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By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By R. A. Beall

Homogeneous zirconium-alloy ingots have been cast on a production basis by the consumable-electrode arc-melting process at the Northwest Electrodevelopment Experiment Station, Bureau of Mines, Albany, Oreg. This paper describes the various methods used to introduce alloying materials into the ingot and evaluates 1 each method by the degree of homogeneity of resulting ingots, as determined in tests on sections cut from the ingots. As many as 30 or more ingots, each 6 to 10 inches in diameter and weighing 300 to 500 pounds, were melted, using each method; and, as most of them subsequently were fabricated to strip 0.1 inch thick, the test results are considered to be representative of production practice. Ingot homogeneity has been considered more difficult to achieve in arc-melting practice than by methods where the molten metal is poured into molds and the addition can be stirred into the total mass of metal before casting. Owing to the unique requirements of consumable-electrode arc melting the addition can be made only to that part of the total mass of the ingot that is molten at one time. Observation of the flowlines in 500-pound ingots produced at Albany indicates that the molten pool has a maximum depth about equal to the ingot diameter. The weight of metal molten at one time is, therefore, not over 100 pounds. Characteristically, the arc-melting process is conducive to segregation, which can be overcome, at least partly, by adding the alloy constituents almost continuously during casting.

Jan 1, 1956

By Williams K. C

This paper presents a brief account of the plant which has been developed at Port Pirie to recover, by vacuum distillation, the greater part of the zinc content of desilverized lead. The present plant is an experimental unit, which is run in conjunction with the normal refinery practice, but can be cut out of the circuit. It will shortly be dismantled and duplicate units will be built on the sites chosen for the final plant installation.The unit described here has treated flows of 16 to 37 tons per hour of desilverized lead, to recover 90 to 95 per cent of the zinc contained in it. It is not intended here to detail all aspects of the vacuum dezincing operation, nor the developments which precededthe adoption of this design. The essential features of the present plant will be described and, where these are peculiar to the present experimental location, the intended alteration for the final plant will also be mentioned. OUTLINE OF PLANT AND PROCESSLead issues from the continuous desilverizing kettle at about 350° C. containing about 0·57 per cent Zn. It is conveyed by a tiled launder to the preheater, where it is heated to 580-620° C.Hot lead from the preheater enters the vacuum vessel via a barometric leg. From a reservoir holding about 19 tons of lead it falls by gravity in a thin film exposed to high vacuum (20-50 microns)3 and leaves the vessel via a barometric leg, entering the lead pot. The lead leaves this pot at 540-560° C., containing 0·03 to 0·06 per cent Zn, which is removed, together with residual antimony of 0.02 to 0·06 per cent, by a separate final refining process.

Jan 1, 1956

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,' Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies' in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,' supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By David Cornell

