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Jan 1, 1969

By E. W. Mehal, R. H. Cox

A planar Gunn oscillator was developed for use in a monolithic microwave integrated circuit. The device was designed to operate in the frequency range of 20 to 30 GHz with a continuous wave output. Selective epitaxial deposition was used to form the n+n-n+ device structure in (111)-B semi-insuluting GaAs. The active n- region was about 5 µ thick and was doped to about 2 x 1015 electrons per cu cm by the reactor background. The mobility was -5000 sq cm v-1 sec-1. The n+ epitaxial deposits were doped to 1 x 10" electrons per cu cm using S2Cl2. Planarity of the three DURING the past few years, new microwave devices in discrete form have been developed utilizing GaAs. The next logical step is to combine these devices in a successive deposits was quite good; total overgrowth was less than 1 µ. Metal ohmic contacts were applied to the n+ or n- regions using a Ag-In-Ge alloy. The n+n-n+ devices had symmetric IV characteristics and could be operated C. W. for both directions of device bias. Metal ohmic contacts made directly to the n-region always Produced asymmetric devices. C. W. operation was obtained over the 22 to 28 GHz frequency range. The best performance obtained was 1.5 mw C. LV. output at 28 GHz. microwave integrated circuit. A potential application would be a radar receiver operating in the millimeter wavelength region. The key component in such an integrated circuit is a microwave oscillator, recently described by Gunn.1, 2 Under the influence of a large electric field, high-resistivity GaAs exhibits a bulk negative resistance, and high-frequency current oscillations result. Since relatively high voltage and

Jan 1, 1969

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.'-'2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;' 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;'" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By J. M. Oblak, W. A. Owczarski

A cellular appearing recrystallization product formed by annealing a cold-worked nickel-base super-alloy at 1800°F has been studied by electron nzicroscopy. Prior to deformation, an equilibrium micro-structure of fcc matrix y and cuboidal ,,', Ni (Al, Ti), precipitates of CuzAu structure had been established by an age at 1825°F. The strain-free recrystallization cells consist of very large rodular y' particles in a y matrix. They precipitate is oriented and coherent both before and after recrystallization. The results showed that y' coarsening accompanies recrystallization at 1800°F. However, it does so as a secondary effect and does not necessarily take place at lower temperatures. The structural similarity of this reaction to cellular precipitation in other systems indicates that lattice strain may also play a significant role during some cellular precipitation reactions. THERE have been numerous microstructural investigations of recrystallization in single-phase materials but two-phase systems have received much less attention. The second phase can either remain inert or be altered along with the matrix during recrystallization. If the second phase is an oxidelm3 or a relatively inert pre~ipitate,~, recrystallization is retarded when the interparticle spacing is less than 1 p. Prior to the onset of recrystallization, these materials show a well-polygonized substructure with the subgrain size limited by the interparticle spacing. Since recrystallization by the motion of preexisting grain boundaries6 is not observed, retardation has been related to particle pinning of the subboundaries. This pinning prevents coalescence' or growth8 of subgrains to a critical size (formation of a high-angle boundary) necessary to initiate recrystallization. In a material such as a nickel-base superalloy both y matrix and y' precipitate are altered by the recrystallization reaction. Haessner et al.' studied the recrystallization of a cold-rolled Ni-Cr-A1 alloy by electron microscopy. The material was initially cold-rolled in the supersaturated condition. upon annealing at 750°C, immediate precipitation of 7'occurred. Presence of this 7' greatly retarded the onset of recrystallization which eventually took place by the development of randomly oriented, strain-free grains. The original •/ was dissolved at the recrystallization interface and reprecipitated as oriented, coherent par-tiles in the new grain. Recrystallization caused a refinement of .)' particle size. Recently ~hillips'' investigated recrystallization of Ni-12.7 at. pct Al. Reduction by cold rolling presumably elongated the p' precipitate into lamellae that remained coherent with the matrix. After recrystallization at 600" to 750°C, there was no unusual change in y' particle size al- though there was a tendency toward clustering along the prior rolling direction at 750°C. Above 750°C, the recrystallized grains were generally free of precipitate. Studies in the somewhat analogous Cu-3.23 wt pct CO" and Cu-2 wt pct'2 systems demonstrated that the coherent cobalt-rich fcc precipitate in these alloys obstructed softening, initiation, and completion of recrystallization. The precipitates were deformed into lam~llae during rolling and those of diameter less than 250A remained coherent. Recrystallization took place by the growth of new grains into the recovered or poly-gonized material. In the first study," both matrix and precipitate reoriented in the same manner upon passage of the recrystallization interface. There was no change in particle size or morphology. Tanner and ~ervi,~ on the other hand, observed that motion of the recrystallization fronts was strongly hindered by the pinning action of coherent precipitates in the deformed material. Particles in contact with a pinned boundary coarsened and coalesced leaving a denuded zone in the unrecrystallized region. When the number of pinning points was sufficiently reduced by coalescence, the boundary swept past these particles and through the denuded zone. The authors1' considered this as a variation of discontinuous precipitation with both chemical driving force and deformation strain energy contributing to recrystallization. Preliminary observations by the present authors had revealed that recrystallization in Udimet 700, a nickel-base superalloy, occurred in an entirely different manner. Optical metallography showed that the recrystallized product formed as cellular colonies containing coarse y' particles elongated in the direction of cell growth. In this investigation the structural features of this reaction were investigated by transmission electron microscopy. EXPERIMENTAL PROCEDURE As-received I$-in. rounds of Udimet 700* were (wtpct) 18.4 15.2 4.95 4.42 3.43 0.06 0.031 0.14 Bal. solution-annealed for 4 hr at 2150" and then fast air-cooled. An initial y-~' structure was established by a 4-hr age at 1825°F followed by a fast air,cool. Essentially the equilibrium volume fraction of ?' at 1825°F is precipitated within 4 hr. Microstructural examination showed no measurable increase in the amount of precipitate after longer aging times. Deformation consisted of swaging to 52 pct RA with 6 pct reduction per pass at room temperature. To reduce the precipitation potential to a negligible amount, recrystallization anneals were conducted at 1800"~ (982"~). Microstructures were investigated by optical and transmission electron microscopy. To prepare foils for electron microscopy, the material was first sliced into 30-mil slabs parallel to the swaging direction. Discs were dimpled and electrolytically cut from

