Search Documents

For the year ending February, 1920 PRESIDENT HORACE V. WINCHELL.. . MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y VICE-PRESIDENTS CHARLES W. GOODALE,1 . . . . District 5 BUTTE, MONT. MARK L. REQUA,1 District 6 SAN FRANCISCO, CAL. HENRY S. DRINKER, District 2 So. BETHLEHEM, PA. ROBERT M. RAYMOND,2 . . . . District 0 NEW YORK, N. Y. EDWIN LUDLOW,3 District 2 LANSFORD, PA. A. R. LEDOUX,3 District.0 NEW YORK, N. Y.

Jan 11, 1919

By J. Paces, E. Miller, K. L. Komarek

The resistivity was determined as a function of temperature over the composition range from pure cadmium to 40 at. pct Cd. Melts with cadmium contents less than 85 at. pct had negative temperature coefficients of resistinity. On cooling below a transition temperature close to the liquidus temperature, the slope of the resistivity-temperature curve changed sharply. The activation energy calculated from the slope was 0.07 ev above the transition temperature and 0.14 ev below. The resistivity vs composition curve shows two maxima corresponding in composition approximately to CdSb and Cd3Sb2. THE relationship between the structure of a liquid and that of the crystal formed on solidification is at present not well-under stood. Various experimental determinations of the properties of liquids indicate that deviations from random atomic arrangements in liquids occur and that the properties of a solid and of its melt are closely related. Thermody-namic activities of liquids usually show negative deviations in systems where compound formation occurs in the solid,' and X-ray data indicate that close-packed solids and their melts frequently have nearly the same coordination number. Electrical resistivities and viscosities of liquids frequently exhibit maxima at compositions corresponding to compounds in the solid state. It should be of interest to study systems which have both stable and metastable compounds in the solid, and to determine if the short-range order in the liquid is affected by the existence of the metastable solid phase. The Cd-Sb system exhibits such a metastable phase. The phase diagram is shown in Fig. 1.3 The stable system has one intermetallic compound, CdSb, crystallizing in the orthorhombic crystal structure, with a melting point of 456°C. The metastable system also has one compound, Cd3Sb2, melting at 420°C and crystallizing in the monoclinic structure. Metastable alloys transform to the stable crystal structure in the temperature range from 250o to 350°C. Several distinct indications of very strong short-range order in the liquid phase have been reported in this system, with a close relation between the ordering in the liquid and the existence of both the stable and metastable solid phases. Scheil and Baach4 have observed distinctly different vapor pressures for liquid Cd-Sb alloys depending on whether the liquid solidified to the metastable- or stable-phase configuration. They observed an unusually sharp increase of the activity in a limited temperature interval immediately above the liquidus temperature of stable alloys, followed by a sudden decrease in slope to what they considered normal values. On cooling, the activity data reproduced the values in the normal range but then deviated from the values obtained on heating. They also observed that specimens of the stable phase upon melting and resolidifying always crystallized in the stable crystal structure as long as the melt was not heated to more than 485° to 525°C; otherwise solidification to the metastable phase occurred. However, in a later investigation, these results were not reproduced (13). The resistivity of liquid Cd-Sb alloys has been investigated by Matuyama 5, Oleari and Fioram, 8 and Belaschenko (141, but only above 500°C, the temperature region where Scheil and Baach observed no vapor-pressure anomalies. The data of Matuyama and of Oleari and Fiorani are reproduced in Fig. 5 and show a maximum in resistivity at 50 at. pct Cd. The data of Oleari and Fiorani, however, show the maximum as being rounded, and their values in general are slightly higher than those of Matuyama.

Jan 1, 1964

By T. Kilner, A. Plumtree

DURING an investigation of electro-deposited silver structures, samples were prepared for metallographic examination by cold mounting in plastic, grinding on successive grades of emery paper down to 3/0, and chemically polishing by swabbing using the chromic acid solution described by Gilpin and Worzala.1 Attempts to etch these samples using the standard solutions described for silver (e.g., 5 pet KCN-5 pet Na2S2O8, H2O2-NH4OH, and various potassium dichro-mate solutions) all failed to give good results due to staining of the samples and to rapid etching. The staining was caused by the chromic acid polishing solution being trapped in small fissures between the sample and the mounting plastic, and also in small fissures in the sample itself. To overcome these difficulties, an etchant was developed which prevented staining at the same time as it slowly etched the sample. This resulted in a very clean, crisply etched surface as shown in Figs. 1 and 2. This etch consisted of 10 ml of orthophosphoric acid, 10 ml of distilled water, and 2 drops of the polishing solution noted above,' which is made by mixing 100 ml of saturated CrO3 solution, 45 ml of 10 pet HC1 solution, and 800 ml of distilled water. The etching procedure involved taking the final polished sample, either immersing or swabbing in the etchant for a period of 1 to 2 min, rinsing as quickly as possible in distilled water, alcohol, and ethyl ether in that order, and then immediately drying. This etch is easily controlled due to its slow rate of etching, and produces samples with clean, sharp surfaces. Pits due to overetching produced varying contrast effects when viewed under polarized light, and are therefore obviously useful for revealing many structural details within the sample. Another effect of overetching was to produce a height varia-

