of composites. Since A13Ni whiskers tested in both bending and tension were found to exhibit no evidence of plastic deformation at room temperature'7'18 this study was initiated to determine whether or not creep of A13Ni whiskers occurred at the elevated temperatures at which creep in the composites was observed. Whiskers were chemically extracted from ingots of unidirectionally solidified A1-A13Ni eutectic, constrained in bending to various elastic strains and heat-treated. The bending constraints were removed after heat treatment and the amount of permanent set was taken as a measure of the time-dependent plastic deformation. EXPERIMENTAL PROCEDURES Ingots of eutectic Al-A13Ni containing nominally 6.2 wt pet Ni were unidirectionally solidified at approximately 11 cm per hr using a process described elsewhere.19,20 The starting materials were 99.99 pct pure. Cylindrical sections cut from the center of each ingot were placed in a 3 pct aqueous solution of hydrochloric acid and the whiskers were extracted as described previously.17 The whiskers nearest the surface were blackened somewhat due to overexposure to the acid while the center of the ingot was being dissolved These partially attacked whiskers were discarded. An intermediate zone of silver-gray-colored whiskers was collected and stored in methanol for use in relaxation experiments. Individual long pieces of A13Ni whiskers were placed on Fisher Precleaned Microscope Slides. These normally straight whiskers were bent elastically into arcs or loops of varying radii by manipulating their ends with a slender probe. The mass attraction between the whisker and the probe was sufficient to cause the whisker to follow the probe. The whiskers were retained in the elastic bend by the surface tension of a fine residual film on the slides. By using long whiskers, the action of the surface tension on the unlooped ends of the whisker allowed high elastic strains to be maintained in the loops. After each whisker was bent, a photomicrograph was taken for use in measuring the bending strain. The range of strains studied was 0.003 to 0.055. The bent whiskers were then encapsulated in Pyrex tubes at pressures between 10"6 and 5 x 10"6 mm of mercury and heat-treated at 320°, 415°, and 510°C (respectively 53, 61, and 70 pct of the peritectic decomposition temperature). After each heat treatment, the liquid film on the slides was found to have dried, but the whiskers were held in their original shapes by a residue on the slide. The minimum radius of curvature of each bent whisker was measured before and

Jan 1, 1969

THERE are three chief production zones of tungsten ore in China. In the Province of Kiangsi mines are located at Kanchow, East River, and West River. Their combined production is understood to amount to 300 to 350 tons of ore per month, and their original exportation is made through the port of Kiukiang, largely to Shanghai. The second zone is in Kwangtung Province, the mines there being at Tayulin. Produc-tion reaches about 200 tons per month and cargo is gen-erally exported through the port of Hong Kong. In the Province of Hunan approximately 25 tons of ore are produced monthly in the mines at Ton-on. Tungsten ore from Kiangsi and Kwangtung Prov-inces is generally about 70 per cent WO, (tungstic acid), while that from Hunan is of lower quality, run-ning about 65 per cent WO3. Kiangsi ore is received from the mines in 100-1b. and Hunan in 224-lb. gunny sacks. No repacking is done except as it is made neces-sary by the condition of the sacks. Kiangsi Province contains the Chinese districts pro-ducing the largest amount of salable wolframite or tungsten. Many districts west and south of Kiangsi have been found to have wolframite deposits.-Com-merce Reports.

Jan 1, 1928

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL FILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE 2 J. H. JANEWAY4 BRADLEY STOUGHTON

