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By Donald P. MacKinnon

"This paper is a commentary on selected trends within the transportation industry.In general, innovations are taking place within all modes of transport (road, rail and water) serving the industrial minerals industry which will affect future distribution patterns, methods and costs. Significant technical innovations in the transportation of solids by• pipeline will also appear, perhaps in the near future, permitting the transport of specific commodities, including some industrial minerals. However, the timing and magnitude of the commercial exploitation of solids pipelines are heavily dictated by marketing factors and distribution system logistics, as well as by the innovations likely to take place within competitive modes of transport. Competitive technological developments will include increased ship capacities, improved bulk-handling facilities, larger and specialized bulk-handling rail equipment, unit trains, containerization, larger ""off-highway"" vehicles and greater inter-modal integration. Equally significant are some ""soft-ware"" techniques such as the growing interest in total distribution cost concepts. However, the impact of the developments will not be spread uniformly over all Canadian industrial minerals."

Jan 1, 1967

By R. Ebeling, M. F. Ashby

The paper is in two parts. The first develops the formulae and method needed to calculate the size, nu)nber, spacing, and volume fraction of hard or inert particles in the interior of a specimen from measurernents made on an extraction replica; throughout, the spread of- particle sizes in a single specimen is taken into account, and the extraction efficiency of the replica is considered. A method for testing whether the particles are randotnly distributed in space is described, and the spacing of randomly distributed particles is discussed. The second Part describes the application of the method to copper containing spherical particles of silica; the description includes an estimate of the errors involved, and a comparison of this with alternative methods. All parameters except uolume fraction can be determined satisfactorily, and the method offers advantages over other electron-,rzicroscopic techniques when dealing with hard particles in a softer matrix, or inert particles in a chem-ically less inert matrix. 1 HE experimental measurement of sizes and numbers of discrete particles of a second phase embedded in a matrix material from opaque, plane sections has been considered by many authors, notably by Fullman.' It is assumed that, when the specimen is sectioned, the particles are also sectioned, so that the diameters of the circles of intersection of particles with the plane of the cross section ("surface diameters") are measured. It is difficult to derive the distribution of true particle diameters ("volume diameters") from measurements of the distribution of "surface diameters" on a plane section. The measurement of size and numbers of small second-phase particles by transmission electron microscopy through thin foils of matrix containing the particles has been described by Cahn and ~uttin~' and by ~illiard.~ Because of overlap and the fact that particles which intersect the foil surface may be sectioned whereas those in the bulk of the foil are not, it is again difficult to measure the true distribution of particle sizes. The use of replicas for this sort of measurement has not been analyzed in detail. A replica made from an opaque cross section, thus replicating the circles of intersection of particles with the plane of section, is analyzed by Fullman's method and suffers from the same difficulties. Under certain circumstances, however, extraction replicas can be used, and offer a special advantage in that they make the determination of the true distribution of particle diameters particularly simple. It is the purpose of this paper to describe this extraction replica method. Consider the example of an alloy consisting of SiOz particles, whose mean diameter is about 1000A, dispersed in a copper matrix. When the alloy is sectioned and mechanically polished, the particles are not sectioned, because they are much harder than the matrix, and so will be either left in the surface or pulled out whole, and because the particle size is smaller than the abrasive size of even the finest abrasive. The particles are chemically inert in solutions which chemically etch or electropolish the matrix, so that chemical treatments do not section the particles either. (Experimental measurements of particle shape in this alloy confirm this—truncated particles are never seen.) Small, hard or inert, particles are therefore not sectioned when the specimen is sectioned and polished. An extraction replica taken from this polished surface shows the true "volume" diameter of each extracted particle; the distribution of diameters seen on the replica is the surface distribution of true "volume" diameters, and the volume distribution of true "volume" diameters is easily derived from it. The extraction replica method is not subject to the difficulties associated with sectioning of particles, and avoids the problem of overlap from which the transmission method suffers. The method is well-suited for studying hard particles in a soft matrix. Examples are provided by internally oxidized alloys, oxide-dispersion strengthened metals like T.D. Nickel, and carbides, nitrides, and strong intermetallic compounds in metals. It should be possible to adapt polishing techniques in alloys containing softer but inert particles to avoid sectioning the particles (say by electropolishing or etching). The method is tested and illustrated in Sections 8 and 9 by applying it to a dispersion of spherical SiO2 particles in a copper matrix. I) SYMBOLS Symbols are defined where they first appear in the text. Volume fractions of particles are denoted by the symbol f, particle diameters by x, center-to-center particle spacings by D, and numbers of particles by N. Mean particle diameters and standard deviations about these means are denoted by x and a. Both arithmetic (subscript A) and geometric (subscript G) means are employed. In this paper we measure the distribution of true diameters of particles which touch or pass through a random-plane section of the specimen. We may want to know the distribution of particle diameters in the

