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By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Robert B. Johnson

The refraction seismic method has been used as an indirect means of exploring for fluorspar in southern Illinois by the Illinois State Geological Survey. Use of the method has been restricted to those areas where mineralization is associated with faults, a restriction necessitated by the operating principles of the refraction method. The seismic data enable the interpreter to locate fault zones in the subsurface and, under ideal circumstances, to make estimates of dip direction and magnitude and vertical displacement provided the local stratigraphic units are known and are geophysically recognizable. In this instance, refraction seismic exploration has been successful in the surface mapping of well-developed faults, both simple and complex with which fluorspar may or may not be associated. However, less clear results have been obtained where faulting has been less severe and where there are numerous accompanying mineralized joints.

Jan 1, 1964

By C. O. Ensign

Results of the application of geo1ogic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphi-cally controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore. A routine program of grade control was started in the White Pine mine in August 1961. The program is based upon development and application of geologic knowledge to assist mine operating personnel to increase the grade of ore, primarily by accurate stratigraphic control and selection of areas for development on the basis of grade distribution trends. Geologists work closely with mine supervisors to offer the necessary geologic guidance. STRATIGRAPHIC POSITION OF COPPER The important rock series in the White Pine area is comprised of three formations of late Precambrian age. In descending order they are the Freda sandstone, Nonesuch shale, and Copper Harbor conglomerate. The Nonesuch shale is about 600 ft thick. Economic copper concentration occurs only in the lowermost 20 to 25 ft of the formation; however, within a restricted area along the southwest side of the mine the uppermost 1 to 7 ft of the Copper Harbor conglomerate (lower sandstone) contain sufficient quantities of copper to be included in the ore column. The ore consists primarily of chalcocite with subordinate native copper disseminated in shales, siltstones, and sandstones. MINE BOUNDARIES AND STRUCTURE The mine area is bounded on the west by the sub-outcrop of basal Nonesuch at bed rock surface and on the southwest by the White Pine fault (Fig. 1). The south and southeast limit of the orebody is reasonably well delineated by thinning or pinch-out of favorable host beds. Northern, northeastern, and eastern limits have not been established. The White Pine fault is actually a wide zone of shearing which strikes approximately N 40° W. It is downthrown on the southwest side and dips steeply to the northeast. Maximum vertical displacement is about 1500 ft.

Jan 1, 1964

By Horace Pops

Isothermal sections in the copper -rich region of the Cu-Si-Zn a1by system have been determined at 8473 760; 6003 and 482°C by means of microscopic examination with confirmatory X-ray diffraction work. The stability of the bee 0 phase decreases both with decreasing temperature and with increasing copper content. The silicon-n&apos;ch 0 phase decomposes upon quenching from high temperatures either by a martensitic or by a "massive" transformation, depending upon the solute content. A two-phase equilibrium is found to exist in the Cu-Si-Zn system between the hep < phase of the Cu-Si system and the bee ß phase of the Cu-Zn system. It is shown that the isothermal limits of the primary solid solution at 760; 6003 and 482°C are in part affected by the intermediate phases which follow them in the ternary system Possible electron-concentration and size effects upon phase boundaries are discussed. ALTHOUGH the mechanical and physical properties of silicon brasses have been measured in great detail, the factors which influence these properties are not well-understood, partly because the knowledge of the phase relationships in the Cu-Si-Zn system is limited. Gould and Ray1 studied the effects of silicon upon the hardness and structure of Cu-15 pet Zn and Cu-40 pet Zn alloys. They proposed an isothermal section at 800°C which was not based upon experimental data, since the binary phase diagrams had not been completely determined. Using Cu-Si-Zn alloys containing approximately 5 wt pet Si, vaders2 determined the boundary, at 750°C, between the copper-rich solid solution and an unidentified second phase. Masing and wallbaum3 examined a vertical section through the ternary diagram in the region between Cu-20 pet Zn and Cu-10 pet Si alloys, but they emphasized uncertainty about their data. Mima and Hasegawa4 studied the liquidus surface of Cu-Si-Zn alloys, phase transformations in high silicon-bearing (20 to 25 at. pet) alloys,5 and the phase relations in low silicon-bearing Cu-Si-Zn alloys.6 Their experiments were based upon thermal analyses and metallographic observations. The compositions of the phase boundaries were not determined with high precision, and the crystal structures of the phases were not reported. Because of uncertainties in the existing literature, it became of interest to determine more accurately the phase relations in copper-rich Cu-Si-Zn alloys. The crystal structures, stability, and phase boundaries of the primary solid solutions and several intermediate phases were determined, and the data are reported as partial isothermal sections.

