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By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By M. S. Burton, J. E. Ritter

The sessile-drop technique was employed to study the effect of atmosphere and alloy additions of titanium and chromium on the surface tension and contact angle of nickel on sapphire substrates at 1500oC. Shear tests were conducted on the solidified sessile drops. The liquid-gas surface tension of pure nickel on sapphire was found to be 1747 ergs per sq cm, with a contact angle of 109.6 deg. The surface tension and contact angle were not affected significantly by the four atmospheres, vacuum, impure argon, pure argon, and pure hydrogen. Small additions of titanium and chromium decreased the contact angle and for the same alloy content, contact angles were lower in pure argon than in pure hydrogen. On the basis of shear-test results , the most probable cause for adhesion in the Ni-Al2O system is the formation of NiO:Al2O3 spinel at the interface; in the titanium alloy-Al2O3 system adhesion is thought to be due to a mechanical interlocking effect; in the chromium alloy-Al2O3 system adhesion is believed to be the result of solid-solution formation involving Cr2O3 and Al2O3 at the interface. In the last few years there has been considerable interest in reinforcing metals with ceramic whiskers. It has been postulated that, by reinforcing nickel with sapphire whiskers, high-temperature strengths su- perior to those of the best current nickel alloys can be achieved.' To fabricate a whisker-metal composite having optimum density and strength, understanding of wettability and adherence in the system is of prime importance. Although there has been some previous research in this a a need for further studies has been cited4-8 to understand better the effects of impurities, alloys additions, and atmosphere on the wetting and bonding of metals to metal oxides. The purpose of this research was to investigate the factors involved in the wetting and adherence of nickel/nickel alloys to sapphire (single-crystal a Al2O3). Sessile-drop experiments were conducted in vacuum, impure argon, pure argon, and pure hydrogen, to determine the effect of atmosphere on the contact angle of the metals on sapphire, and the liquid-gas surface tension of pure nickel. The solidified sessile drops were sheared from the sapphire substrate to measure the bond strength between the metal and ceramic. The alloy additions chosen were titanium and chromium since both enhance the wetting of nickel on sapphire.2, 3c Also, titanium is commonly used when brazing metal-to-ceramic seals to improve adherence. Since chromium forms an oxide that is completely soluble in sapphire, it was thought that the oxide could serve as a transition phase to promote bonding between the Ni-Cr alloy and sapphire. I) EXPERIMENTAL APPARATUS AND PROCEDURE The sessile-drop apparatus was a horizontal furnace, with an induction-heated, cylindrical molybdenum susceptor in a water-cooled Pyrex chamber. This apparatus was patterned after that of Williams and Nielsen.7 A flat Pyrex window at each end of the furnace allowed temperature measurements to be made at one

Jan 1, 1968

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

By Fathi Habashi

Chalcopyrite can be readily leached with HNO3, but the recovery of elemental sulfur does not exceed 50% under the most favorable conditions. Preheating at 500°C in a slightly reducing atmosphere increases the recovery of elemental sulfur to about 65%. Chalcopyrite can also be treated with HNO3 in a pressure reactor at 110°C to solubilize selectively the copper while iron remains in the residue as an oxide. The recovery of elemental sulfur also improved when preheated chalcopyrite is treated in this way. Stainless steel should be an adequate material of construction.

Jan 1, 1974

By R. C. Hall

We are pleased to confirm some of the mechanical data presented by Dr. Detert on the 18 pct Ni marag-ing steel.15 Bar 3 in. in diam and containing 0.02 wt pct C, 18.5 Ni, 8.9 Co, 5.1 MO, 0.55 Ti, 0.05 Al, and balance iron has been examined in our laboratory. Cylinders 0.5 in. high and 0.4 to 0.5 in. in diam were cold-compressed from 3 to 40 pct reduction in height. Table VI shows some typical data; deformation in-