Jan 1, 1967

By Adrian J. Mathias

This report presents the results of an investigation of a mine production-scheduling model and a critical path analysis for long-range mine planning. An example is given to illustrate how these techniques might be used to plan long-range development and production scheduling for a large underground mine. The model, based on estimated ore block grades and tonnages, and on designed mine development layout, simulates mining of ore blocks in a sequence necessary to fulfill mill requirements for ore tonnage and grade evaluation within pre-established system restrictions. Simulated production schedules are obtained as output from the model. These production schedules are then incorporated into a critical path analysis to determine the sequence for the long-range development work so as to fulfill the production schedules and thereby meet the ore grade and tonnage requirements of the mill.

Jan 1, 1967

By A. E. Kurie

The Great Salt Lake occupies about 1000 square miles whereas its predecessor, Lake Bonneville occupied 20,000 square miles and its shoreline reached 1000 feet above the present lake level. The sediments of Lake Bonneville range from peripheral gravel and sand deposits to central basin calcareous clays and silts, gypsum sands, and saline precipitates. The drilling and engineering tests conducted by the Utah State Department of Highways for many highway structure sites and the construction of Federal Interstate freeway provided engineering and hydrologic properties of Lake Bonneville sediments. Ground water and surface brine exploitation have contributed hydrologic and chemical data; the geologic and mineralogical data are scientific research contributions.

Jan 1, 1967

By C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By H. Y. Jennings

An extensive field and laboratory experimental program was carried out to compare the waterflood behavior of carefully preserved soft and unconsolidated cores with measurements on the same cores after extraction. Results obtained from using idealized consolidated and unconsolidated porous media in which wettability could be carefully controlled were contrasted with the preserved core data. The controlled tests on idealized porous media investigated the effect of wettability, flood rate, core length, core permeability and consolidation on the displacement of high viscosity oils. It was concluded from these studies that waterfloods are more favorable when carried out with crude oil in preserved soft and unconsolidated cores than with the same cores after they have been extracted and re-saturated. Waterfloods are usually more favorable when carried out with crude oil in extracted .soft and unconsolidated cores than with refined oil of the .same viscosity in the same cores. The less favorable behavior of extracted soft and unconsolidated cores compared to preserved cores is due to alteration of the core by extraction. Preserved cores saturated with native water and oil should be used for laboratory displacement experiments because they more accurately reflect true reservoir behavior INTRODUCTION The demand for low gravity crude oil created by refinery modernization has focused attention on increasing the production of this viscous crude oil. Billions of barrels are in place in fields that are depleted, or nearly depleted, by primary production mechanisms. Since low gravity reservoirs are relatively recent, geologically, the solid matrix material is usually soft and unconsolidated sand. Such formations are also characterized by a high clay content. Evaluation of sophisticated oil recovery processes with the associated high capital investments has increased the demand for special core analysis tests on material from these soft and unconsolidated sand reservoirs. Data in this paper have resulted from an extensive field and laboratory experimental program. The initial objective vras to provide soft and unconsolidated sand cores for laboratory measurements with as little alteration as possible from their reservoir condition. A secondary objective was to compare the waterflood behavior of these carefully preserved cores with measurements on the same cores after they had been extracted and resaturated. When the comparison showed markedly different behavior the final objective was to attempt to explain the difference by making measurements on idealized porous media free of clay in which initial wettability could be carefully controlled. EXPERIMENTS MATERIALS Core Material The preserved cores used in this study were obtained with as little alteration as possible from their reservoir conditions. Special techniques were developed to satisfy this objective. The cores were cut with native crude whenever the crude had the necessary properties to satisfy the minimum drilling fluid requirements. A pure hydrocarbon chromatographic tracer was added to the crude to provide a simple, safe and inexpensive method to distinguish between oil filtrate and formation oil. Details of the tracer technique used in this study and the procedures used to handle and process the soft, unconsolidated cores have been published.' The core samples were then preserved and packaged at the well site with a dip-applied strippable plastic, or by using a rubber sleeve from a rubber-sleeve core barrel. The final step was to insure that the carefully taken and preserved samples were not altered by processing in the laboratory. Some soft and poorly consolidated sands were carefully shaped in the lab and encased in a protective mounting without disturbing their three-dimensional integrity. Many samples were so poorly consolidated that they literally flowed from the package when the seal was broken. A technique was developed to obtain cylindrical plugs from these samples by using liquid nitrogen as the drilling fluid in a conventional core-drill, drill-press assembly. The idealized porous media consisted of sintered rods of Alundum RA 139, outcrop sandstone identified as Al-hambra sandstone and packs of No. 130 Nevada sand. This sand is 95 per cent 140-200 mesh. (Physical properties of these porous media with those representative of preserved cores are in Table 1.) The natural cores and most of the idealized porous media were 1 1/2-in. in diameter and 3-in. long. The samples used to study the effect of core length were 1 1/2-in. in diameter and 12-in. long. Liquids Water and oil produced from the formations being studied were protected from the atmosphere and collected in carefully cleaned glass or plastic-lined containers. The production was free of chemical additives such as emulsion breakers and corrosion inhibitors. The crude oil was