Jan 1, 1964

By Philip N. Adler, Harold Margolin

Univariant equilibria between the Ibcc, IIhcp, and UIfee phases of thallium have been determined and indicate a triple point at 110°C and 37 kbars. Calculated II —I transformation curves are compared with the experimental. Transformation volumes and/or enthalpies are calculated and enthalpies are compared with available data. ThE triple point of solid thallium has been reported by Bridgman as 153°C and 38 kbar.&apos; More recently, Jayaraman et at.2 have reported the triple point as near 115°C and 39 kbars. Meyerhoff and Smith,3 assuming the elevated-pressure modification of thallium is fcc, as Kaufman suggested,4 and that it is continuous with the room-temperature fcc phase in the Tl-In system, have used pressure data up to 5 kbars to predict the triple point at 162°C and 35.8 kbars. Piermarini and weir5 have indeed found the elevated-pressure phase to be fcc. The effect of variations of pressure and temperature in the IIhCp — Ibcc transformation in thallium have also been reported by werner6 and more recently by Ponyatovskii.7 The work reported here is part of an investigation of the effects of temperature and pressure on the Tl-In system. I) EXPERIMENTAL PROCEDURE The onset and progress of transformation were determined by changes in resistance. A commercially available tetrahedral-type pressure apparatus was used. Specimens of 0.060 in. diam, representing 0.63 pct of the cell volume, were encased in AgCl and mounted in pyrophyllite, as shown schematically in Fig. 1. It can be seen that the specimen is in series with the graphite furnace. Resistance changes of 0.1 pct could be detected with a Kelvin bridge. Resistance of the sample was of the order of 1 milliohm. Other pertinent details in regard to calibration and cell-assembly design are given elsewhere.&apos; Temperature calibration of the cell was carried out in two ways as a function of input wattage. Through a hole drilled in the graphite furnace, a chromel-alumel thermocouple was inserted into the AgCl to a point 0.010 in. from the sample, with the

Jan 1, 1964

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By G. W. Form, W. A. Spitzig

The effects of hydrogen and vacuum shtering treatments on the physical and mechanical properties of arc plasma-sprayed tungsten were inuestigated. Temperatures examined ranged from 3000" to 4000°F in vacuum and 2000" to 3000°F in hydrogen for both single and duplex sintering cycles. Densities of 92 pct of theoretical density were obtained when a long-time hydrogen treatment at 2000°Fpreceded sintering in vacuum at 4000°F for 4 hr. This cycle also produced the highest ualues for modulus of rupture and bend angle. The results of this investigation point out the desirability of using a low-temperature long-time hydrogen treatment prior to a high-temperature vacuum sinter for arc plasma-sprayed tungsten. ADVANCES in the development of arc plasma-generating equipment have provided a high-temperature heat source that makes the fabrication of tungsten shapes possible by a metallizing process. Tungsten in the as-sprayed condition is very brittle. It has a density between 80 and 85 pct of theoretical density, a lamellar structure with elongated pores, and a high interstitial impurity content. To improve these properties, sintering treatments can be applied to the as-sprayed material, similar to those used for the densification of compacted tungsten powder. However, in view of the differences in the density and microstructure of as-sprayed tungsten as compared with compacted tungsten, responses to sintering were expected to be different. EXPERIMENTAL PROCEDURES The tungsten powder used in this investigation had a particle size varying from 3 to 13 p with an average diameter of 8p. The impurity level was less than 0.1 pct. The arc plasma spraying was done with an F-40 Thermal Dynamics Corp. plasma jet. Spraying was performed in air and thus required cooling of the substrate by an air blast in order to minimize oxidation. The spraying parameters employed in the fabrication of all specimens are listed below: Power input, kw 12 Arc-gas flow, cfh 95N2 + 5H2 Powder feed rate, g per min 33 Powder carrier gas flow, cfh ION, Spray distance, in. 3 Traverse rate, in. per min 30 Mandrel speed, rpm 100 Nozzle orifice, in. 7/32 These values of the spraying parameters correspond to optimum conditions ascertained in a previous study. Sintering was conducted at 3000°, 3500, and 4000°F in vacuum (< 0.1 Hg), and at 2000 and 3000°F in hydrogen. Duplex sintering treatments investigated are listed in Table I together with the designations that will be used for reference throughout this paper. The samples were fabricated by spraying onto a copper mandrel which was removed prior to sintering. The specimens used for the sintering analyses had the shape of small hollow truncated cones 1 in. high with an inside diameter varying from 0.500 to 0.125 in. and a wall thickness of 1/8 in. Specimens for bend testing were taken from hollow hexagonal prisms 1-1/2 in. high with a 1-in. diam across the flats and a wall thickness of 1/8 in. The bend-test specimens were ground to the dimensions 0.085 by 0.350 by 1-1/2 in. Prior to bend testing 0.0025 in. of stock was removed from each surface by electro-polishing. Density measurements were made by the water-displacement method. In addition, a porosimeter was used to determine the amount of interconnected porosity for representative samples. Strength and ductility were determined from recorded values in transverse bending using a cross head speed of 0.020 in. per min. The load was applied at the midpoint of a 1-in. span. The deflection data reported herein refer only to the plastic portion of the total deflection. RESULTS AND DISCUSSION The as-sprayed samples had a density corresponding to 83 pct (l pct) of the theoretical density of tungsten. Fig. 1 shows a representative as-sprayed tungsten structure.