Jan 1, 1969

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By C. M. Mason

A series of gelatinous permissible explosives was prepared with increasing sodium nitrate content and subjected to an improved technique for evaluating incendivity in coal dust-air and coal dust-gas-air mixtures. Those explosives containing an appreciable amount of sodium nitrate were found to be very hazardous in coal dust-air and coal dust-gas-air mixtures.

Jan 1, 1969

By R. A. MacGregor

The Stanreck mine of Stanreck Uranium Mines Limited in located on Quirks Lake in the Elliot lake - Blind River area of Northern Ontario. It is approximately 25 miles north of the north shore of Lake Huron, equidistant between the cities of Sudbury and Sault Ste. Marie. The property was developed ad brought into production at a rate of 3,000 tens of ore/day during the uranium boom of the mid 1950's. By 1960 mine waters were becoming quite acid through the activity of bacteria. Treatment of this water was begun for pollution control and a small amount of uranium which had been leached from the ore by these acid waters was recovered. Development of bacterial leaching with a view to increasing production by this method commenced in December 1962. Subsequently, it was succeesfull in producing 10,000 - 15,000 lbs. of U308/month. Since late 1964 uranium production has been obtained solely from bacterial leaching. A rare earth concentrate was also made for its yttrium content during 1966 and 1967. This paper describes the development, operation and methods used in the underground bacterial leaching process.