Jan 1, 1967

By Stephen D. Cramer

The objective of the present studies was to develop thick adherent and coherent coatings of platinum and palladium on refractory metals and other substrates of industrial and engineering importance. Existing platinum and palladium electrolytes were modified to make them suitable for the electrodeposition of thick deposits. The optimum operating conditions for these electrolytes were established. Pretreatment procedures for columbium, copper, graphite, molybdenum, nickel, stainless steel, tantalum, titanium, tungsten, vanadium, and zirconium substrates were studied. New pretreatment procedures for columbium, molybdenum, stainless steel, tantalum, tungsten, and nickel were developed. The internal stress and hardness of selected electrodeposits were measured. The effects of heat treatment upon the properties of electrodeposits were studied.

Jan 1, 1967

By Arcy R., D&apos George

A process for removing sulfate from Great Salt Lake brines and other natural brines, including sea water, has been developed. Sulfate is quantitatively removed by precipitation as barium sulfate in a cyclic process employing ion-exchange techniques. Barium is continously recovered and recycled, and sodium carbonate and sulfur or sulfuric acid are produced as byproducts in quantities sufficient to more than defray the cost of desulfation.

Jan 1, 1967

By Russell E. Griffin

Dielectric constants and dissipation factors were measured for six rocks over the 20-to 100-megahertz frequency range by means of the susceptance-variation method. Results for both dry and moist specimens are presented and compared with data reported by others. Loss factors calculated from the data presented are important to the Bureau's study of rock fragmentation by means of dielectric heating.

Jan 1, 1967

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By A. J. Rergis

During the past ten years a number of papers have appeared describing zeolite occurrences in the western United States in Mesozoic sedimentary rocks, altered bedded Tertiary pyroclastics, playa lakes, hot springs, and amygdaloidal basalts. With the emergence of natural zeolites as economic industrial minerals it appears, useful to develop a system of classification to delineate those zeolite deposits of economic interest which were not discovered until the middle 1950's. The first attempt at a classification of naturally occurring zeolites was made in 1914 by Lindgren l when he classified the zeolites into eleven groups based on their mode of occurrence. The zoned zeolites in the Mesozoic rocks of New Zealand and elsewhere were classified according to the mineral assemblages by Fyfe, et al.2 in 1958 as a zeolite facies corresponding to low grade regional metamorphism. In 1966, Hay suggested as an alternative to the preceding classification one which would "classify as diagenetic all mineral assemblages produced in sedimentary rocks under conditions in which zeolites are formed." In this paper a classification is proposed with the objective of providing an overall perspective of the zeolite occurrences in the western United States.

