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By B. J. Dotson, P. N. McCreery, R. L. Slobod, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By P. N. McCreery, R. L. Slobod, B. J. Dotson, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By R. S. Rickard, B. Ball

INTRODUCTION Pyrite responds to the flotation reagents normally used in sulfide flotation systems. For example, it is well known that xanthates are good collectors for pyrite, and cyanide, sulfide and hydroxides are depressants. The particular response of pyrite to these and other reagents is used to advantage in several areas. By careful control of depressant and collector additions, pyrite can be separated from other sulfides by flotation. This is of obvious importance in base metal sulfide flotation where pyrite depression is often required to produce a marketable grade concentrate. Flotation of pyrite has long been employed in gold ore processing, and it appears that pyrite flotation from coal may become important in the future (1). It is probably a direct consequence of this relative ease of separation, plus the low economic value of pyrite, that detailed investigations on the chemistry of its flotation and depression are relatively limited. Gaudin (2, 3, 4) and others, in the mid-1950's published data on the flotation of pyrite, but detailed or consistent mechanisms were lacking. In 1955, Sutherland and Wark's book (5) was published, in which a large , amount of empirical information, especially earlier work of Wark and Cox, was presented. More recently, in 1968, significant contributions have been made by Fuerstenau et al. (6, 7) and Majima and Takeda (8). These papers introduced electrochemical explanations of the effects observed with xanthate and cyanide ions.

Jan 1, 1976

Members whose deaths were reported from Apr 7, 1923, to Apr 5, 1924 Elected Died 1918 ADKINSON, HENRY M 1923 1900 AGNEW, WILLIAM C 1923 1894 ASHLEY, H H 1923 1897 AUSTIN, KENNETH 1924 1903 AYERS, EMMA L C 1923 1913 BAECHTOLD, CHARLES A 1924 1900 BAIN, HUGH A 1924 1919 BASHORE, E GORGAS 1923 1920 BATTELLE, GORDON 1923 1923 BAYLES, GERARD L 1924 1881 BROCK, CHARLES 1923 1903 BROOKE, HENRY 1923 1876 BROWN, HARVEY H 1923 1904 BROWN, THOMAS E 1923 1919 BUCK, DANIEL M 1924 1906 CHALMERS, THOMAS S 1924 1881 CLEMES, JOHN H 1923 1896 COLLINS, HENRY F 1924 1871 COURTIS, WILLIAM M 1923 1915 CRESSON, B F, JR 1923 1921 CROWE, WALDO P 1923 1920 DARNELL, J ORA 1923 1911 DAVIS, HENRY G 1924 1918 DAVIS, ROBERT S 1923 1916 DEANE, WILLARD A 1924 1901 DEMPSTER, WILLIAM 1924 1911 DEVEREUX, W B, JR 1923 1895 DICKENSON, F M 1924 1904 DRUM, FRANK G 1924 1875 DUDLEY, P H 1924 1916 EATON, ARTHUR 1923 1919 EATON,SHERMAN 1924 1911 GRIFFITH, WILLIAM 1924 1919 HILSDALE, PAUL 1923 1922 HODGES, I F 1923 1916 HOFIUS, MAX, T 1924 1914 HUGHES, HOWARD R 1924 1919 HUMMEL, CARL B 1923 1874 HUNT, ROBERT W 1923 1921 JONES, ERNEST EVANS 1923 1917 JOSLIN, CHARLES T 1923 1918 KASJENS, JACOB G 1923 1899 KIRKEGAARD, PETER 1924 1920 KLAUS, HARRY C 1923 1892 KNOERTZER, HENRI1924

Jan 1, 1923

By W. W. Coblentz

THE constants in question pertain to the total radiation and the spectral radiation of a uniformly heated enclosure, or so-called black body. These constants have been determined for the range within which temperatures can be measured with thermocouples. Conversely, using these constants and suitable instruments, such as an optical pyrometer, for example, it is possible to determine temperatures far above the range attainable with the most refractory thermocouples. The formula of Stefan Boltzmann for expressing the total radiation of a black body is R = kT4 in which k is the coefficient or "constant" under discussion. In view of the fact that total radiation pyrometers are usually calibrated on an arbitrary scale, there is no great demand for an exact value of the coefficient of total radiation in absolute value. However, it is intimately connected with the constant of spectral radiation; hence, an accurate determination of the constant k gives a check on the constant of spectral radiation. The distribution of radiation in the spectrum of a black body is represented by Planck's equation, E? = C1?-5 (e c/?T - 1)-'. The spectral radiation constant c, in this formula, is useful in optical pyrometry and in establishing a high temperature scale. The numerical value of the constant c has been determined in the range of temperatures measurable with thermocouples and, also, by extending the temperature scale to higher temperatures by means of total radiation measurements.