Jan 1, 1969

By M. J. Pool, P. J. Spencer

Using liquid tin as the solvent metal, the heats of solution of silver and gold in dilute Ag-Au-Sn alloys have been determined at 723°K by solution calorimetry. From the values obtained, the various enthalpy interaction coefficients in the liquid solutions have been calculated. The self-interaction coefficients Au and Ag values of 2413 and -6322 cal per g-atom in binary Au-Sn and Ag-Sn alloys, respectively. For an alloy containing 0.04 mole fraction Ag, Au is equal to 2443 cal per g-atom, and in an alloy containing 0.04 mole fraction Au, Ag has a value of —8883 cal per g-atom. Ag Au has been determined as —2650 cal per g-atom. ADDITION of a second solute to a dilute binary alloy may cause striking changes in the thermodynamic characteristics of the alloy. As yet, such influences cannot be reliably predicted and it is only by accumulation and critical assessment of data that definite patterns can be established. Solute interactions in dilute solutions were first treated mathematically by Wagner,1 who derived expressions for the Gibbs energy interaction coefficients. For an alloy consisting of. two dilute solutes, i and j, in a solvent s, these coefficients are given by: where yi is the activity coefficient of component i and x represents the mole fraction of solute or solvent. Other interaction coefficients have since been established in terms of the various partial molar thermodynamic properties of an alloy; the definitions of these are summarized in a recent paper by Lupis and Elliott.2 Mathematical and experimental studies of such coefficients have received much attention recently, providing a very useful theoretical background to an understanding of the nature of solute interactions taking place in dilute solutions. One of the definitions to arise from such work has been the extension of Wagner's treatment by Lupis and Elliott4 to include an enthalpy interaction coefficient, defined as. where ?Hi is the relative partial molar enthalpy of component i. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hio, and to the enthalpy interaction coefficients by the expression: Values of ?Hi can often be obtained with a high degree of accuracy by calorimetry, and, if the composition of the alloy is carefully controlled by making calculated solute additions throughout a series of measurements, application of Eq. [2] will enable reliable enthalpy interaction coefficients to be determined. Partial heats of solution must be investigated as a function of solute concentrations down to xi = 0, and, since ? values are obtained from the slope of mi plotted against x, great care must be taken to obtain precise data. The data for binary systems which are presently available often require extrapolation of ?Hi values from compositions as great as xi = 0.05 or even 0.1 to obtain limiting heats of solution. Reliable enthalpy interaction coefficients are thus impossible to obtain from published data for most of the alloy systems already investigated. The aim of the present work was to determine values of Au, Ag, Ag, and Au in the limit xsn -1 for the relatively simple Ag-Au-Sn system and from these results to gain some insight into the possible influence

Jan 1, 1969

Jan 1, 1969

By Edward S. Bell, Frank Angebrandt

"Nuclear reactors must have very large heat outputs to compete with conventional sources and the only feasible applications are in the production of electric power or large quantities of process steam. This paper considers alternative fuels for electric power generation in Canada. In a publicly owned utility, nuclear stations are economic for base-load generation for unit sizes of 500 mega• watts or larger where competitive fossil fuel costs are higher than about 30 cents per million Btu. In British Columbia, Alberta and Saskatchewan, fossil fuels will continue to be in adequate supply at costs lower than 30 cents per million Btu and thus, except for the special case of Vancouver Island, power generation in Western Canada will continue to be the hydraulic and conventional thermal type. In Eastern Canada, fossil fuel prices are likely to be higher than 30 cents per million Btu and most utilities will be able to install units of 500 mw or larger, so that nuclear power plants will provide much of the base-load generation required. Base-load generation comprises about two-thirds of the energy generated by power utilities. By 1990, the total annual electrical energy load will be over 600 billion kwh, with two-thirds of this load in Eastern Canada. Allowing for additional hydraulic resources which may be developed in Quebec, British Columbia and Manitoba, hydraulic generation is forecast to provide a little more than a third of this electrical energy, nuclear generation a third and fossil-fuelled generation about a quarter."