Jan 1, 1968

By B. J. Harlan

THE trying times experienced by the steel industry during the past four years have emphasized the necessity of producing pig iron at the lowest possible cost. The trend in both design and operation of blast furnaces has been toward this end rather than securing maximum production from a unit or group of units. In the following discussion the trend in design of stacks and auxiliary equipment will be taken up before operation is considered. Although few furnaces have been constructed in the past few years, the trend is definitely toward larger furnaces with a hearth diameter of 24 or 25 ft. Such a furnace is very flexible, being able to produce efficiently any desired daily tonnage between 500 and 1000 or more. The detail of the design of furnace stacks, with the exception of the top, has changed little in recent years.

Jan 1, 1934

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 E. A. Elevatorski

Wollastonite, named after William H. Wollaston, an English chemist, is a calcium metasilicate, CaSiO3. It has a short history as an industrial mineral. The earliest production of wollastonite is reported to be from a deposit near Code Siding, located north of Randsburg, Calif. At this locality small tonnages of wollastonite were quarried during 1933-34 and 1938-41, and processed into mineral wool. This operation was largely experimental and virtually no United States production was again reported until the 1950s when a large deposit near Willsboro, N.Y., was developed by the Cabot Corp. A processing plant was placed on-stream in 1953, with nearly continuous production to date, and it is currently operated by Interpace Corp. Since 1958, wollastonite deposits in the Little and Big Maria Mountains of Riverside County, and in the Panamint Range of Inyo County, both in California, have operated intermittently for production of both ornamental and commercial wollastonite. During 1973, the United States was the major producing country, furnishing about 75% of the world's output. Recent production also has come from Finland, Mexico, and Kenya. Small amounts have been shipped intermittently from India, USSR, New Zealand, Republic of the Sudan, Republic of South Africa, and South-West Africa. The principal use of wollastonite is in the manufacture of ceramics, especially wall and floor tiles. Other uses are for paints, fillers, adhesives, reinforcing agents, plastics, fluxes, and glazes. Mineralogy Pure wollastonite, CaSiO3, has the composi¬tion of 48.3 % CaO and 51.7 % SiO,. However, it is seldom found in the pure state due to the ease with which it takes into solution the metasilicates of manganese, magnesium, iron, and strontium. Predominantly, wollastonite occurs as a contact metamorphic deposit forming between limestones and igneous rocks. Commonly associated minerals are garnet, diopside, epidote, calcite, and quartz. It has a specific gravity of 2.8 to 3.0, and hardness of 4.5 to 5 on Mobs' scale. When pure, it has a brilliant white color, but with impurities it may be grayish or brownish. Luster is vitreous to pearly. Melting point of wollastonite is about 1540° C. Wollastonite occurs in coarse-bladed masses, rarely showing good crystal form. It is usually acicular or fibrous, even in the smallest of particles. The most unique property of crushed and ground wollastonite is its cleavage. Fragments of crushed wollastonite tend to be needle-shaped, imparting a high strength, and this property is the basis for many of its uses. The fiber lengths are commonly in the ratio of 7 or 8 to 1, length to diameter. Some crystals of wollastonite fluoresce under short-wave or longwave ultraviolet light, or both; colors ranging from yellow-orange to pink-orange. Specimens may also show phosphorescence. The brightness of wollastonite is a property of considerable importance to the paint industry. Material, 99% pure, with a size of -325 mesh, has a General Electric reflectance rating of 92 to 96%. Chemically, wollastonite is inert and this property makes it useful as a filler and reinforcing agent. There are two polymorphs of calcium silicates: wollastonite, a low temperature form, and pseudowollastonite, a high temperature form. Inversion of wollastonite to pseudowollastonite occurs at about 1120° C, resulting in an increase in the coefficient of expansion and a color change. Pure white wollastonite, on inversion, may change to a cream tint, or various shades of red or brown. The color change is thought to be due to the presence of iron and strontium.