Jan 8, 1919

By R. W. Smith, M. E. Brookes

The temperature at which th: quenched 0' (ordered bcc) phase transfo.rms to the ( (complex hexagonal) phase on heating has been examined for certain Ag-Zn and Ag-Au-Zn alloys using an electrical resistivity method. The transition temperature decreases by approxinzately 7°C as the zinc content is reduced by 1 at. pct. The critical temperature, Tc, for long-range order has also been measured for a number of Ag-Au-Zn alloys. Extrapolation to zero gold content suggests that Tc decreases by approximately 5°C per 1 at. pct reduction in zinc content. The 0 phase of the Ag-Zn system exists over a narrow range near the composition Ag zn,' Fig. 1, and has a bcc structure which is disordered above 272°C. Slow cooling to temperatures below the range 274"/258"C allows the complex hexagonal phase, r° to form.2 This is the stable structure at room temperature.3 Upon quenching 0 -phase alloys from high temperatures, it is found that the 0 — (' transformation is suppressed; but ordering takes place (i.e., 0 -0'). This ordered structure can also be obtained by the room-temperature aging of cold-worked (0.4 Deformation of the 0' phase gives rise to a fur- ther hexagonal phase ( (of nearly ideal axial ratio) which reverts to b' within a few hours.= In view of this, it has been suggested that the equilibrium struc-

Jan 1, 1969

GEORGE F. BECKER Dr. George Ferdinand Becker, notice of- whose death appeared in the May Bulletin, was born in New York City Jan. 5, 1847, the son of Alexander Christian Becker, member of a Danish family, and Sarah Cary Tuckernian Becker of Boston. Dr. Becker was the last member of the group of distinguished geologists who, in 1879, were associated with Clarence King at the time of the organization of the United States Geological Survey. He was a leader in mining geology and geophysics, and for many years had been the chief of the Division of Chemical and Physical Research in the Geological Survey, and the investigations under his direction led to the establishment of the Geophysical Laboratory of the Carnegie Institution of Washington. Dr. Becker was a graduate of Harvard University and received the degree of Doctor of Philosophy at Heidelberg, and in 1871 passed the final examinations at the Royal School of Mines in Berlin. He was for four years an instructor of mining and metallurgy in the University of California, from which he went to the United States Geological Survey. In 1896 he examined the gold and diamond mines f South Africa and at the time of the Spanish-American War was detailed to serve as geologist on the staff of General Bell with the army in the Philippine Islands. He died at his hone in Washington, D. C., on Apr. 20'.1