Back pressure test data on natural gas wells are short time test data of unsteady state nature. Performance curves from which unsteady state effects have been eliminated, called stabilized performance curves, are necessary for understanding the behavior of gas wells and for scheduling gas fields for periods up to 20 years. A calculation procedure has been developed whereby three day, seven day, 30 day, or other duration stabilized performance curves may be calculated from back pressure test data. Such curves are essential for correct gas deliverability calculations and gas field scheduling. I NTRODUCTION The manner in which a back pressure test is made will affect the slope of the back pressure curve because the radius of drainage changes with the length of time that the well is allowed to flow. The reciprocal of the slope of the back pressure curve is defined as n in Equation 1 and varies from 0.5 to 1.0. If the flow is viscous and the radius of drainage constant, n will have a value of 1.0. Because of turbulence in the formation near the wellbore, the pressure drop is usually greater than the viscous flow pressure drop and the exponent n is frequently less than 1.0. In addition, since the radius of drainage moves away from the well-bore during the test, the gas flows a greater and greater distance as the test proceeds, with a resulting increased pressure drop at the high flow rates, and, again, n for the test tends to be less than 1.O. The effect of the changes in the radius of drainage may be calculated and the results used in preparing stabilized performance curves for fixed values of the radius of drainage. Such curves can be made for a defi- nite time period, such as three day, seven day, or 30 day stabilized performance curves. These cukes will show the effect of turbulence near the wellbore and can be used to predict the performance of the gas well at any flow rate or for any production period. In order to discuss the importance of the radius of drainage quantitatively, it should be defined. Muskat" defines the radius of drainage as follows: "... the radius of drainage gives the distance from the well to which the approximately steady state condition has been established ... it being assumed that no gas is removed from any point until the radius of drainage has passed that uoint." An eauivalent definition of the radius of drainage is that radius at which the extrapolated portion of the steady state portion of the pressure gradient gives a pressure equal to the shut-in reservoir pressure. This definition is also implied in the back pressure equation. The radius of drainage is, then, the distance into the reservoir from which the gas appears to originate at any time. It is, however, only a useful concept and does not actually exist. Fig. 1 illustrates the definition of the radius of drainage. At the end of each flow period the radius of drainage may depend on three factors: (1) the duration of each flow period; (2) the rate of gas production; and (3) the rate and duration of the previous flow periods. In general, back pressure tests are conducted with various lengths of production time and at various flow rates. Each individual back pressure test, therefore, requires an individual analysis. The calculations of the change in the radius of drainage have been made, however, for the case of equal flow periods for all four production rates and several sets of increasing flow rates. Fig. 2 illustrates the results of such calculations made by the method of Cornell and Katz2 for the case of 8, = 50,000 and the flow rate increasing in the ratio 1.0:2.0:3.0:4.0 for each flow period. The increase in the radius of drainage during the test is apparent.

Jan 1, 1956

By R. D. Reiswig, D. J. Mack

THE use of pyrophoric alloys in ignition devices dates back more than fifty years to a German patent granted to Carl Auer von Welsbach in 1903.' This patent named a composition essentially the same as that used in most present-day cigarette lighter "flints:" 70 pct mischmetal, 30 pct Fe, referred to here as "Auer alloy." Among the few current exceptions to this composition are those "flints" based on titanium or zirconium. The rare-earth metals of which mischmetal is composed are so similar chemically and physically remarkable similarity in their alloying behaviors would be expected. Comparison of the binary phase diagrams2 of these elements with nonrare-earth metals shows that this is true to a striking degree, so much so, in fact, that it appears that a mixture of these elements may be treated as a single component of alloys without fear of serious error. In considering alloys containing mischmetal, therefore, the mixture of rare-earth elements will be referred to merely as "cerium," the predominant element in mischmetal. In polishing cerium alloys for metallographic examination, it was soon discovered that aqueous polishing media were highly corrosive. Free cerium in the alloys acts similarly to calcium (though not quite so rapidly) in evolving bubbles of hydrogen at the metal-water interface; thus, special metallographic techniques are required. The simplest polishing technique found to be satisfactory consisted of slow hand grinding on dry emery papers through