Jan 1, 1967

By O. C. Baptist

The gravitational pressure gradient (GPG) in porous sandstone containing free gas was determined to define the proper GPG to use when calculating the rate of downdip flow of oil in the Sub-Scalez No, 1 sand, Elk Hills field, Naval Petroleum Reserve 1. The GPG was determined at several gas saturations using long, artificially consolidated sandstone models that were mounted vertically in some tests and horizontally, with rotation, in others. Also determined by laboratory and field tests were relative permeabilities, capillary pressure relations; critical gas saturation, water sensitivity, and depletion drive performance. The critical gas saturation in the models having an absolute permeability of 1 to 2 darcys was about 2 percent of pore volume. The GPG with the critcal gas saturation was that due to the weight of the gas-saturated oil. The GPG in the upper part of the models was reduced as gas saturation increased to a value considerably larger than the critical. The exact gas saturation at which the GPG became less than that due to the weight of the oil could not be determined but was estimated to be of the order of 10 percent of pore volume. Tests indicate that the rate of oil production is not permanently reduced by exposure of the sand to fresh water but that the rate of injection of fresh water will be considerably less than that to brine, Methods for determining the factors mentioned above are discussed.

Jan 1, 1967

By Robert W. Ageton

Optimal planning for mining the deep, lead-zinc-silver deposits of the Coeur d'Alene mining district, Shoshone County, Idaho, could be facilitated by a knowledge of the magnitude and direction of the pressure acting in the virgin rock. The distribution of primary stresses should be considered in order to prevent possibly destructive mining-induced stress concentrations. This particular investigation was concerned with determining stress in a zone 4,000 feet below the surface and known to be ender stress concentrations due to mining operations. Disking of the stress-relief cores obtained in a vertical down hole permitted qualitative evaluation from visual observations; the results indicate that a high lateral stress existed at the time the measurements were made. Stress-ellipsoid determinations gave a compressive principal stress of -13,000 psi oriented about N 45° W and nearly horizontal, a compressive principal stress of -11,000 psi oriented about S 45° W and abut 60° off the vertical pointing away from the vein, and a compressive principal stress -5 -7,000 psi oriented N 45° E and about 60° off the vertical, pointing toward the vein. Subsequent to the overcoring stress-relief drilling, a rock burst occurred about 100 feet northwest of the test site.

Jan 1, 1967

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By M. J. Mullikin, J. B. Conway

for use in describing combined first- and second-stage creep data. In the above ?o represents the instantaneous strain on loading, ?t the limit of transient creep, ?S the steady-state creep rate, t the time, and ? a constant leading to the exhaustion rate of transient creep. It was noted that this equation was similar in form to that proposed originally2 by McVetty. This type of equation was also suggested by Andrade and Aboav3 in studies of the shear strain of cadmium. Calculation of the constants ?o, ?t, ?, and ?s, in Eq. [ l] is somewhat involved due to the slight complexity of this relationship. In the paper by Garofalo a computer approach based on a least-squares analysis was recommended. Such an approach involves a trial and error solution but when a computer facility is available the difficulties in this calculation are of little consequence. It does mean however that the evaluation of this type of equation would become quite tedious if computer facilities were not available. Some recent studies have identified a fairly straightforward method for calculating the constants in the Garofalo equation. While not leading to a least-squares evaluation the approach is accurate and is recom-

Jan 1, 1967

By J. Bednar, R. R. Rogers, W. Dingley

"Zinc is by far the most important metal used for protecting steel from the ravages of corrosion, and cadmium is also used extensively for this purpose. These metals are applied by electrodeposition in cyanide baths when a particularly good appearance and high throwing power are required. One great disadvantage in using these baths has been the decrease in cyanide concentration and the increase in carbonate concentration that takes place during the plating. Another disadvantage has been the development of serious embrittlement in high-strength steels. The present authors have developed new cyanide baths for electroplating both zinc and cadmium on steel. These baths are stable in composition during plating, they have not produced appreciable embrittlement in the high-strength steels that have been investigated up to the present time, and they permit the use of considerably higher plating current densities. In addition, they produce extremely fine grained coatings that are attractive and have excellent adherence and covering properties. Brighteners can be used in the plating baths if bright finishes are required."