Jan 6, 1919

By Carl Altstetter, Emmanuel deLamotte

The influence of an external stress and plastic deformation on the allotropic transformation of single crystals of a Co-30.5 pct Ni alloy was investigated. Experimental results were obtained from dilatometry, X-ray diffraction, and optical and electron microscopy. The effects of stresses could be conveniently divided into three stress ranges. In range I, from 0 to about 400 g per sq mm, the specimens exhibited a multi-variant phase change on cooling and a considerable amount of retained cubic phase. In range II, from 400 g per sq mm to the elastic limit, hexagonal regions of a given orientation grew in size and the cubic phase disappeared with increasing stress level. In range III, just above the elastic limit, specimens transformed into hexagonal single crystals. It was found that plastic deformation, not applied stress, was the factor which determined whether a single-crystal product was formed. The observed macroscopic shear directions were mainly (112) on cooling, but the behavior was more complicated on heating under stress. To explain these properties of the phase change, a model based on the nucleation of partial dislocations is proposed. IT is well-known1 that, on heating, hcp cobalt transforms into an fcc arrangement by shearing on close-packed planes. The crystallographic orientation relationship of the phases is as follows: the habit plane is (OOO1)hcp ?{lll}fcc and a (1010)hcp direction is parallel to a (112)fcc direction. The temperature at which the transformation occurs in pure cobalt is around 420.C 1,2This temperature decreases with increasing nickel concentration: and at about 30 pct Ni it reaches room temperature. However, many of the transformation characteristics remain essentially the same, particularly the crystallographic features.495 A convenient way of studying the transformation is to alloy cobalt with nickel, thus avoiding the difficulties of doing experiments at the high temperatures needed to transform pure cobalt. Due to the hysteresis of the transformation it is possible to choose a Co-Ni alloy with an Ms temperature below room temperature and an A, temperature above room temperature. Either structure of such an alloy could then be studied at room temperature, depending on whether it had just been heated or cooled to room temperature. The choice of nickel is further favored by the small difference in lattice parameters between cubic cobalt and nickel and the similarity of their physical, chemical, and electronic properties. Co-Ni alloys are reported to have neither long- nor short-range order.6 The main purpose of this work was to investigate the influence of an external stress on the transformation characteristics of Co-Ni single crystals. It may be expected that slip, twinning, and transformation should have many features in common in cobalt, because the (111) planes of the cubic phase operate as slip planes when plastic deformation by slip occurs, they are the twinning planes, and they are the habit planes for the transformation. Many previous investigators7-&apos;6 have concluded that dislocations must play an important role in the nucleation and propagation of the transformation, just as they do for slip and twinning propagation. An external stress will affect their motion, and a study of its influence should yield further information about the atomic mechanism of transformation. The present work extends that of Gaunt and christian17 and Nelson and Altstette18 in both qualitative and quantitative effects of stress. The basic concept underlying all the present theories of the transformation of cobalt and Co-Ni alloys is the motion of a/6<112> partial dislocations over {1ll} planes of the cubic lattice. The ABCABC... stacking of the close-packed planes of the cubic phase can be changed into the hexagonal ABABAB... stacking by the sweeping of an a/6 <112> partial on every second plane. Twinning, on the other hand, requires a shear of a/6 <112> on each close-packed plane. The reverse transformation can be effected in a similar way by a/3 (1010) dislocations moving over every other basal plane of the hexagonal phase. Transformation theories2, 7- 12,14 differ in the details of the nucleation of the transformation and the propagation of the partial dislocations from plane to plane. EXPERIMENTAL PROCEDURE Nickel and cobalt rods supplied as 99.999 pct pure were induct ion-melted together under a vacuum of about 10-5 torr in a 97 pct alumina crucible. An alloy containing 30.5 pct Ni was found to have the desired transformation range, with an Ms near -10°C and an j4s in the vicinity of +10O°C. The ingots were swaged to &--in. rod and electron beam zone-leveled in a 10-6 torr vacuum. This procedure resulted in 12-in.-long single fcc crystal rods (designated I to VII) from each of which several tensile specimens of identical orientation were made. Chemical analysis of the bar ends indicated no contamination or gross segregation and no micro segregation was seen in electron micro-probe scans. Tensile specimens with a 9/32-in.-sq by 1-in.-long gage section were spark-machined from the rods and then electropolished or chemically polished to remove the machining damage and to provide a flat surface

Jan 1, 1970

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.&apos;-&apos; Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,&apos;8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By C. A. Stickels, C. M. Yen