Jan 1, 1956

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

Commercially pure molybdenum specimens were irradiated in the Materials Testing Reactor for an estimated exposure of 1.9 to 5.9x10 20 thermal nvt. Prior to irradiation, the material was ductile in the tension test; whereas after irradiation, it was brittle. The results of tension tests conducted at various temperatures revealed that the transition temperature for this material had been increased from —30' to +70°C as a result of the radiation exposure. From metallographic studies, it is concluded that the embrittlement is due to submicroscopic changes which raise the flow stress-temperature curve of the material. PRIOR to ten years ago, the bombardment of metals with high speed heavy particles such as protons, deuterons, a particles, and neutrons was primarily of academic interest. These particles existed in extremely small numbers in a few laboratories and only under very special conditions. With the introduction of the nuclear power reactors, these particles are now available in enormous quantities and it has become important from a practical standpoint to learn how well metals withstand severe reactor radiations. The principal radiations of concern in reactors are neutrons and y rays, since the heavier charged particles exist only in limited regions of reactors. Seitz,' in a theoretical approach, has shown that all of these high energy particles, except y rays, have enough energy to knock atoms from lattice sites and that these knocked-on atoms have enough energy to cause additional displacements of neighboring atoms. The result of this process would be a lattice containing many imperfections in the form of interstitial atoms and vacancies. Hence, it would be expected that the properties of metals can be changed by reactor radiations, and such has been found to be the case. Only a limited amount of data have been published in the open literature,2,3 and these data have been for relatively low integrated-neutron-flux exposures. In general, one effect of reactor radiations on the mechanical properties of metals has been to increase strength and decrease ductility. It is now possible to irradiate specimens in the Materials Testing reactor at much higher fluxes and to higher integrated exposures than previously possible.' The data which are being presented here describe the effects of a relatively high exposure on some mechanical properties of molybdenum. Experimental Procedures Material: The molybdenum used in this investigation was obtained from the Climax Molybdenum Co. The two heats from which the material originated were melted under a vacuum of 5 to 30 microns and cast in 7 in. diam water-cooled copper molds. One ingot contained 0.061 pct C and the other 0.066 pct. Both ingots were hot worked by extrusion and rolling into % in. diam rods, after which they were annealed and straightened. The rods were subsequently heated to 1100°C in a hydrogen atmosphere and swaged to ½ in. diam rods at the Research Laboratory of the General Electric Co. The resulting material had an average hardness of 264 VPN, or 99.2 Rb, and had an average of 5000 grains per sq ml in the transverse section, Test Specimens: Substandard-size tensile specimens were prepared according to the specifications shown in Fig. 1. These specimens were used also for hardness measurements. The metallographic specimens were small disks which were polished, etched, and photographed at X1000 prior to irradiation. The field studied was

Jan 1, 1956

Coal Division Industrial Minerals Division Minerals Beneficiation Division Mining, Geology and Geophysics Division Council Will Mitchell, Jr, Chairman (MBD), Kenneth L Cook, Vice-Chairman (MGGD). Edward L Clark (MGGD), Raymond B Ladoo (Ind Min Div), Sandford S Cole (Ind Mm Div), Norman L Weiss (MBD), C T Hayden (Coal), H F Yancey (Coal), Clayton G Ball (MED), P De Bruyn (MIED), Arnold Buzzalini, Secretary, AIME, 29 West 39th Street, New York 18, N Y Mining Branch Advisory Committee Will Mitchell, Jr, Chairman, Grover J Holt, J B Morrow, J L Gillson, Edward G Fox, S S Cole, Roger V Pierce, Norman L Weiss. H C Weed. J R Van Pelt

Jan 1, 1956

By H. E. Lake

VERY EARLY in the initial stages of underground development work at Eldorado's Beaverlodge operation, the decision was made to use mill tailings as a backfill product. Mining and milling commenced in June, 1953, using locally available sand as backfill, while test work and installation of a plant was carried out to prepare ?and deliver the tailings to the mining areas. The first use of tailings was made in February, 1954, a sandslime separation being carried out with hydraulic cyclones. To date (January. 1956), approximately l 40,000 tons of fill have been used in the stoping areas, providing very effective support in a 50 deg. Vein system of cut-and-fill mining. The recoverable portion of the mill tailings amounts to 40 to 45 per cent, which has resulted in a product giving a percolation rate of 6 to 10 inches per hour. Owing to the fact that Eldorado has milled from 15 to 2 5 per cent more ore than it has mined, through the purchase of custom ore, the degree of control on the sand-slime separation has not been as critical as it might normally be when the filling operation must depend only on the tailings from ore mined. A description of the conditions involved and of the plant as finally installed is given below. It might be mentioned here that, with the impending increase in milling capacity from 700 tons to 2,000 tons p.er day, the present plant will be considerably altered within the ensuing year to handle the increased tonnage and distribution.