Jan 1, 1968

By Nicholas J. Grant, Italo S. Servi

Extensive data of minimum creep rates and rupture times for high purity and commercial aluminum confirm the existence of a transition range from the low temperature-type to the high temperature-type behavior. The data are analyzed in line with the suggested theories of deformation of metals. CONSIDERABLY more work has been done on the rupture and creep behavior of commercial alloys than on the less complex, high purity metals. As a result, certain fundamental behaviors are overlooked. One of the lesser known variables affecting the high temperature behavior of metals is the impurity content (or alloy content). Impurities are known to affect strongly the recrystallization temperature, electrical resistivity, and other properties of metals, but the effect on creep and other high temperature mechanical properties has been determined for very few materials. In view of these facts aluminum appears to be a fairly ideal metal, since it is available in a wide range of purity contents from 99.995+ down through the 2s (99.0 + Al) and 3s (1.2 Mn) grades in small steps. It is highly resistant to oxidation and other surface instabilities, leaving recrystallization and grain growth as virtually the only instabilities. Control of grain size is also well standardized. Limited data on the creep of aluminum have been obtained by Dushman et a1.l for high purity aluminum; by Sherby2 on 2s aluminum of variable grain size; and by Dorn and Tietz³ on cold-worked 3s aluminum. Experimental Procedure The apparatus consisted of a constant stress, creep testing unit similar to the type described by Hop-kin.' The specimens were held at temperature for 30 min before loading. The loading time was less than 2 min. Factors affecting the accuracy of the data were: 1-—the temperature gradient and control, ± 3°F; 2-the stress determinations, ± 1.5 pct; and 3—elongation measurements (1 in. gage), ? 0.001 in. Three grades of aluminum were tested: 1— high purity (99.995 pct Al), 2—2s (99.3 pct Al), and 3—3s (98.2 pct Al). The spectrographic analyses of these materials are reported in Table I. The specimens were annealed then electropolished in a perchloric-acetic mixture before testing. Data on heat treatments and grain size obtained appear in Table 11. The entire creep curve was determined for almost all of the tests. A few tests were interrupted after the beginning of the third stage of creep, and in these cases the rupture time was estimated. Experimental Results Constant stress creep-rupture testing gives a much longer, more accurately measurable second stage of creep than constant load testing. This behavior is in agreement with the results obtained by Andrade for lead (see Fig. 1). If the test is run to completion, the third stage of creep appears as soon as stress intensification occurs. In the case of specimens which fail in a ductile manner, the stress intensification begins when the sample starts "necking". This differs from the "high temperature brittle" specimens in which the stress intensification is caused by intercrystalline cracking. These specimens

Jan 1, 1952

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T'K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall' who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,' consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By D. E. Trout, W. R. Hibbard

Previous investigations have shown that the cold rolling textures1n2 and the drawn wire textures3 of copper change their secondary components after the addition of about 1 pct aluminum and 5 pct zinc, but do not change after the addition of as much as 30 pct nickel. However, few data are available on compression textures. Barrett4 reports from unpublished work with E. L. Layland that compression rolled copper develops a texture which is predominately (110) in the compression plane with a secondary spread to (113) and weaker spread to (100) as shown in Fig 1. However, 70-30 alpha brass similarly treated develops a texture again predominately (110) in the compression plane and with a weak secondary spread to {113} but with moderate (111) secondary intensities illustrated in Fig 2. Experimental Procedure Specimens of the compositions shown in Table 1 remaining from a previous investigation3 were annealed to a grain size of 0.090 mm average diam and machined to cylinders 0.20 in. diam and 0.20 in. high. Cylinders were compressed 90 pct reduction in height between lubricated steel blocks in a tensile machine. Glancing X ray photo-grams using copper K-alpha radiation were taken at an angle of 0 degrees to the compression surface. (111), (002) and (220) rings were analyzed to define the textures shown in Table 1. The results are in agreement with Barrett4 as to types of textures and are essentially in agreement with previous work1,2,3 as to the effects of composition. In the wire study3 it was reported that the 4.99 pct zinc alloy had a brass-type texture, while the data in Table 1 indicate a copper-type texture for compression. The wire specimen of the 4.99 pct zinc alloy was re-examined by X rays and it was established that the [loo] component still exists in the wire axis. Therefore, Table 2 of Ref. 3 is in error and should indicate a double [ill], [loo] copper-type texture for this alloy. This correction results in complete consistency with regard to compositional effects, namely that copper and its alloys containing up to approximately 1 pet aluminum, 5 pct zinc and at least 30 pct nickels develop a copper-type texture and more concentrated copper-aluminum and copper-zinc solid solution alloys will form a brass-type texture. Summary Compression textures developed in copper and its alpha solid solution alloys of aluminum, nickel and zinc are essentially the same types as those re- ported by Barrett4 with compositional effects occurring at approximately the same percent additions as previously reported for rolled sheet182 and drawn wire.3 The Scovill Manufacturing Co., Waterbury, Conn., furnished the copper and brass alloys, performed certain chemical analyses and supplied laboratory facilities where needed. References 1. Brick, Martin and Angier: Tram. A.S.M. (1943) 31, 675. 2. Dahl and Pawlek: Zlsch. Melall. (1936) 28, 266. 3. Hibbard and Yen: Trans. AIME 175, 126. Melals Tech.. Feb. 1948, TP 2334. 4. Barrett: Structure of Metals, mc- Graw-Hill (19421, 386.