Secondary recrystallization was investigated in vacuum-melted electrolytic iron to which 70 pm N was vacuum-meltedadded. The secondary texture is "near {554}<225>" for material cold-rolled 75 to 90 pct, the sharpness of the texture increasing with increased rolling reduction and with decreased annealing temperature. At reductions of 95 and 97.5 pct the secondary texture is &apos;"near {322)(296)". Both secondary orientations also exist as major components of the primary re-crystallization texture. Development of a strong "near {554) (225)" secondary texture appears to depend on the evolution of the Primary texture to a transition texture depleted in orientations near the secondary orientation before the onset of secondary growth. A variety of qualitative experinzents have been used to show that nitrogen is important in limiling primary grain growth. The presence of nitrogen does not seem essential for the establishment of a transition texture, but a loss of nitrogen during annealing may facilitate growth of grains in the secondary orientation. Secondary grains we shown to form initially at the specimen surface. This is not thought to indicate that surface energies are important in the growth process. It is proposed that the quasi-two-dimensional character of surface grains permits discontinuous growth parallel to the surface before secondary growth of interior grains is possible. An earlier study of recrystallization textures in 90 pct cold-rolled electrolytic iron showed that secondary recrystallization occurred after annealing for several days at 700C1 This type of secondary recrystallization, which had not been reported previously, results in the formation of a strong texture, best described by the indices "near {554}(225)". The purpose of the present work was to investigate the effect of various processing variables on secondary recrystallization in this material and determine the mechanism of secondary grain growth. LITERATURE REVIEW An understanding of the mechanism of a secondary recrystallization process depends on knowing: 1) how grains in the secondary orientation come to be in the primary recrystallization texture; 2) why normal grain growth does not occur; and 3) what factors determine the strength of the secondary texture. For secondary growth of grains of a particular orientation, a certain minimum fraction of the grains must be in that orientation after primary recrystallization. This requirement is apparently satisfied "naturally" in certain systems, i.e., when the primary texture obtained by rolling and recrystallizing material initially randomly oriented contains a sufficient fraction of primaries in the secondary orientation. However, in other cases, e.g., {110}<001> and {100}<001> secondary growth in silicon iron,2 it is necessary to enhance the fraction of primary grains in the secondary orientation by rolling and recrystallizing textured material. In the present case, the "near {554}<225>" orientation is contained within the spread of orientations found in the primary recrystallization texture of iron or bbc iron-base alloys. In systems where the main driving force for secondary growth is the reduction in total grain boundary energy, secondary growth is observed only when normal grain growth is minimized. Four ways in which normal grain growth can be limited are: 1) Limitation by a strong primary texture. When a very strong primary texture consisting of a single component or twin-related components develop, most primary grains are separated from one another by relatively immobile small-angle grain boundaries. The classic instance of this is secondary growth into the primary cube texture in some fcc metals. 2) Limitation by precipitates. Precipitates present in the proper volume fraction with a suitable dispersion will limit primary grain growth. The role of MnS inclusions in impeding normal grain growth in Si-Fe is well-documented.5 3) Limitation by sheet thickness. Normal grain growth slows drastically when the mean grain diameter is of the same order as the sheet thickness. This effect has been used to obtain secondary recrystallization in thin sheets of high-purity silicon iron.&apos; 4) Limitation by solute impurities. It is well-established that certain impurity elements in solution can have a large effect on grain boundary mobility.&apos; However, there does not seem to be any secondary recrystallization process in which primary grain size stabilization has been shown to be due to the drag exerted on grain boundaries by dissolved impurities. In certain systems, e.g., secondary recrystallization in silver,&apos; the means by which normal grain growth is limited has not been identified, and solute-impurity limitation might be suspected. In order to understand the factors which determine secondary texture strength in three-dimensional growth, it is necessary to examine in more detail the current picture of general secondary recrystallization processes. Following Cahn,9 it is assumed that the primary grains have a range of sizes and that secondary growth of one of the large grains in this distribution is possible when it exceeds a critical size with respect to its neighboring grains. The critical size depends on the ratio ?S/?p, where ?s is some sort of average grain boundary energy between the potential secondary and the primary grains and ?p is some sort of average grain boundary energy between primary grains. For a constant primary grain size, the critical size for secondary growth increases as ?$/?p increases. May and Turnbull5 have incorporated the

Jan 1, 1969

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

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

Jan 1, 1970

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET&apos;s and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.&apos; More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET&apos;s. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET&apos;s with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.&apos; The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite&apos; as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,&apos; but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion&apos; in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ&apos;. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3&apos;4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By D. P. Pope, T. Vreeland