Jan 1, 1956

By E. N. Mazza, H. S. Kalish

The effect of sintering types 302, 3028, and 430 stainless steel powder compacts in hydrogen and dissociated ammonia was investigated. It was found that sintering in dissociated ammonia resulted in as much as 0.5 wt pct increase in the nitrogen content of stainless steel even though the dissociation of the gas was complete. Sintering in hydrogen, on the other hand, reduced the nitrogen content of the stainless steel to less than 0.01 wt pct. In the case of the 302-type stainless steel, the low nitrogen content resulted in a material that was largely ferritic, whereas the high nitrogen content rendered the material fully austenitic. Sintering in dissociated ammonia resulted in lower density, generally lower tensile strength, less ductility, and higher hardness than sintering under equivalent conditions in hydrogen. The reduction of oxides on both stainless steel and iron particles was found to be effected by hydrogen partial pressure in the sintering atmosphere. Compacting pressure was found also to effect oxide reduction during sintering. DISSOCIATED ammonia often is used as a substitute'.' for hydrogen in sintering and in annealing, since economic advantages sometimes can be obtained by such a substitution. In addition, anhydrous ammonia contains very little impurity. Thus, dissociated ammonia gas is very dry whereas tank hydrogen often must be freed of oxygen and water vapor prior to use in many applications. The sintering of stainless steel powder compacts as well as bright annealing is well recognized as requiring a hydrogen atmosphere and for the foregoing reasons dissociated ammonia is frequently substituted. It has generally been overlooked, however, that the nitrogen in dissociated ammonia might have an important effect on the sintering process and on the properties of stainless steel compacts. Considered an inert gas in many applications, nitrogen, on the other hand, is very reactive with cer- tain metals. Dissociated ammonia could not be used for hydriding zirconium or titanium. Nitrogen reacts with columbium, tantalum, chromium, uranium, thorium, and many other active metals. Iron and iron-base alloys are, for the most part, inert in nitrogen but there are many borderline cases. It has been reported that stainless steel stabilized with columbium or titanium should not be sintered in dissociated ammonia.3 olybdenum has been reported as reacting with dissociated ammonia to a minor extent.' Although most of the reactions with iron-base alloys are attributed to the action of un-dissociated ammonia and the action of nascent nitrogen, Uhlig4 showed how readily pure molecular nitrogen reacts with and diffuses into 18-8 stainless steel at 1150°C. He also pointed out how readily nitrogen diffuses out of 18-8 stainless steel when heated in pure dry hydrogen, and these thorough investigations on the subject show that commercial stainless steels are nitrogen-bearing, since they are melted in air. The effects of nitrogen in stainless steel, particularly the 18-8 Cr-Ni type, previously have received considerable attention." In 1926, it was pointed out

Jan 1, 1956

By D. E. Wolfson

As a part of its overall program of coal carbonization, the Bureau of Mines is studying the coking properties of coals that may be used for metallurgical purposes. The objectives of this study were given in detail in a previous report The inherent suitability of coal for metallurgical purposes depends primarily on (1) chemical composition, (2) preparation characteristics, and (3) carbonization behavior. The first two factors, Be well as the amount of available reserves, are considered in selecting coals for carbonization tests. The selection of coal beds in Harlan County, Ky., for coking tests was based, in part, on recent studies of coal reserves by Wallace,3/ who estimated the recoverable reserves in beds 28 inches or more thick, in tons, as follows:

Jan 1, 1956

By Allen F. Agnew

Detailed stratigraphic studies in the Wisconsin-Illinois-Iowa district have made it possible to map the folds and faults that controlled the deposition of the zinc-lead ore. Prospecting on the basis of this mapping and prospecting in lower zones that are potentially ore-bearing have led to discoveries of ore. GEOLOGIC studies for the Federal and State governments in the Wisconsin-Illinois-Iowa zinc-lead district were begun in 1835, and subsequent surveys were made in the three states at intervals until 1916, see Table I. The current study of the district, Fig. 1, by the U. S. Geological Survey was begun in 1942 in the hope that a systematic investigation would help increase production of zinc and lead, then in extremely short supply. Major emphasis of the USGS program was on detailed mapping of the geologic structure and ore deposits. Preliminary maps and reports covering localities of intensive mining activity have been published during the course of this study, Fig. 2. By 1950 the objectives of the study by the USGS were revised; 71/2-min quadrangles of relatively unprospected localities as well as intensively mined localities are now being mapped in Wisconsin. Since 1945 the investigation in Wisconsin has been made in cooperation with the Wisconsin Geological and Natural History Survey, and since 1951 the geologic mapping of areas of particular interest in Iowa has been performed in cooperation with the Iowa Geological Survey. At intervals since 1943 the Illinois State Geological Survey has mapped the geologic structure and ore deposits of localities in the Illinois part of the mining district, see Fig. 2. Geology was applied by mining company personnel as early as 1853, but only sporadically, with periods of greater application between 1890 and 1925. Much of the so-called geologic work was in reality mining engineering. Since 1946 the major mining companies in the district have employed geologists who have successfully applied geologic techniques in the search for ore. History of Mining Occurrence of galena in the district was known as early as 1658 or 1659, when French explorers heard of lead mines that were apparently in the vicinity of Dubuque, Iowa. In 1690 a trading post was established near Dubuque to obtain galena. The first significant attempt at mining by white men took place in 1788 when the Indians granted to Julien Dubuque mining rights for 20 miles along the west side of the Mississippi River, including the vicinity of Dubuque, Iowa. By 1805 lead was being mined near Galena, Ill. In 1819 permanent settlement of the region was begun, and most of the important lead-producing areas had been found by 1830, see Fig. 3. Lead production in the Wisconsin-Illinois-Iowa district between 1830 and 1871 far exceeded that of any other district in the U. S.' Smithsonite was first mined in 1859, and sphalerite was mined as early as 1867. After 1873 the production of sphalerite exceeded that of smithsonite. In 1873 annual zinc production from the district first equaled lead production, and from then until 1893 production of zinc and lead was roughly the same. Since 1893 the ratio of zinc to lead mined has generally ranged between 5:l and 20:l. In 1942 the Wisconsin-Illinois-Iowa zinc-lead district ranked 14th among zinc-producing districts of the U. S. From 1946 until February 1953 the dis-