Jan 1, 1950

By Walter Kauenhowen

GeRmany's crude-oil production during 1936 totaled 3,112,494 bbl., an increase of 5.2 per cent over the 3,007,711 bbl. produced in 1935. The official monthly production figures published in 1936 report only the individual production figures of the three old established fields, whereas since 1936 official reports combine the production of all other fields into one figure. According to these published data, and using a conversion factor of 1 metric ton equaling 7 bbl., the oil production of Germany in 1936 was as follows:

Jan 1, 1937

By D. H. Wertz, R. R. Furlong

A. E. LEE*—I would like to ask Mr. Neale if he has determined the moisture content of his dried retort. Also, has he ever experienced difficulty with bending in the dry room where the green wel retorts contain 17 pet moisture and are placed 3 in. apart? M. M. NEALE (replying for authors)— I cannot answer your first question as we have had no experience with that. Setting the retorts 3 in. apart, we had no trouble with bending. We thought we would, anticipated we would, but did not. L. P. DVVIDSON*—You mention,

Jan 1, 1950

By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By J. O. Brittain, E. P. Lautenschlager, F. Felberbauer

This investigation was undertaken to evaluate the effect of a dispersed phase in a iron upon the strain hardening and the stress dependency of dislocation velocity as inferred from the strain-rate sensitivitv. Experiments were made in a-iron specimens with controlled amounts of carbon and/or A12O3. They were tested at various temperatures between 195' and 373 'K under a variety of conditions oj-concentration, strain rate, and quench aging. The resulting yield strength, flow strength, and strain hardening increased with addition of Al2O3. The parameter m, measured from changes in strain rate, was xsed to describe the stress dependency of the dislocation velocity. m was found to increase with additions of A12O3, increasing carbon in solution, and with increasing temperature. When applied to a recent model for yielding based upon dislocation multiplication and velocity characteristics, the values of m alone did not successfully predict yielding for the materials of this investigalion, but had to be adjusted with a consideration of the number of unlocked dislocations nucleated heterogeneously at discontinuities or inclusions. The change of yield strength with Al2O3 Interpar-ticle spacing appeared to obey a theory of Orowan. EVER since the concept of dislocations has been introduced to explain plastic deformation in crystalline materials, the origin of dislocations and the source of the number of dislocations required to account for plastic deformation have been persistent questions. Ruling out the possibility of homogeneous nucleation,' Gilman2 drew attention to the various cases of heterogeneous nucleation as the source of dislocations, whereas Frank and Read3 introduced the Frank-Read source. However, Gil-man found that the Frank-Read sources did not play a dominant role in the deformation of LiF crystals, but that small precipitates are often, if not always, associated with the nucleation of dislocations. In LiF crystals, however, most of the dislocations arose through the multiplication of moving dislocations in a mechanism described by Koehler4 and Orowan,5 Thus, relatively few precipitates could account for a large number of dislocations. A similar observation of dislocation nucleation at inclusions of precipitates was made by Stein and LOW' on Si-Fe crystals. Their crystals contained