Jan 1, 1969

By W. N. Hiatt

The mathematical theory of the flow of two-phase, incompressible fluid through porous media is clarified, and the development of a general fluid displacement equation for two-phase, incompressible vertical flow through porous media is outlined. The relationship between the three components of the equation — the "fluid drive effect", the "gravity effect", and the "capillary effect'' — is discussed, as well as implications of the analysis in connection with the study of certain types of petroleum reservoirs. INTRODUCTION The purpose of this paper is to clarify and summarize the mathematical basis of the theory of two-phase incompressible fluid flow through porous media, particularly as it pertains to vertical flow, and to present a qualitative* exposition of the controlling factors involved in circumstances where this type of flow may exist. Although the generally accepted theory of heterogeneous fluid flow through porous media was developed a number of years ago by Muskat,1 and Buckley and Leverett2, 3 using the basic premise of Darcy, (and since then expounded upon by many others) there is a need for an over-all summary and clarification of this theory, especially regarding certain types of applications in connection with so-called "gravity-drainage-type reservoirs". The source and derivation is outlined for what is referred to here as the "General Fluid Displacement Equation for Incompressible Vertical Two-Phase Flow through Porous Media''. This equation would apply under the condition where the pressure drop along the path of flow is negligible in comparison with the pressure level on the system, or where compressibility and solubility effects are negligible. These conditions exist ordinarily in gravity-drainage-type reservoirs. Specifically, it will be shown that this general equation may be developed directly from the basic equations, which, according to present theory, govern the general case of viscous heterogeneous flow through porous media. This general equation has appeared in the literature previously, but in most cases its development from basic theory is not indicated clearly, or the equation is presented in terms of groups of constants and variables involving reduced or dimensionless quantities. This presentation is expedient in cases of experimental or computer applications; but it may make it difficult for the practicing petroleum engineer to identify all the factors involved or to understand the relationships between them. Therefore, in the following development, only ordinary mathematical parlance will be used, and no terms involving groups of other equations or reduced or dimensionless quantities will be used. DERIVATION The following equations for two-phase oil and gas flow result from analogy with Muskat's general equations,** if solubility and compressibility effects are neglected, and if all volumes are considered in terms of reservoir conditions, and the water phase, if present, is considered to be immobile (or effectively a part of the porous medium.) In this case, the sum of the oil and gas saturations may be taken as unity, and the saturation of each phase is in terms of the total hydrocarbon saturation. Note that in Eqs. 1 and 2, and in the derivation following, z is taken as positive in the vertically downward direction,

Jan 1, 1969

A belt of serpentinized ultrabasic rocks intrudes a moderately folded geosynclinal sequence of fine to coarse sediments, acid, intermediate, and basic volcanics as well as a batholithic mass of granitic rocks. The ultrabasic body contains small included masses of melanocratic and leucocratic rocks, together with chromium, copper, zinc, and nickel mineralization.

Jan 1, 1969

By Bruce F. Bohor

Silica sand has been mined in Illinois from the St. Peter Sandstone since the turn of the century, especially in the area around Ottawa on the Illinois River in the north-central part of the state. Production of this sand, consumed mainly by the glass and foundry industries but also sought after for many other uses, has grown with the economy, and last year's output in Illinois exceeded 4,000,000 tons. Such an important commodity was given the early attention of the Illinois State Geological Survey, and a very complete report was issued in 1928, authored by J. E. Lamar. The mining and processing of the sand has changed very little during the intervening 40 years, so that much of Lamar's data and descriptions are applicable today. More recently, the stratigraphy of the St. Peter Sandstone in north-central Illinois has become better known from the work of Willman and Payne (1942). The present authors have borrowed generously from Lamar's publication, and we wish to acknowledge the contribution of both of these studies to our work.

