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By Lars Osen

This investigation was undertaken to contribute to the understanding of underground pull tests by conducting laboratory tests under closely controlled conditions. Steel bolts, instrumented with electrical resistance strain gages, were anchored in an aluminum block, a granite block, and a steel sleeve, and were subjected to pull tests. The bearing plates used were either flat7 dished, or embossed. In pull testing a bolt that is prestressed, there is a range of loading during which bolt load is greater than the jack-applied load, This study showed that preload, the size, shape, and type of bearing plate; and the geometry of the system determine the point at which bolt load and applied load become equal. The effects on bolt load of both a theoretical solution and actual pull tests were analogous and led to similar results.

Jan 1, 1965

By Leonard Obert

This Bur of Mines investigation considers the deformational behavior (creep) of pillars made from three quasi-plastic rocks--salt, trona, and potash ore. The first phase of this study considers the design of a model pillar suitable for creep tests; in the second phase, six model pillars prepared from salt from two sources, from trona, and from potash ore. The pillars in each group were subjected to a different but constant axial stress, and the axial strain was measured for 1,000 hours.

Jan 1, 1965

By James F. O?Neil

Brown iron ore deposits in Quitman County, Ga., were investigated by the Federal Bureau of Mines in cooperation with the State of Georgia, Department of Commerce, and the University of Alabama. Ninety-one holes were drilled, having an aggregate footage of 2,188 feet; seventy-one holes penetrated 248 feet of iron mineralization. Average thickness of the ore zone was 3.5 feet under an average thickness of 14.7 feet of overburden. The drilling developed inferred reserves containing nearly 30 million long tons of crude ore with an average analysis of 28 percent iron plus minor quantities of manganese. Test work done by the Bureau on the crude ore samples indicated that they would upgrade by current lug washer practice, with the use of a 1i8-inch screen, and yield 4.4 million dry long tons of concentrate with an average analysis of 52.1 percent iron plus manganese. The weight recovery obtained was 14.7 percent. Research studies made by the Bureau showed that the weight recovery would be increased by changing the screen size without any appreciable sacrifice of grade. The average weight recovery was increased to 18 percent with a 10-mesh screen and 22.8 percent with a 20-mesh screen. Screen tests studies indicated that there was no appreciable interlocking of the iron and manganese minerals and the clay and silica waste particles of the materials retained on a 200-mesh screen. Clay was prominent in micron-size slimes. Silica was deleterious in the minus 20-mesh size.

Jan 1, 1965

By J. M. Stuve

Provisional values for the heat of formation of europium trichloride and europium sesquioxide were determined by solution calorimetry utilizing europium metal of more than 99-percent purity. The resulting values for the heats of formation of Eu203 (cubic) and EuCls (hexagonal) were -386,970 ±l,200 cal/mole and -218,740 ±650 cal/mole, respectively, measured at 298.15° K.

Jan 1, 1965

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By Frank B. Fulkerson

Three of the five primary aluminum producers in the Pacific Northwest have facilities in the region to make aluminum mill products. Only one of the three, however, produces a variety of shapes and forms. The principal reason for the lag in development of an aluminum mill products industry was found to be transportation cost. The long range outlook is for expansion, based mainly on growth of the western market for aluminum used in construction, containers and packaging, electrical applications, diesel trucks, mobile homes, and irregation pipe. Consumption of western aluminum mill products in 1985 is projected at 1.1 million tons, compared with estimated consumption of 250,000 tons in 1961.

Jan 1, 1965

By R. E. Campbell

Uranium metal of improved purity was prepared by electrorefining commercial magnesium-reduced uranium in a molten sodium chloride-uranium trichloride electrolyte. The best operating conditions for the preparation of refined metal were established as follows: an electrolyte containing 8.7 to 13.3 weight-percent uranium; initial cathode current densities from 300 to 1,500 amp/sq ft; and a molten salt temperature of 860° C. Ingots produced from electrorefined uranium crystals prepared with these operating conditions were substantially free of metallic impurities. The only impurities in the refined and consolidated metal were present in low or undetectable amounts.

Jan 1, 1965

By R. Schuhmann

Jan 1, 1965

By Claude H. P. Lupis, John F. Elliott

IN the recent past, extensive use has been made of the interaction coefficient in treating the thermody-namic behavior of components in solutions at dilute concentrations. The development of this concept by wagner1 and chipman2,3 is sufficiently well-known so that its elucidation here is not necessary. The present discussion is focused on the relationship between E and e. The usual forms of the coefficients are:

Jan 1, 1965

By H. C. Chao, L. H. Van Vlack

Small MnS inclusions with known crystallographic orientations were placed inside powder compacts of low-carbon steel. After the metal was axially campressed with negligible end friction, the deformstions for the metal and the inclusions were compared. The MnS inclusions deformed more when the [100] direction was aligned with the compression axis than when the [111] direction was parallel to this axis. The deformations of the inclusions in the two principal radial directions were equal for each of the above orientations. Inclusions with [110] compression alignments did not deform with radial symmetry. The relative deformation of the inclusion and metal was closely dependent upon the relatiue hardness of the two phases. The relative deformation of the two phases was not sensitive to the rate of deformation. RECENT studies by the authors1.&apos; suggested that the plastic deformation of MnS in steel would probably be highly sensitive to the orientation of the inclusions and to the temperature of the metal. This paper reports an investigation of these factors upon MnS behavior within steel. Manganese sulfide (MnS) possesses an NaCl-type structure and typically has extensive (l10) {110} slip as a separate (noninclusion) crystal.&apos; A secondary slip system, ( l 10) { l l l}, has also been observed where the major slip system is restricted. In general, MnS inclusions must be rated as a highly deformable second phase.3 The amount of sulfide deformation varies, however, with several composition and processing factors. Some of these have been only partially assigned. For example, it is known that minor amounts (<0.01 pct) of silicon within free-machining steels will increase the amount of MnS deformation,4 but the mechanism of the added deformation can only be surmised at the present. Manganese sulfide and steel have sufficiently comparable deformation characteristics so that slip which is started in steel may be continued through the sulfide inclusions and back into the steel if the crystal orientations are favorable.5 A more detailed discussion of previous work on the plastic deformation of NaC1-type crystals and on the plastic deformation of inclusions within a metal is given in Chao&apos;s work.6 EXPERIMENTAL PROCEDURE The manganese sulfide which was used in this study was prepared by previously described methods.&apos; Single crystals of MnS, both as cleavage cubes and as spheres, were oriented within steel powder compacts so that the desired crystal directions were parallel to the direction of axial compression. A four-stage hydrostatic compaction procedure was used and involved the following steps. In the first stage part of the powder was placed in a metal die 1 in. in diameter with a thick (1 in. OD, 5/8 in. ID) rubber liner which had one end plugged. The steel powder was hand-rammed, making it as dense as possible before placing a carefully sized MnS crystal (either as a sphere or as a cube) near the center. The crystal was oriented with the chosen direction vertical; viz., [001], [011], or [111], with the aid of a X10 microscope. A pair of tungsten wire threads 0.020 in. in diameter was inserted along the side of this (&apos;core compact" to locate the desired plane after the compression tests. After the crystal was positioned in the center of the die, more powder was added and carefully rammed by hand. The die was then capped with a rubber plug of the same hardness and thickness as that of the liner. The whole assembly as shown in Fig. 1 was compacted by a ram load of 54,000 lb (about 70,000 psi). In the second stage a smaller, 3/4-in, rubber-lined die was used to give a stress of approximately 120,000 psi. The above process was repeated with the initial compact serving as a core for a larger compact. The final product after sintering was a cylinder 1 cm long and 1 cm in diameter, having a density of 7.54 g per cu cm. This was close to the theoretical density since the metal contained a non-metallic phase. There was no evidence of MnS deformation during the hydrostatic compaction or subsequent sintering. Elevated-temperature hardness data were obtained by procedures previously described.2 Compression tests for inclusion deformation utilized the cylinders which were described above. The critical problem in these tests was the lubri-

Jan 1, 1965

By T. A. Sullivan

High-purity vanadium metal was prepared by electrorefining commercial vanadium in a molten sodium bromide, potassium bromide, and vanadium dibromide electrolyte. Variables investigated were operating temperature, current densities, electrolyte composition, and condition of the anode. The purity of the refined metal was in the range of 99.95 percent vana-dium. Iron and oxygen in the 50- to 250-ppm range were the only major impurities. Metal with hardness numbers of 50 to 60 in the Rockwell F scale was prepared from feed material with a Rockwell B hardness of 90. The arc-melted metal was highly ductile and could be cold-worked into sheet or foil.

Jan 1, 1965

The 8 ft by 91/2 ft drive which joined No. 7 Shaft with Browne Shaft on the 1,480 ft level was extended from both ends and met at a point approximately 12,000 ft from No. 7 (2,000 ft from Browne).The surveying required for this 2 1/2 mile haulage drive called for greater accuracy than was obtainable from South Mine standard methods. Procedures and devices from published information were tried and modified as required to suit local conditions. Several new methods were applied and improved as the drive advanced. The control of angular, linear and level measurements was perhaps considerably in excess of the requirements, but this was offset by abnormally large discrepancies resulting from shaft plumbing. The accuracy of the final breakthrough, although not to the standard desired, was sufficient to complete the connection without inconvenience and added cost.INTRODUCTIONThe acquisition of the Browne Shaft leases in January 1962 presented the management of Broken Hill South Limited with the problem of transporting ore from these leases to its mill. It was eventually decided that diesel locomotivehaulage through a 2t mile drive on the 1,480 ft level between the two mines was the best solution. The drive was advanced from both ends after Browne Shaft was deepened by 80 ft to reach the 1,480 ft level horizon. Each end advancedabout 15 ft/day with the miners working three 7 hr shifts. Blasting was restricted to the end of the shift.The survey work involved five shaft plumbings and 78 theodolite stations in a traverse, underground and surface,of more than 5 miles. Because of the exceptional length of the drive, an unusually high degree of reliability was required.The aim was for a maximum error at breakthrough of 1 ft 1 in 30,000, and to secure this, precise methods of linear measurement were necessary. Shaft plumbing in particular posed special difficulties.