Jan 5, 1918

By D. B. Masson

THE martensitic transformations occurring in ,B AgCd as a result of cold working at room temp.. a-ture and cooling below room ten1erature have been reported by Masson and Barrett.1 These authors found that simple cooling to 127°K caused body-cen-tered-cubic AgCd containing 53.0 at. pct Ag to transform to an orthorhombic structure, while mechanical deformation at room temperature was found to induce a hexagonal structure. Furthermore, they observed that the temperature at which martensite first appeared on cooling, Ms, and that at which the transformation was complete, MI, as well as the corresponding temperatures for the reversion on heating, As and Af, could be ascertained to ± 1°K, although they report these temperatures only for the alloy containing 53.0 at. pct Ag (51.96 wt pct). In the work reported here the temperature range of the transformation on cooling was studied as a function of composition, and further consideration was given to the relationship between the original bcc structure and the transformation-induced hexagonal and orthorhomic structures. EXPERIMENTAL PROCEDURE All samples studied were in the form of annealed 300-mesh powder and were prepared from the constituent metals in the manner described previously.1 The compositions in weight and atomic pct are listed in Columns 1 and 2 of Table I. Method of determination of transformation temperature was the same as utilized previously1—measurement of the intensity of X-rays diffracted by the transformation product. A diagram of the low-temperature sample mount is shown in Fig. 1. This mount was made to fit a GE model XRD-3 X-ray diffraction unit. The powder sample was varnished to a flat surface on a copper sample holder at A. This sample holder was soldered to a brass rod, B, which was in turn soldered to a second copper rod, C. Rod C could be cooled to 78°K by inserting it into a reservoir of liquid nitrogen, D. A heater coil of nichrome wire was wound at E on the sample holder, and by varying the current through the heater a thermal gradient could be maintained along brass rod B. Sample temperatures from 78°K up could be attained and held as long as needed. The sample holder and nitrogen reservoir were insulated by Styrofoam, F, and the sample itself was protected by two radiation shields, G. The X-ray beam entered and left the sample chamber through windoys in the supporting container at H and I. Sample temperatures were measured by a calibrated copper-constantan thermocouple varnished to the sample holder just out of the beam at A. The low-temperature structure had been found to possess orthorhombic symmetry1 and the expected positions of the diffraction maxima were known. Therefore the sample was aligned in the X-ray beam and the Geiger counter of the spectrometer set to receive the most intense orthorhombic reflection without an adjacent interfering cubic reflection. This

Jan 1, 1961

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By Robert Maddin

The application of electrolytic polishing of metals introduced a new technique for preparing surfaces, especially for single crystals. This procedure generallv has been assumed to eliminate the strain introduced by mechanical polishing and to result in a more truly representative surface, particularly in the case of soft metallic materials. However, apparently little information is available concerning specific characteristics of a surface prepared electrolytically. The conventional method of mechanical polishing is known to produce a layer of distorted metal which is usually removed by a suitable chemical etchant. To what depth the strain introduced by mechanical polishing penetrates into the lattice is still obscure. The present investigation illustrates the apparently anomalous appearances of glide ellipses on electrolytically polished surfaces of aluminum single crystals. Experimental Procedure and Results Aluminum single crystals, 99.975 pct pure, remaining from the investigation of Found,' were polished electrolytically using a solution of fluoboric acid and a low current density. Laue back-reflection technique, interpreted after the manner of Greninger,2 was used to determine the orientation and the specimen axis rotation of the crystals. Three flat surfaces about 4 mm wide parallel to the specimen axis, one perpendicular to the theoretical slip direction and the other two 120° apart, were polished mechanically and repolished electrolytically. A tensile load was applied using a Southwark-Emery tensile machine at a rate of about 40 lb per min. Elongation was measured by noting the initial and final gauge lengths. X ray diffraction was used to obtain the usual x and X values in order to calculate the elongation and shear by plotting stereographically the specimen axis rotation by means of the Schmid-Boas formula.³ In Table I may be found the value of the gauge diameter, measured elongation, calculated elongation and shear for the crystals investigated. Fig I shows the initial and final positions of the specimen axes of the crystals. At a low magnification the slip lines developed on specimen Al-I appeared straight and rather evenly spaced. However, at a high magnification, the slip lines were seen to be composed of small markings which were present throughout the length of the specimen (Fig 2). The distance between the markings was fairly constant and their directions all parallel to One another' Fig 3-57 photographed On different surfaces of the specimen, illustrate the interesting appearance of these lines. It may be noticed from Fig 4 that the markings, which present the appearance of

Jan 1, 1949

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By E. J. Haug, K. L. Clifford, K. L. Purdy

St. Joe’s Minerals Corp.’s Southeast Missouri Mining and Milling Division produces lead, zinc and copper sulfide concentrates at three of its operations. The Viburnum and Fletcher mills have been described in previous papers. The new Bushy Creek mill, dedicated in May of 1973, is an updated version of the Fletcher mill incorporating 8.5m3 (300 cu ft) lead and zinc

Jan 1, 1980

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,' in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.' Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.' The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964