Jan 1, 1964

By A. Lawley S. Schuster

The tensile behavior of copper foils prepared from rolled bulk material has been studied over the thickness range 2 to 53 , and for a range of pain sizes. For foils of comparable grain size, having the cube texture and tested along (100), yield strength increases with decreasing foil thickness t below -26p, with a corresponding decrease in ductility. Deformation occurs in the form of localized slip clusters distributed throughout the gage section. To the extent that the tensile strength (10 to 18 kg mm-) is unaffected by foil thickness, and that the foils possess fair ductility, the stress-strain behavior resembles that of bulk material rather than that of whiskers or evaporated films of comparable dimensions. The dependence of yield strength o on foil thickness t below -26p is of the form: oy = oo + kt-1/2. Possible explanations for the stress increase are considered based on 1) the dependence of active dislocation source length on foil dimensions, 2) the locking of surface sources, or the blocking of mobile sources at the surface due to surface film. It is now well-established that filamentary whiskers of many materials show exceptionally high strength compared with bulk crystals.&apos;-11 As the diameter of the whiskers decreases to -1, the observed fracture strength approaches, and in certain cases exceeds, the calculated shear stress for the nucleation of slip in a perfect crystal.&apos; In general, the stress-strain curve is entirely elastic, with strains at fracture approaching 1 pct. Similarly, thin films12-24 of evaporated or electrodeposi-ted material have been shown to possess tensile strengths three to seven times that of bulk material, with total strains at fracture -1 to 2 pct. In the present study, attention has been directed to the room-temperature tensile behavior of thin foils of copper over the thickness range 2 to 53, prepared from rolled bulk material. Yield stress, ultimate tensile strength, elongation to fracture, and work-hardening behavior are measured as a function of grain size and foil thickness. Structurally such foils are superior to either evaporated or electrodeposited films, and in the recrystallized condition exhibit considerable ductility. Apart from preliminary work by Sumino and Yamamoto25 on the work-hardening behavior of rolled and recrystallized copper foils, no systematic tensile studies have been carried out on material of this form. EXPERIMENTAL PROCEDURE Tensile specimens were prepared from 99.995 pct purity rolled copper foils of thickness 2, 6, 12, 26, and 53, obtained from the Hamilton Watch Co., Lancaster, Pa. Irrespective of specimen shape, it is necessary to use tensile foils with edges free from notches or tears. To this end, any form of cutting operation was excluded, and the tensile foils prepared using a photoengraving process, the details of which are described elsewhere.26 Since tensile data are required under conditions of uni-axial stress, the specimen shape is extremely important. Ideally, the foil should be infinitely long, allowing a gradual taper from the grip area to the gage section; however, from a practical standpoint, long foils are easily damaged during testing. A modified tensile specimen was therefore selected having a parallel gage section 1.25 by 0.20 in. with a tapered shoulder section increasing to 0.5 in. at the grips, and an over-all length between grips of 4 in., Fig. 1. In practically all tests, these foils fractured within the parallel gage section. By approximating the foil contour (Fig. 1) to a hyperbola it is possible to analyze the stress distribution in the tensile foil using two-dimensional elasticity