Jan 1, 1969

By A. E. Aho

"The material presented in this paper will be subject to modification as new data become available, but it is presented in the hope that it will inspire more intensive mineral exploration and geologic studies of what appears to be one of Canada's richest mineral provinces. A metallogenic province 400 by 150 miles in extent, lying mostly northeast of Tintina trench, encompasses most of the base metal deposits of Yukon, as well as deposits of other metals. Its main features are northwesterly trending arcuate fold belts, with several orogenic axes, which include most of the metamorphosed rocks, granitic intrusives and mineralization; and which are modified by regional uplifts, northwest-striking fault trenches, and lesser transverse folding and faulting.The main base metal occurrences and their regional controls are summarized briefly. Most of the replacement-type deposits are localized in late Proterozoic to early Paleozoic rocks, particularly Lower Cambrian -probably because these are the most physically and chemically favourable hosts encountered in an appropriate temperature and pressure environment; perhaps because of early age of deposition. Most of the deposits also occur near heat sources or intrusives with associated structural uplift, which has, moreover, served to expose the older rocks. They also tend to occur near known or suspected regional fault trenches, such as Tintina, Macmillan and Hess, although this relationship may be fortuitous. In detail, they may be localized in fold axes, flat-lying beds or other appropriate structural traps. Vein-type deposits are fracture-controlled and localized by dilational localfties, the competence of wall rocks and ""damming"" effects.In the Anvil district, large stratiform iron-zinc-lead replacement deposits lie parallel to gently plunging flex-ures in phyllite in a zone parallel to the Tintina trench, along the southwest flank of the arch-like Anvil batholith. About 80 million tons of massive sulphide ore probably existed before erosion of the Faro orebody, the Vangorda deposit could have been of similar magnitude before erosion and much more tonnage probably remains to be discovered in the district. The Anvil deposits may differ from others found to date in Yukon, but resemble the Sullivan orebody of southeastern British Columbia in their large size, localization in essentially non-limy peptic to arena-ceous host rocks of Proterozoic or early Paleozoic age and proximity to the Rocky Mountain -Tintina trench sys-tem. These features suggest an origin from primordial subcrustal sources.More major ore deposits, not only of lead, zinc and copper but probably of other metals as well, will no doubt be found in similar environments in Yukon or Alaska. Thus, the base metal province of Yukon offers challenging opportunities for prospecting, development, field studies and basic research."

Jan 1, 1969

By W. A. Gow, V. F. Harrison, H. H. Mccreedy

A semi-continuous bench-scale, countercurrent-decantation system, in which the ore was moved countercurrently to the flow of leaching solution, was used to conduct acid-leaching tests on uranium ore with the aid of bacteria. This method, which involved a low degree of agitation, was successfully applied to extract uranium in practical amounts and at practical rates. The acidity of the leaching solution was the main variable investigated in the bench-scale tests done at the Mines Branch, Ottawa. Over 90 11er cent of the uranium was extracted in a six-stage system. The results suggest that this technique could be ap-plied in the utilization of bacterial oxidation and leaching as a method for treating Elliot Lake uranium ore.

Jan 1, 1969

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By A. H. Harvey, M. Delangen, A. D. Fernie

"A large-scale expansion to Pacific Coast Bulk Terminals Ltd. has now been completed and placed in operation. The original plant, built approximately eight years ago, consists of the direct rail-car to ship transfer of bulk commodities. The extension includes additional rail-car unloading, a transfer house system for directing commodities to storage or ship, major storage and reclaim facilities, a second shiploader and a second deep-sea berth. In addition to the facilities for overseas shipments, a wood-chip loader and a barge berth have been installed for domestic shipments of wood chips and, occasionally, for other local commodities. The design considerations imposed by the nature of the products to be handled are covered in this paper."

Jan 1, 1969

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969

By Joe B. Rosenbaum

Waste solutions from sea water desalination processes are enriched in minerals by a factor of two or three. This suggests that extraction of selected mineral components from the concentrated brine might help pay desalination costs. The possible recovery of gold has received particular mention. Sonstadt, in 1872, reported the gold content of sea water as 65,000 micrograms per cubic meter, or 65,000 parts per trillion. At $35 an ounce, this is equivalent to $0.065 per ton of sea water. Fritz Haber, however, after his abortive venture to restore Post War I Germany to economic health by recovering gold from the sea, concluded the gold content was 4 micrograms per cubic meter. Haber's analysis is equivalent to 0.0004 cent per ton. In the past 10 years, investigators using advanced analytical techniques reported from 4 to 27 micrograms per cubic meter. Our brief experiments to determine a threshhold value for the gold in sea water employed solvent extraction for initial concentration, evaporation of the gold-loaded organic for further concentration, and atomic absorption analysis of the gold in the concentrated organic. Radioactive gold was used as a tracer for monitoring the gold through the concentration and analytical steps. Our method established that sea water contains about 11 parts gold per trillion parts sea water, or 0.001 cent worth per ton. This agrees closely with results of recent studies by other investigators employing ion exchange resins and neutron activation techniques.

Jan 1, 1969

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3'7

Jan 1, 1969