Observations of dislocations in zinc using Berg-Barrett X-ray micrography confirm the validity of a dislocation etch for (1010) surfaces. A technique for measurement of the depth in which dislocations can be imaged in X-ray micrographs is given. This depth on (0001) surfaces of zinc was found to be 2.5 µ using a (1013) reflection and CoKa radiation. BUCHANAN and Reed-Hill (B & RH) have recently questioned the ability of a dislocation etch to reveal all of the basal dislocations which intersect (1010) surfaces in annealed zinc crystals.&apos; This etch was developed by Brandt, Adams, and Vreeland who conducted a number of different experiments to check its ability to reveal dislocations.2,3 B & RH prepared (0001) foil specimens for transmission electron microscopy from annealed crystals and observed dislocation densities of about l08 cm per cu cm in the foils, while the etch indicated densities of the order of l04 cm per cu cm in their annealed crystals. As this etch has been used in a number of studies of dislocations in zinc, it is of considerable importance to reassess its validity in the light of the B & RH results. The X-ray work reported here was undertaken to check the ability of the etch to reveal dislocation intersections on (1070) surfaces of zinc. The X-ray technique was chosen for this check because it could be applied to the as-grown crystals with a relatively small amount of specimen preparation. We believe that the possibility of accidental deformation in preparation of the bulk specimens is considerably less than that for thin foil specimens suitable for transmission electron microscopy. Unfortunately, basal dislocations are not visible on Berg-Barrett topo-graphs of (1010) surfaces, which are the surfaces on which the etch is most effective. Therefore, a one-to-one correspondence between the etch and X-ray observations could not be made. Basal dislocations near (0001) surfaces have been observed by Schultz and Armstrong4 using the Berg-Barrett technique, but they did not report the as-grown dislocation density observed in their crystals. We have applied the X-ray technique in this study to surfaces oriented from 1 to 2 deg of the (0001) to determine the basal dislocation density, and have compared this density with that observed using the etch on a (1070) plane of the same crystal. The X-ray observations permit determination of the depth in which basal dislocations can be observed under the diffracting conditions used. SPECIMEN PREPARATION High purity zinc crystals are very soft, so a good deal of care must be exercised in the preparation of observation surfaces. As-grown crystals approximately 2.5 cm in diam and 20 cm long were acid cut into 1.25 cm cubes. A thin slab was cleaved from an (0001) surface to produce an accurately oriented reference surface on the specimen. Some of the cubes were examined in the as-machined condition while some were annealed in argon at 410°C for 2 hr. Heating and cooling rates were less than 2°C per min. Some of the specimens were scratched on a (0001) surface with a razor blade to produce fresh dislocations. Approximately 2 mm of material was acid lapped from one face of a cube to produce a surface oriented between 1 and 2 deg from the basal plane and parallel to the [1210] direction. A (1070) surface was also acid lapped. The lap used a 1 to 3 pct solution of HN03 in water to saturate a soft cloth which was backed by a stainless steel plate. The cloth was moved over the crystal surface at a rate of 20 cm per sec while a normal force of about 4 g was maintained between the cloth and the specimen. As-lapped surfaces were examined as were surfaces which were chemically and electrolytically polished after lapping. The small angle between a lapped surface and the (0001) plane was measured to 0.1 deg using a Unitron microgoniometer microscope (the cleaved surface was used as a reference in this measurement). The microscope was modified so that the intensity of reflected light could be continuously monitored on a meter. This modification produced nearly a ten-fold increase in the reproduceability of orientation readings. OBSERVATIONS The Unitron Microgoniometer observations indicated that the lapped surfaces had a terraced structure with the terraces quite rounded and spaced about 0.1 mm in the [1010] direction. The maximum change in slope between terraces was 0.25 deg, indicating a terrace height of about 0.1 µ. A Unitron measurement of the average angle between (0001) and a lapped surface was checked by micrometer measurement of the specimen and found to agree within 0.1 deg. The Berg-Barrett micrographs using (1013) reflections and CoKa radiation5 revealed subboundaries, short dislocation segments, spirals, and loops near the surfaces which were oriented from 1 to 2 deg of the (0001). Micrographs of surfaces prepared by lapping appeared very similar to those of the chemically and electrolytically polished surfaces. The loops and spirals were not extinct in (1013) or (0002) reflections, indicating that they have a nonbasal Burgers vector. Extinctions of the short, straight dislocations indicated that they belonged to an (0001)(1210) system. Fig. 1 is an example of a micrograph which shows a subboundary, and dislocation segments which are pre-

Jan 1, 1970

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,&apos; will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By K. P. Mukherjee, K. P. Gupta, J. Bandyopadhyaya