Jan 1, 1964

By Luke L. Y. Chang, Bert Phillips

ThE tendency toward further oxidation of the intermediate oxides and the high volatilization rates of the higher oxides have prevented direct attainment of equilibrium data for the system tungsten-oxygen. As a result, St. Pierre et al.1 have proposed a phase diagram (to 800°C) based on thermody-namic data to 1200°C for the known tungsten oxides (WO2z, W18O49, W20O58, and WO3) and a report on a tungsten suboxide W3O.2 Recent modification of a technique previously described3 5 now permits adequate preservation of compositions of mixtures of metallic tungsten and metal oxides (e.g., of tungsten, cobalt, calcium, samarium, titanium) in order that condensed phase relations may be established to 1700 This method has been applied to study the high-temperature stability of tungsten oxides. In the method used, the desired compositions were sealed in nonreactive containers such that only a small gas volume remained. Each sample then established its own equilibrium atmosphere at temperature. This method has advantages in the study of systems of the W-0 type where knowledge of the condensed phases is desirable but for which composition and pressure of the gas phase are not readily attainable because of oxide volatility. Mixtures of 99.99 pct tungsten metal powder and purified tungsten anhydride (WO3) or in some cases W18O49* were equilibrated in pellet form in sealed

Jan 1, 1964

By P. L. Russell

The use of nuclear explosives for excavation has been demonstrated to be feasible and practical. Application of nuclear explosives for overburden removal from large ore deposits appears to offer economic advantages over present methods, but under the present pricing schedule, high-yield devices must be used to obtain an economic advantage. The use of nuclear explosives presents problems not inherent in the use of conventional explosives, and thus they can be used only in areas where large explosions and associated phenomena can be tolerated. Stripping of coal with nuclear explosives does not appear practical at this time, but stripping overburden from copper or iron ore deposits may be a potential use. Even here, however, the use of nuclear explosives would require isolation, favorable topography, favorable ground-water conditions, and a low population density. If these basic requirements can be met, the use of nuclear explosives for overburden removal would offer both economic and time advantages. The possibility of using nuclear explosives for peaceful purposes was a subject for speculation as early as 1945. The PLOWSHARE Program was formally established by the AEC in June 1957 for the purpose of developing and demonstrating peaceful applications for nuclear explosives. The technical direction of the program is the responsibility of the Lawrence Radiation Laboratory, Livermore, Calif. Mining and excavation were two fields that received early consideration as areas in which nuclear explosives might be used. Knowledge gained from underground weapons testing increased this possibility, and the development of the thermonuclear device which has a small fission-to-fission ratio, reduced the hazard of radiation, and spurred interest. Nuclear explosives appear to have the greatest potential in the following mining operations: 1.— Surface Mining a) Stripping of waste for open-pit excavation b) Breaking of ore in open-pit mining c) Quarrying d) Blasting for production of aggregate, riprap, etc. 2. — Underground Mining a) Block caving application b) Crushing of ore for in-situ leaching, etc. c) Preparation of underground waste disposal areas Of the potential applications, excavation is perhaps the most obvious and the best understood, and probably the most practical for use in the near future. Large quantities of rock and earth can be moved by proper emplacement of nuclear explosives, but economic and practical relationship must be determined between the known capabilities of nuclear explosives and the required excavating to remove overburden. REMOVING OVERBURDEN IN OPEN-PIT MINING Removing the overburden is one of the largest jobs in open-pit mining. In 1960 open-pit mines produced approximately 130 million tons of coal, 108 million tons of copper ore, and 135 million tons of iron ore. To obtain this much production, an estimated 3-billion tons of overburden were removed from the coal, 216 million tons from the copper ore, and 135 million tons from the iron ore. These figures do not include the initial stripping required before ore production. For example, the ASARCO Mission mine started stripping operations in August 1959 and by mid-November 1961 had removed 46.3 million tons of material including 1.2 million tons of ore.* Initial excavation of this type offers the most favorable conditions for utilizing the earth-moving ability of nuclear explosives. EXPLOSIVE CASTING FOR REMOVING OVERBURDEN The use of explosives to remove overburden is not a new idea. Conventional explosives have been used for this purpose for many years with varying degrees of success. Several small coal strip operators have used this idea to increase production. At these mines about one-third or more of the overburden is thrown by explosives across the pit and onto spoil piles. The additional costs of drilling more blast holes and more explosives are more than compensated for by a reduction in the time required to uncover the coal, and by an increase in coal production.