Jan 1, 1956

By E. C. W. Perryman

The recovery and recrystallization characteristics of superpurity aluminum have been investigated using electrical resistivity, X-ray line breadth, and hardness measurements for the former and the micrographic method for the latter. The three different properties recover at different rates and have different activation energies. The recrystallization results agree well with Avrami&apos;s theory and furthermore indicate that the perfect subgrains formed during recovery are not the nuclei for re-crystallization. WHEN a metal is plastically deformed, its physical and mechanical properties generally undergo considerable changes and by subsequent annealing these changes are partly or wholly annihilated. Thus, a recovery process can be discussed, taking this term in its general sense. In practice, however, there is reason to discriminate between two apparently different processes, one most easily followed at low temperatures, in which the properties return to an almost constant value between that of the cold worked and fully annealed material, and a second process in which the properties return to their original values before cold working and which is accompanied by the formation and growth of new grains having an orientation different from that of the matrix. In this paper the word recovery will be taken to mean the changes in some property as a function of annealing time which occur either without the appearance of new grains or under conditions such that the new re-crystallized grains are very small (= 2 microns), are very few in number, and substantially do not affect the property being measured. This definition is rather abitrary, for it will depend upon the sensitivity of the technique used for the observation of new recrystallized grains, which in the present work was about 1 to 2 microns. However, it is helpful to use the term recovery in this sense and to reserve the term recrystallization for the processes of nucle-ation and growth of new grains in the cold worked matrix. Although considerable work has been done on recovery and recrystallization, most workers have based their study on the measurement of one or perhaps two parameters. Since very small amounts of impurities have such a profound effect on the recrystallization characteristics of a pure metal, it becomes extremely difficult to correlate one piece of work with another. With this in mind, the present work on recovery and recrystallization was done on the same material. Experimental Procedure Material Used and Fabrication: The composition of the superpurity aluminum used throughout this investigation was 0.002 pct Cu, 0.003 pct Fe, 0.003 pct Si, and <0.001 pct Mg. The ingot was hot rolled to 0.250 in., annealed, and cold rolled to 0.034 in. A large number of reductions and intermediate anneals were carried out so as to produce material with a minimum of preferred orientation and maximum homogeneity. For the recovery part of the investigation, the final cold reduction was 20 and 80 pct and for the recrystallization part, 20 pct. After each pass in the cold rolling process, the material was quenched in cold water in order to keep the rolling temperature as near room temperature as possible. Annealing Procedure: For the recrystallization work, specimens 1x1 in. were cut from the 0.034 in. cold rolled sheet and a hole was drilled in each through which a wire was threaded to support it in the salt bath. The temperature of the salt bath was controlled to +2°C and the time taken for a specimen to reach temperature was approximately 5 sec. These 1 in. squares were then divided into three groups, one of which was given 5 min at 318°C and another 2 hr at 244°C. These treatments were such that recovery was almost complete and a well defined subgrain structure produced. Separate specimens of each group were annealed for different times at 301°, 318°, 355°, and 373°C, i.e., three specimens for each annealing time. The delay between finish of cold working and start of annealing was about 1 hr. For the recovery work, strips 0.062 in. thick were cut from the cold worked sheet, annealed, and then given the last cold rolling operation. This was done for each annealing temperature. By this means it was possible to minimize the delay between cold working and annealing. In general, all measurements were carried out within 1 hr of the last cold rolling operation. Annealing at low temperatures was done in an oil bath the temperature of which was maintained constant to +1°C. Electrical Resistivity Measurements: Strips 20x0.5x0.05 in. were machined and the electrical resistance measured using a Kelvin double bridge. Measurements were made in an oil bath maintained at 20rt0.1°C. The same specimen was used for the complete isothermal annealing curve.

Jan 1, 1956

By P. M. Gruzensky

Several experiments have been carried out in efforts to evaluate qualitatively a variety of electrolytes for refining bismuth. Most extensive work was done with the basic tartrate, hydrochloric acid, and hydrofluosilicic acid electrolytes. Deposits that are smooth and adherent can be obtained from these three electrolytes if low cathode current densities are employed. All three electrolytes were effective in purifying crude bismuth considerably, with additional purification indicated in each instance by a reelectrolysis step. With the basic tartrate electrolyte best results were obtained when the electrolyte was at 40° C, and contained at least 100 grams of bismuth per liter, An apparent disadvantage was depletion of bismuth from this electrolyte, causing the deposits to become spongy and nonadherent.