Jan 1, 1964

By Wheeler P. Davey

In an article in the General Electric Review, January, 1915, reference was made to the X-ray examination of a steel casting 9/16 in thick. Fig. 1 shows one of the radiographs thus obtained. All these radiographs showed plainly the tool marks on the surface of the casting. All but one showed peculiar markings the shape of which strongly suggested that they were indeed the pictures of holes in the interior. A circular piece, 1 in. in diameter, was punched from the casting at a point where the radiograph shown in Fig. 1 indicated that a blow-hole should be found. (Location of sample shown by circle in Fig. l.) Fig. 2 is a photograph of the end of the punching, showing the hole that was found. Since that article was written it has seemed desirable: (1) to obtain data from which the exposure necessary for any thickness of steel could be at once calculated; (2) to find the thickness of the smallest air inclusion which could be radiographed in a given thickness of steel; (3) to determine in what direction to hope for further progress; and (4) to develop the technique of radiographing metals. In order to gain some preliminary data, several pieces of 1/2-in. (12.5-mm.) boiler plate were obtained, 5 by 7 in. (12.5 by 17.5 cm.) in size. In one of these, holes were drilled in such a way that the axis of each hole was midway between the faces of the steel and parallel to those faces. The diameters of these holes were as follows: Hole number Diameter I.........................................1/4 in. =6.3 mm 2........................................1/8 in. =3.l mm. 3................................... 1/16 in. = 1.6mm. 4....................................... 1/32 in. = 0.8 mm. 5........................................1/64 in. = 0.4 mm. Exposures were made on Seed X-ray plates at 20 in. (50 cm.) distance with Coolidge tube X-117, operated on Scheidel-Western induction coil with mercury turbine break. The X-ray plate was placed on a sheet of 1/8in. (3.1-mm.) lead. The steel was placed above this and a Iead

Jan 1, 1916

By Eric Sinkinson

MANY of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally enclosed in-serpen-tine masses, somewhat decomposed, and in mining it wall rock is inci-dentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumna, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18° C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact; MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18° C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H20) or (4MgCO3.Mg(OH)25H20), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2. The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates. The range in published figures for solubility

Jan 1, 1936

By Rodney P. Smith

THE solubility of columbium nitride in ? iron has been determined for the temperature range 1191o to 1336°C from the nitrogen content and metallogra-phic examination of a series of Fe-Nb alloys.* (0.0 to 0.92 pct Nb) equilibrated with a purified gas mixture of 1 pct hydrogen in nitrogen. The method is the same as that used by Darken, Smith, and Filer' to determine the solubility of aluminum nitride in y iron. The variation in the furnace temperature during an equilibration period was about ± 2.0°C. Each sample was approximately 1/2 in. wide, 2 in. long, and 1/16 in. thick. A time series at 1200°C using samples of highest columbium content indicated that one day was sufficient for equilibrium; however, to be on the safe side all samples were left in the furnace for either two or three days. Afterequilibration, the samples were brought to room temperature by quenching in water. The experimental results are shown in Fig. 1. To be in accord with the values reported by Wriedt and Gonzalez2 and the temperature coefficient of our results at higher temperatures, the nitrogen content of iron at 1191oC is assumed to be slightly lower than our experimental value. Our data for the single-phase regions are not sufficiently accurate to establish an interaction coefficient for nitrogen in these alloys. However, the change in nitrogen content with change in alloy content for a number of systems (Fe-N-A1;3,1 Fe-N-Ni;372 Fe-N-Si.3949 Fe-N-V;3,5 Fe-N-Cr;3,6 Fe-N-Mo3,7) has practically the same value for the liquid alloy at a temperature near 1600°C as for the solid alloy at temperatures near 1200oC when the alloy content is below a few percent. On this basis the lines through the single-phase regions have been drawn with a slope corresponding to an increase in nitrogen of 0.0013 pct per 0.1 pct Nb.3 The straight lines through the two-phase regions were drawn with a slope corresponding to a one-to-one atom ratio of nitrogen to columbium in the nitride. The X-ray