Jan 1, 1965

By G. C. Gould

The nature of freckle segregation is determined by chemical analyses, microradiograplzy, and electron microprobe. In addition, the influence of chemistry variation on freckle formation is studied in laboratory experiments. It is demonstrated that controlled laboratory solidification can produce freckle segregation. "FRECKLE" segregation is a discontinuous, rod-like segregation observed in vacuum consumable -electrode ingots. Figs. 1 and 2 show this segregation as pencil-like, dark etching areas of segregation found in longitudinally and transversely sectioned consumable-electrode ingots. In most cases the segregation is perpendicular with respect to gravity and parallel to the longitudinal axis of the ingot. The segregation is most often encountered at or around midradius in large vacuum consumable-electrode ingots. The austenitic alloys, A-286* and 718, † have shown particular susceptibility to this mode of segregation. The origin of these rodlike pockets of segregation is not well-understood. It has been suggested that the segregation is a result of a portion of the electrode dropping off and passing through the arc un-melted. On the other hand, smeltzer1 has demonstrated the freckle segregation in A-286 to be comprised of low-melting constituents relative to the matrix melting point. The discontinuous nature of the segregation is the most perplexing facet of the freckle-segregation problem. It was to gain some insight into this part of the problem that this work was undertaken. I) PROCEDURE At the outset of the work identification of the phases present and the elements concentrated in the freckle areas was undertaken. The electron micro-probe was used to determine general enrichment as well as -specific phase chemistry. Microradiography using cobalt and chromium radiation was also used on the freckle areas again to determine the elements involved in the segregation. X-ray diffraction patterns were made from portions of these same foil specimens. Optical microscopy and Knoop hardness measurements were also used

Jan 1, 1965

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin&apos; examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan&apos; have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

By J. E. Forciea, R. W. Salmi

Operating and research personnel at U.S. Steel&apos;s Pilotac concentrator have evolved specifications for magnetic separators suitable for use in beneficiation of Mesabi magnetic taconite. These specifications were developed as a result of investigations into the operating and metallurgical problems at the Pilotac concentrator over a period of some ten years. This paper discusses primary magnetic separator specifications, but much of the information is also pertinent to secondary and tertiary magnetic separators. Of particular significance is the proposal of a new basis for specifying the magnetic field which includes consideration of both field strength and field gradient. Other areas of discussion include flowsheet service, operating conditions such as drum speed and pulp level, tank configuration, magnet strength including field gradient, sleeve bearing design, designation of corrosion resistant materials and other details that result in a metallurgically efficient machine that has low repair and maintenance requirements. The mechanical and metallurgical design of magnetic separators at the Pilotac plant, Minnesota Ore Operations, United States Steel Corp. has progressed from the original single-stage, belt-type machines to the present multiple-stage, drum-type units, In ten years of operation, the plant operating and research personnel, in consultation with manufacturers, have made design changes to improve mechanical, electrical and magnetic features to meet process needs as flowsheet designs developed and to incorporate new permanent magnet materials as they became available. Separator specifications were an end result of this effort. The latest specifications which were developed for the Minnesota Ore Operations&apos; plant were not all-inclusive listings; they covered only those points indicated by plant experience. For example, magnet pole piece design and dimensions were not stated. The manufacturers were given freedom to use any design as long as the field pattern was as specified. The selection of the items to be included in the specifications was undoubtedly influenced by particular conditions at Pilotac such as composition of plant water, concentration characteristics of the ore, repair and maintenance facilities available and the research programs that had been conducted. Only the developments leading to the specifications for a primary or "cobber" magnetic separator are presented in this paper. However, the same general concepts are used to specify secondary and tertiary separators. The areas of interest discussed include flowsheet service, tank configuration, magnet design, bearings, materials of construction, and some minor mechanical details. FLOWSHEET SERVICE The primary magnetic separators in the Pilotac Concentrator flowsheet are located after the first stage of grinding as shown in Fig. 1.

Jan 1, 1965

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01&apos; and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-&apos; cm-&apos;). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-&apos; cm-&apos;). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.&apos; Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines&apos; diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c&apos;i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."&apos; The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall&apos; reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel&apos;&apos; structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,&apos; whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By Manuel Gomez

Carbon number distributions were obtained for tar acid fractions from five low-temperature tars by low-ionizing voltage mass spectrometry. Quantitative data for phenols representing seven structural compound types were examined by statistical analysis. It was shown that for the phenols discussed, the data could be represented by regression equations expressing phenolic concentration as a function of the reciprocal of the carbon number and the carbon-to-hydrogen ratio of the parent coal. The total concentration of each structural type present was found to depend on the molecular weight and boiling point of the initial member of the group. Carbon distribution data for the tar acid fractions studied support the view that low-temperature tars contain the same chemical compounds but in different proportions.

Jan 1, 1965