Jan 1, 1964

By L. A. Hanson

Jan 1, 1964

By D. W. Fuerstenau, P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the balls at different stages of pelletiz-ing are also discussed. In many industrial chemical processes, particulate matter can only be utilized if it is in an agglomerated form, such as pellets. Pelletizing is now widely used in iron ore technology1, and it has also been applied to a number of diverse fields such as the production of cement-kiln feed2, fertilizers3, and fluorspar4. Recently, it has been proposed to pelletize dispersion-type ceramic nuclear fuel elements5. In iron ore technology, for example, the production of agglomerates by pelletizing involves two major steps: 1) the preparation of green balls by rolling particles in a suitable balling device and 2) the firing of the green balls to form compact, strong bodies upon sintering. The critical step in a successful iron ore pelletizing operation is generally considered to be the balling operation1. In this paper, which is not concerned with the sintering of green pellets, the words green pelletizing and balling will be used interchangeably. Green pelletizing, or balling, will be defined as the process of forming larger bodies by rolling fine particles on a surface without the application of direct pressure. Two recent literature surveys6" indicate that in spite of the considerable amount of industrial pelletizing, very little is known about the fundamental principles of balling and its kinetics. The first reported research on the kinetics of pelletizing is the work of Newitt and Conway-Jones8. Using silica sands of different sizes in a batch laboratory balling drum, they found that the average green pellet diameter increased linearly with time at constant drum speed, and qualitatively the growth rate increased with moisture content. Generalized conclusions cannot be drawn from their research since the materials which they pelletized were sand and sand-silt mixtures rather than comminuted materials. Moreover, Newitt and Conway-Jones used testing sieves to estimate the size distribution of the green pellets, and this technique limited the range over which they could study the growth kinetics of the pellets. Bhrany and co-workers9 investigated the kinetics of balling iron ore fines on disk pelletizers ranging in diam from 1 to 18 ft. In their investigation, balling was carried out as a continuous operation, and growth kinetics were studied in terms of retention time of the material on the disk. Although the feed material in their study was quite coarse (the maximum size being about 1/2 in.), they also found qualitative relationships between pellet growth and water content, and feed size. In the present investigation, a number of innovations were introduced that refined the experimental measurements and established the reproducibility of balling experimentation. This enabled extension of the range of measurements to include study of agglomerate nucleation phenomena in the fractional mm size. This paper presents a detailed analysis of the nucleation and growth of green pellets in a laboratory balling drum. MATERIALS AND METHOD Pulverized limestone of specific gravity 2.72 was used as a model system in these studies. It has already been established that the balling characteristics of limestone and silica are similar to those of iron ore concentrates 2,8,10, depending on physical, rather than chemical, properties of the particles. The size distribution of the limestone was determined by a wet-dry sieving technique in the sieve range and by a sedimentation balance in the sub-sieve range. Fig. 1 presents the size distribution of the limestone used in this research. This figure shows that the material is finer than 200p (65 mesh) and that 25% of it is finer than 12. The specific surface area of this powder, as measured by BET gas adsorption methods,

Jan 1, 1964

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.&apos; On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.&apos; In this paper the terms "size broadening" and "strain broadening&apos;&apos; are used in the general sense adopted by warren.&apos; In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.&apos; To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By Hsun Hu

The microstructural changes during rolling and at various stages of recrystallization in (111)[112] oriented single crystals of Si-Fe have been studied by transmission electron microscopy. At very low deformation, the dislocation structure consists of jogged dislocation lines, edge dislocation dipoles, and numerous dislocation loops, which may be interpreted by the jog-formation mechanism in moving screw dislocations. Up to 70 pct rolling reduction, no sharply defined cells are formed. Subgrain forma- tion takes place somewhat earlier in the annealing process than in a similarly processed (110)[001] crystal. This may be partly responsible for the reported difference in the rate of recrystallization between (111)[112] and (110)[001] crystals. Evidence indicates that the formation of recrystallization nuclei occurs largely by the coalescence of sub -grains. This is consistent with previous observations on other Si-Fe crystals. AVAILABLE data in the literature indicate that the main features of rolling and annealing textures in (111)[112] and (110)[001] crystals are essentially similar. A (111)[112] or (111)[112] crystal can be rolled 70 pct without changing its initial orienta-

Jan 1, 1964

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm&apos;3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.&apos; The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5&apos;9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1&apos; at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.&apos; It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