Jan 1, 1962

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

The Ortiz Mountain property is located approximately 40 km (25 miles) southeast of Santa Fe and 13 km (8 miles) from the village of Cerrillos. The property embodies a Spanish mineral grant from which Gold Fields acquired about 2, 200 hectares (900 acres of surface and mineral rights. Following a period of exploration, metallurgical testing and development of a feasibility study in 1974, the decision was made, because of the higher gold price in the fall of 1978, to place the property into production. the gold is confined in a quartzite breccia; it is an unusual occurrence because the gold in this host rock is leachable at minus 19 mm (3/4 in. ). Total ore reserves are estimated at approximately 3.6 million mt (4 million st) averaging 1.89 g per mt (0.055 oz per st) based on a cut-off of 0.7 g (0.02 oz). The ore will be recovered by open pit mining at a stripping ratio of 1. 2:l. Production is scheduled for 13,600 mt (15,000 st) of ore per week or approximately 680,000 mt (750,000 st) per year. Primary crushing of pit-run material is by a 1,070 by 1,015 mm (42 in. by 40 in.) jaw crusher. Crushed ore is conveyed to stockpile and then to a 2.13 m (7 ft) standard crusher with the screened over- size crushed in a 1.5 m (5 ft) tertiary cone crusher. The screen undersize, the final product for leaching, is minus 19 mm (3/4 in. ). A 1, 360 kg (3,000 lb) sample is cut from the crushed ore stream, further crushed in a small jaw crusher and then sampled in two more stages by Vezin samplers to produce a final 13.6 kg (30 lb) sample for assaying. Pebble lime is then added to the ore on the belt as it is sent to the conveyor gantry spanning the leach pads. A tripper on this moving gantry stacks the leach ore without compaction. The entire crushing plant and conveying system is of open-air construction. Leach pads have a total length of 515 m by 60 m (1,700 ft by 200 ft) wide with usable dimensions of 490 m by 58 m (1,600 ft by 190 ft). The directional length slope is 3. 870 with 370 on the width. The pad is constructed of 175 mm (7 in. ) thick asphalt containing a rubberized asphalt membrane. It is divided by a 300 mm (1 ft) high curb into eight segments. Each segment is loaded with 13,600 mt (15,000 st) of ore, which is one week's production. Optimum working height of a pad is considered to be 3. 0 m (10 ft) with a maximum height of 4. 0 m (14 ft).

Jan 1, 1981

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,' the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.' It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By Eric Sinkinson

MANY of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining' of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally. enclosed in serpen-tine masses, somewhat decomposed, and in mining it wall rock is inci-dentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumina, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18° C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact, MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18° C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H20) or (4MgCO3.Mg(OH)25H20), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2, The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates.. The range in published figures for solubility

Jan 1, 1936

By C. H. Li, R. J. Stokes, T. L. Johnston

A portion of the Ni3Cr-Ni3Al phase dzagram has been investigated, including the precipitation of 1 (Ni3Al) as well as the existence of ordered Y (Ni matrix), Extensive metallographic studies by electron microscopy have been carried out and X-ray diffraction diagrams have been taken at both elevated and ambient temperatures, No long-range ordering of the phase was found above 893°C (1639°F) in the compositional range investigated. The high rate of formation of the ordered ?1 phase upon quenching has been confirmed, a phenomenon which up to the present Lime has retarded the understanding of this phase diagram, Specimens with controlled amounts of ?1 exhibited up to a six-fold improvement in yield and creep strength compared with single-phase Ni-Cv-A1 alloys. MOST of the important high nickel heat-resistant alloys are related to the nickel-chromium-aluminum system. One of the important functions of the aluminum, often accompanied by titanium, is to produce a precipitate of the very fine ?1 phase (Ni3A1, X) where X may be Ti, Cr, or other elements. A number of investigators1-" have demonstrate the presence of y' in these alloys but most of their materials contained large amounts of other elements resulting in appreciable amounts of con- fusing phases such as carbides. Further clouding of the precise role of y' has been the suspected existence of an ordering reaction in the y matrix itself, ro-3,12-17 It appeared from these investigations that aluminum in Ni-Cr alloys would raise the ordering temperature of the matrix from 540°C at NisCr to 1300°C at Ni,Al. In support of this possibility, the matrix phase in the parallel Ni-Fe-A1 system is ordered to very high temperatures.1 OBJECTIVES OF THIS RESEARCH From this survey of the literature it appeared desirable to conduct an investigation of the simple Ni-Cr-A1 system using the alloys of the highest available purity to avoid the complication of foreign phases and thereby isolate the structures in the Ni-Cr-A1 system. Procedures were developed to study ? - ?o and ? - ?1 equilibria. Preliminary mechanical tests at elevated temperatures were also conducted.

Jan 1, 1962