Jan 1, 1975

By S. F. Frederick, G. F. Pittinato

The deformation mechanisms operating in Ti-5Al-2.5Sn at 20°K under uniaxial and biaxial stress fields were determined by using both optical and electron microscopy. In the uniaxially stressed specimens, de-fu~rnation twins were found only in the immediate vicinity of the fracture. Twinning was, however, established as a deformation mechanism under biaxial stress conditions. The same slip systems were opera-tiz,e under both uniaxial and biaxial stress. Prismatic slip was identified as the major slip syslem; however, basal and first-order pyramidal slip also occurred, but to a lesser degree. The interaction of moving dis-locations on intersecting slip planes resulted in the formation of jogs and dipoles. Hexagonal dislocation networks were formed only under biaxial stress conditions. A discussion is given on the formation of hexagonal dislocation networks. IT has been shown that titanium alloys can exhibit unusually high strengths when tested in a biaxial stress field.'-" The high biaxial strengths are a consequence of a strong basal plane sheet texture which results in distinctly anisotropic flow properties. This texture strengthening appears to decrease with decreasing temperature2 and would seem to indicate a change in deformation modes. For example, in a uniaxial tensile test, Ti-5A1-2.5Sn yields isotropically at 20°K but is strongly anisotropic at room temperature. The increase in biaxial ultimate over uniaxial strength at 20°K is also much less than at room temperature. It is known that titanium car] form deformation twins more readily at cryogenic temperatures than at room temperature.4 Since the formation of deformation twins will reduce the degree of basal texture in sheet material,' an accompanying decrease in texture strengthening would be expected. To investigate more fully the nature of texture strengthening at cryogenic temperatures, the deformation modes of Ti-5A1-2.5Sn tested in uniaxial and 1:1 biaxial tension at 20°K were studied by optical and electron transmission microscopy. EXPERIMENTAL PROCEDURE The uniaxial and biaxial stress test specimens were prepared from 0.020-in. thick sheets of Ti-5A1-2.5Sn ELI having the composition shown in Table I. Uniaxial stress conditions were obtained by using flat tensile specimens machined from the sheet material. The longitudinal axis of the tensile specimens was aligned perpendicular to the rolling direction of the sheet. Tile biaxial test specimens were prepared by rolling precut, 19-in.-lengths of sheet into 4-in.-diam cyl- inders. Following longitudinal butt welding, the cylinders were stress relieved at 1000°F for 4 hr. A 9-in. sq "window" was then chemically milled into each cylinder's surface reducing the wall thickness in the milled area to approximately 0.006 in. The testing procedure consisted of pressurizing the cylinders while simultaneously applying a tensile load. Using this technique, a 1:l axial to hoop stress was obtained. Complete details of the specimen and testing procedures are given in Refs. 1 and 2. The biaxial and uniaxial stress specimens were all tested in liquid hydrogen. Specimens for electron transmission microscopy were prepared by first chemically milling to a thickness of about 0.001 in. followed by electrolytic polishing to electron transmission thickness. The chemical milling solution, consisting of 800 ml of water,

Jan 1, 1970

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 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

By Samuel S. M. Chan

The magnetic susceptibilities of some ores and the major rock formations of the Precambrian Belt Supergroup in the Coeur d'Alene mining district were determined both in the laboratory by the use of the Gouy method and in the field with a Bison susceptibility unit. Trace element analysis of the same group of rock samples was also made using the atomic adsorption technique. Results of this preliminary study indicate that some correlation exists between the magnetic susceptibilities and the various rock formations. This may be useful for regional mapping and mineral exploration.

Jan 1, 1974

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 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 J. Handin, S. J. Bauer, M. Friedman

Deformation mechanisms in room-dry and water-saturated specimens of Charcoal Granodiorite, shortened at 10-4s-1, at effective pressures (Pe) to 100 MPa and temperatures to partial melting (?1050°C) are documented with a view toward providing criteria to recognize and characterize the deformation for geological and engineering applications. Above 800°C strength decreases dramatically at effective pressures ? 50 MPa and water-weakening reduces strength an additional 30 to 40% at Pe = 100 MPa. Strains at failure are only 0.1 to 2.2 percent with macroscopic ductility (within this range) increasing as the effective pressures are increased and in wet versus dry tests. Shattering (multiple faulting) gives way to faulting along a single zone to failure without macroscopic faulting as ductility increases. Microscopically, cataclasis (extension microfracturing and thermal cracking with rigid-body motions) predominates at all conditions. Dislocation gliding contributes little to the strain. Precursive extension microfractures coalesce to produce the throughgoing faults with gouge zones exhibiting possible Riedel shears. Incipient melting, particularly in wet tests, produces a distinctive texture along feldspar grain boundaries that suggests a grain-boundary-softening effect contributes to the weakening. In addition, it is demonstrated that the presence of water does not lead to more microfractures, but to a reduction in the stresses required to initiate and propagate them.

Jan 1, 1982

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 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 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

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

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