THE tensile and notch tensile ductile-to-brittle transition characteristics of several refractory metals and alloys have been well documented.1-3 Electron-beam melted tantalum and columbium have been shown to retain excellent ductility at very low temperatures. Some indications of brittle behavior (low ductility and cleavage fracture) were observed with columbium tested at -253oC, but no similar effects were noticed with tantalum. Increasing the interstitial oxygen content in these two materials resulted in the detection of indications of brittle behavior at higher temperatures, although good ductility was retained in both bases at -196°C when they contained about 1 at. pet 0. Detailed descriptions of the impact transition behavior of these two materials at various purity levels have not been available. This technical note describes the effect of interstitial oxygen on the impact properties of wrought, fibered tantalum and columbium and compares the transition behavior to the previously determined tensile transition characteristics. Tantalum and columbium impact specimens with three different interstitial oxygen levels indicated in Table I were tested at temperatures ranging from -196o to 300°C. Oxygen additions were made to 1/2-in.-diam bars of electron-beam melted material in a Seiverts Apparatus. The oxygenated bars were then homogenization-annealed to obtain uniform cross-section hardnesses and swaged to

Jan 1, 1964

By D. R. Bomberger, M. Deul

An automatic microscope has been developed to measure the size and populations of macerals and minerals in fine coal particles. Differentiations are made on the basis of reflectance. This study is concerned with the size distribution of pyrite inclusions. Most fine coal cleaning processes do not remove pyrite as completely as a straight density separation. Consideration of the pyrite size distribution is suggested as a more accurate method of predicting sulfur reduction by a cleaning process. Analyses of float-sink results and Deister Table operation in terms of pyrite particle sizes are made. Other potential applications of automatic microscopy are also discussed. In the study of coal cleaning by pseudo-gravity methods (tables, cyclones, hydrotators, etc.), it is customary to express the deficiency of the process relative to float-sink measurements in some form of "percent efficiency". These have been calculated in many different ways in order to provide a means of extrapolation of test data to untested coal feeds. This works quite well with coarse coal (here defined as larger than one-eighth in.). Large, heavy pieces of refuse are rejected rather thoroughly by many cleaning processes, and the efficiencies relative to float-sink results approach 100%. In coarse coals, the difference in the sizes of fine pyrite is masked by the averaging effect of the large coal envelopes. The existence and fate of fine pyrite is often hidden in the larger numbers representing coarse (and easily removed) pyrite. There are cases where it is desirable to subject fine coal (here defined as smaller than one-eighth in.) to cleaning processes. This is true of naturally occurring fie coal streams and in cases where comminution followed by cleaning is necessary to provide the quality desired. It is in this area that the use of process efficiency relative to float sink fails. Percent efficiencies decline to very low figures, and equivalent separation densities become a matter for conjecture. The net result is that an attempt to estimate product quality from float-sink data and a process efficiency figure often results in large errors. This work represents a new approach to the problem by observing the fate of pyrite particles, grouped by sizes, in a cleaning process. Examples are given which relate pyrite size measurements to float-sink washability and to a Deister Table operation. EXPERIMENTAL WORK The automatic microscope used here has been previously described.&apos; Briefly, it is an instrument which measures the diam of particles (as defined by a range of reflectance) exposed on a polished specimen. The instrument scans a sample briquet, measures diam of exposed pyrite inclusions and records the data by size intervals. Preparation of the briquet is critical, due to the automatic nature of the process. The principal requirement is for an optically flat surface, so that focus will be maintained as the motorized stage moves the specimen under the lens. The various substances present must be polished to the same level in spite of the wide difference in hardness between coal substance and minerals. The polishing method must not pluck out small grains, which might be rather loosely held by surrounding coal. The procedure below was successful in producing all of these results. The coal sample (8 mesh or finer) was riffled (a micro vibrating riffle is essential) to obtain 15 g. One volume of Lucite powder (thermosetting plastic mounting medium) was mixed with three volumes of coal and mixed thoroughly. A briquet was formed using a cylindrical die (1 1/4 in. diam) at 3000 lb per in.* pressure and 150°C. Preparation of the optical surface was accomplished on automatic polishing equipment, according to the following schedule: 1) Grinding: 3 stages, using successively fine Carborundum grits of 180, 320 and 600 mesh. 2) Rough polishing: 2 stages, using 3µ alumina on cast iron, followed by 1µ alumina on lead. 3) Fine polishing: 2 stages, using 0.5µ alumina on napless broadcloth over bronze, followed by 0.1µ alumina on silk filament cloth over bronze. Raw data were corrected for the fact that the chords

Jan 1, 1964

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.&apos; The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964