Jan 1, 1967

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of' the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak's theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967

By Stanley A. Feitler

This Bureau of Mines report deals principally with the resources and economic aspects of feldspar in the United States east of the Mississippi River. Although in a strict sense, all phases of the feldspar industry affect its economic structure, emphasis in this study is on supply, demand, and marketing. Although feldspar was originally mined for use in the manufacture of pottery and other ceramics, the glass industry, which began to use feldspar in the mid-1920's, now consumes more than half of the annual output. Most mining is open cut, and the methods used are similar to those used in mining crushed b stone. Excess plant capacity has been chronic, and production is usually about 30 percent of capacity fur the industry as a whole. Since 1947, feldspar consumption has grown more slowly than the average for all U.S. industry. This has fostered intense competition, especially for the glass market. Prices have not kept pace with inflation, and profits are small. The trend of consumption through 1970 for glass feldspar is expected to be upward; less rapid in consumption of ceramic feldspar is anticipated.

Jan 1, 1967

By Paul J. Fopiano

SOME relationships between the flow characteristics of iron single crystals of 99.9 pct purity and the behavior of imperfections have been investigated. X-ray rocking-curve measurements and etch-pit counts were made as a function of plastic strain, and compared to the stress-strain curve obtained on a modified Polyani tensile machine. Crystals grown from rolled strips of vacuum-melted iron by the strain-anneal method1 had a high preference for a (110) longitudinal direction and a (211) face normal. The tensile specimens were prepared from 2 by i by 0.040 in. single crystals having a gage area of 3 by \ in. Rocking-curve measurements were carried out with a highly perfect germanium monochromating crystal in which the dazz spacing was matched to that of the dZl1 in the ir0n.l Well-collimated CuKal radiation was used throughout. These procedures practically eliminated errors due to geometrical and wavelength resolution. Inasmuch as the rocking-curve half breadth may vary markedly from point to point in the specimen being irradiated, the crystals were strained in place by mounting a hydraulic loading device on the double-crystal spectrometer. The rocking curves were taken after each increment of strain in the unloaded condition, since no observable difference was found in the rocking-curves between the loaded and unloaded states. The rocking-curve half breadths of the as-grown specimens were in the range 90 to 120 sec of arc when the beam irradiated an area of about -£ by -& in. on the specimen. DeMarco and weiss3 have shown that, for a well-colli- mated X-ray beam, irradiating about 10"! sq in. of the very same material, half breadths within 10 pct of the Darwin natural half breadth were observed. Since the rocking-curve specimens were stressed by the load-unload technique, the strain achieved at any given stress depended on the time of holding because of low-temperature creep. Fig. 1 shows the rocking-curve half breadth (also area/peak height) as a function of plastic strain for a relatively short holding time (2 to 5 min) at each stress level. For strains less than 0.1 pct the rocking-curve breadth is essentially constant; it is only for larger strains that there occurs a significant increase in this breadth. Where the holding times at each stress level were longer (by well over an order of magnitude) there occurs a significant increase in the rocking-curve breadth only after plastic strains of the order of 0.6 pct had been introduced into the specimen. This observation is related to the time dependence of creep phenomena and emphasizes the difficulty in comparing data obtained by two such different straining methods. Etch-pit results were obtained using a 2 pct nital etch on specimens strained in the range of 0 to 1 pct. Prior to etching, all specimens were annealed for 3 hr at 150°C, the carbon content being sufficient to decorate the dislocations for strains of at least 1 p~t.~ The data points were all taken from parts of the same single crystal which had been strained with short holding times at stress in increments of strain of the order of tenths of 1 pct. The (211) plane is particularly difficult to etch-pit in vacuum-melted iron and therefore it is felt that these values are as much as an order of magnitude low. Fig. 2 shows the etch-pit density as a function of plastic strain. The smooth curve passing through the data points is not meant to infer a quantitative correlation with the rocking-curve data. What is of interest, however, is the change in etch-pit density in the region of 0.2 pct plastic strain. The first three increments in strain (points 2,3, and 4) did not produce a measurable change in the etch-pit density while subsequent increments did produce a measurable change. While the absolute values of these results do not appear to be cor-

Jan 1, 1967