Even though a lot of work has been done in the past to establish phase equilibrium in the Cu-Si system a re cent investigation casts some doubt about the existence and crystal structure of some of the phases that form in the composition range of 15 to 25 at. pct Si in Cu. The present investigation was carried out using high temperature X-ray diffraction technique along with other standard techniques to study the phases in this composition range. The high temperature 6 phase appears to be tetragonal with parameters a,, = 8.815A, c, = 7.903A, and co/ao = 0.896. The reported bcc E phase exists at room temperature and at least up to 780°C and appears to undergo a transformation near 600°C. The phase appears to be cubic but not of the bcc type. The ? phase appears to undergo a transformation, as has been indicated by earlier investigators, and the low temperature form of .? phase is tetragonal with parameters a, = 7.267A, co = 7.8924, and co/ao = 1.086. THE Cu-Si binary system has been investigated by several investigators1" and several intermediate phases,?,e,?&apos; at lower temperatures and ?,ß,0,e, and ? at higher temperatures, were observed between terminal solid solutions of copper and silicon. Even though the existence of the e phase and the transformation in the ? phase were reported in many early works, in a recent study of this system Nowotny and Bittner6 doubted the existence of the e phase and phase at 550°C. Among the high temperature phases, the 6 phase was reported to have a complex cubic structure with parameter a, = 8.805A.7 Nowotny and Bittner, however, suggested that the structure of the 6 phase might be of CsCl type. In order to check these contradictory reports the present study was taken up to investigate the Cu-Si binary system in the composition range of 17 to 25 at. pct Si. EXPERIMENTAL PROCEDURE Weighed amounts of copper (99.99 pct) and silicon (99.9 pct) were induction melted in recrystallized alumina crucibles under argon gas atmosphere. The alloys containing 17, 18, 20, 21, 21.2, 22, and 24 at. pct Si were annealed in evacuated and sealed quartz capsules at 700°C for 3 days and subsequently water quenched. Other than this annealing, the 21.2 at. pct Si and 24 at. pct Si alloys were annealed at 550°C for 10 days, the 17 at. pct Si alloy was annealed at 750°C for 3 days, and the 22 and 24 at. pct Si alloys were annealed at 780°C for 2 days. All annealing temperatures were controlled to within *l°C. Alloys after quenching were subjected to metallographic and X-ray diffraction investigation. A solution containing 5 g FeC13 + 10 cc HCl + 120 cc H2O diluted with six times its volume with water was used as etching reagent. A 114.6 mm diam Debye Scherrer camera was used for obtaining diffraction patterns. The 17, 21.2, and 24 at. pct Si alloys were subjected to high temperature diffractometry using a Tempress Research High temperature attachment and a GEXRD VI diffractometer. For the 6 phase (17 at. pct Si alloy) powder specimen from a 750°C annealed alloy was reheated to 750°C in the high temperature attachment for 1½ hr before taking a diffraction trace. A 550°C annealed and slowly cooled phase (24 at. pct Si) alloy was first reheated to 550°C. a diffraction trace was made after annealing it for 2 hr, and subsequently it was heated to 716OC and kept at this temperature for 2 hr before taking a diffraction trace. For the e phase (21.2 at. pct Si alloy) a 550°C annealed and slowly cooled specimen was heated first to 425°C and annealed at this temperature for 2 hr before taking a diffraction trace. Subsequently, the specimen temperature was raised to 495", 540°, 603", 635", 682", 720°, and 748°C and homogenized at each temperature for 1 hr before taking diffraction traces. The powder specimen temperature was controlled to within +2oC at each temperature and argon gas, purified by passing it at slow rate through a fused CaC12 column, hot (800°C) copper and titanium chips and finally through a P2O5 column, was used to prevent oxidation of the powder. For all X-ray work copper-radiations at 25 kv, 15 ma (for Debye Scherrer technique), and 40 kv, 20 ma (for diffractometer tech-nique) were used. RESULTS AND DISCUSSION At 700°C the alloys containing 17 to 21 at. pct Si showed two phases while the 21.2 at. pct Si alloy was found to be single phase. The X-ray diffraction patterns of the two-phase alloys were consistent with the phase (ßP-Mn type structure) and the phase (21.2 at. pct Si) patterns. The diffraction patterns of the 17 at. pct Si alloy quenched from 750" and 700°C were identical. According to the accepted Cu-Si phase dia-gram4,5,10 the 17 at. pct Si alloy at 750°C should be in the (k + 6) two-phase region and very close to the -phase boundary. The identical patterns possibly resulted from the decomposition of the 6 phase on

Jan 1, 1970

By Malcolm McColl, C. A. Mead

Thin films (of mica have unique attributes that are exceptionally good for studies of high-field conduction mechamisms in thin-film insulators and the quantum mechanical tunneling of electrons from metal to metal. The principal advantages of using mica films are that the films are crystalline and the cleavage planes occur every 10Å. This property results in films whose thicknesses are integral multiples of 10Å and whose surfaces are uniformly parallel over sizable areas. Hence, very well-defined metal -mica-metal structures are possible. Furthermore, the fact that the insulator is split fro??! a bulk sample allows the index of refraction, dielectric constant, forbidden energy gap, and trapping levels and their density- to be obtained directly from measurements performed on thick samples Of mica rather than requiring that these properties be interred from the conduction characterrsties alone. In the work to he described, all the cleaving was done in a high vacuum just prior to the evaporation of metal elertrodes so as to avoid air contamination at the interfaces. Results of these studies indicate that the current through the 30 and 40Å films exhibited quantitative agreement with the theoretical voltage and temperature dependence derived by Strallon for the tunneling of electrons directly from metal to metal. Thicker films at room temperature exhibited volt-ampere curves suggesting Schottky emission of electrons from the cathode into the conduction band of mica. However, the thermal activation energy was smaller than that found from other measurements, and the experimsntal Schottky dielectric constant was larger than the square of the index of refraction. These facts would indicate that the electrons were being injected into polaron stales ill the iusulator. At low temperatures and high fields, the current through the thicker films did not exhibit the Fowler -Nordheim dependence as would be predicted by a simple extention of the theory of field emission into a vacuum. THE mechanism of electrons tunneling through insulating films has received considerable attention in the last few years due to the devices possible utilizing tunneling&apos;-4 and the success of tunneling in the study of superconductivity.5,6 Until the recent paper by Hartman and chivian7 on the study of aluminum oxide, there had been no reported successful quantitative experimental fit to the theory. Their method of fabrication necessarily results in a polycrystalline insulator, the stoichiometry of which is nonuniform from one side to the other. This structure also introduces complications to the shape of the barrier which is set up by the insulator since the insulator possesses a spatially nonuniform band structure and dielectric constant. Due to these facts an analysis of the data in terms of a pviori barrier shape is of questionable validity. The use of muscovite mica not only overcomes these disadvantages but, as an insulating thin film, provides physical properties (dielectric constant. trapping levels and their densities, forbidden energy gap, and so forth) that are identical to the easily measured values of the bulk sample. Furthermore, it is a single-crystal insulator whose cleavage planes (10Å apart8,9) provide uniformly parallel surfaces of well-known separation. This material is therefore ideally suited to the study of electron-transport phenomena. Von Hippel10 using a 6.5-µ-thick sample was the first to observe the high-field conductivity (=5 x l06 v per cm) of mica. No attempt was made to develop an empirical formula, but Von Hippel concluded from intuitive arguments that the current was being space-charge limited by trapped electrons. Mal&apos;tsev11 in a more recent investigation at high fields observed a dependence of the conductivity a on the field F of the form exp(ßF1/2). This dependence was attributed to the Frenkel effect,12,13 a Schottky type of emission from filled traps. No mention in the English abstract was made of the thicknesses of his samples or, and more important, of how well the value of ß fit Frenkel&apos;s theory. In 1962 Foote and Kazan14 developed a technique for splitting mica to a thickness of less than 100Å and observed a dependence of the current density j on the field of the form j = jo exp(ßF1/2) on a thin sample thought to be 40Å thick. Assuming that this was a Schottky emission process and that the appropriate dielectric constant for such a mechanism would be closer to a low-frequency value of 7.6, Foote and Kazan calculated from ß an independent thickness of the mica of 36Å. No further investigation was made of the phenomenon. However, the work reported in this paper indicates that the film measured by Foote and Kazan was probably 60Å thick, the error arising from the measurement of the very small metal-insulator-metal diode areas that were used, along with the diode capacitance and dielectric constant, to calculate the thickness. In the research reported in this paper, Foote and Kazan&apos;s technique was modified to cleave muscovite in a vacuum of 10-6 Torr, immediately after which metal electrodes were evaporated creating Au-mica-A1 diodes. Aluminum was chosen because of its strong adhesion to mica, as necessitated by the

Jan 1, 1965