Jan 1, 1956

THE strike and dip of bedded formations is readily determined by trigonometry if some marker horizon is intercepted by three holes. If no marker can be identified and if orientation of the cores is unknown, as is the usual case in diamond drilling, the determination still can be made readily by the use of a stereonet if the bearing, inclination, and angle the bedding makes with the core axis is known for each of the three holes. Such determination, valid only if the bedding orientation is fairly uniform within the area drilled, is considered simpler, faster, and more effective than any solution previously published. Method: The steps of this procedure are as follows: 1) Mark north and south poles on tracing paper placed over stereonet.* 2) Plot the three diamond drillholes by drawing a line from the center of the net in the direction of the bearings of the holes. Then rotate the paper until each line, in turn, lies along the equatorial diameter of the net; the end of each line is determined by the inclination of the hole measured in degrees from the periphery toward the center of the net along the equatorial diameter. Fig. 1 illustrates a vertical hole and a hole inclined at —23" due east. 3) With the projection of one diamond drillhole along the equatorial diameter, measure from the end of the hole, to the east and then to the west, a dis- tance in degrees equal to the core axis-bedding plane angle. Find two more points by measuring the same number of degrees north then south along the great circle from the end of the drillhole. Draw a circle, the center somewhere along the direction of the projection of the drillhole, to connect these four points. Draw circles for the other two diamond drillholes in the same manner. See Fig. 1 for two circles representing core axis-bedding plane angles of 35" and 23" and Fig. 2 for these plus a third circle representing a core axis-bedding angle of 42" in a hole bearing S 50 W inclined at —52". 4) Rotate the tracing paper until one great circle on the stereonet is found which is tangent to all three of the circles or parts of circles derived in the previous step. Trace this great circle on the paper and join its ends with a straight line passing through the center of the net. The bearing of this line is the strike of the bedding. In Fig. 2 the bedding strikes N 77 E. 5) Rotate the paper until the strike is along the polar diameter of the net. The dip of the bedding is determined by measuring along the equatorial diameter the distance in degrees from the periphery of the net to the great circle derived in step 4. The dip of plane illustrated in Fig. 2 is 55" to the N 13 W. Fig. 3 indicates the solution for three holes whose bearings and inclinations are N 20 W and —43o, due E and —30°, S 30 W and 23" with core axis-bedding angles of 30°, 50°, and 43" respectively. The bedding (stippled area) strikes N 44 W and dips 70" to the southwest.

Jan 1, 1956

By W. G. Pfann

Under certain conditions, a molten zone can be made to move through a solid by impressing a stationary temperature gradient across the solid. This phenomenon can be utilized in fabricating semiconductive devices, growing single crystals, joining, boring fine holes in solids, measuring diffusivities in liquids, small scale alloying, and purification. Fundamentals and exemplary applications are outlined. ANEW aspect of the travel of a molten zone through a solid is considered in this paper. Whereas, in previously described zone melting techniques,&apos;-&apos; zones were usually caused to move by changing the position or temperature of a heat source, in the present technique a zone is made to move by impressing a temperature gradient across it. For example, a thin layer of molten A1-Si alloy, sandwiched between two silicon slabs having a temperature gradient normal to the layer, will travel through the hotter slab. One feature of temperature gradient zone melting, as this technique will be called here, is that zones of unusually small dimensions can be maintained. This leads to such diverse uses as have been listed in the abstract. In this paper fundamentals of the movement of a molten zone in a temperature gradient, and some practical applications thereof, are outlined. Assumptions The movement of a molten zone through a solid body of solvent substance in which a temperature gradient exists will be discussed. The length of the zone will be its dimension in the direction of motion. The direction of the temperature gradient will be toward the region of higher temperature. To be considered is a binary or higher order solute-solvent system in which the concentration of solute in the molten zone is sufficient to produce a lowering of the freezing temperature of the solvent which is at least of the order of the temperature range impressed on the charge. While we discuss primarily molten zones in a solid matrix, the principles are applicable to solid or vaporous zones in a solid matrix, a requirement being that the diffusivity in the zone be substantially greater than in the matrix. Diffusion of solute into the surrounding solid will be assumed negligible. In general, its presence will not basically alter the conclusions to be drawn. For illustration, a system represented by the partial constitutional diagram of Fig. la will be discussed, in which k, the distribution coefficient defined in the figure, is constant and less than unity. However, the technique is applicable to any solute- solvent system in which one component lowers the melting point of another component. Movement of a Molten Zone in a Temperature Gradient Consider, in the system AB of Fig. 1, where B is designated the solute and A the solvent, the effect of sandwiching a thin layer of solid B between blocks of solid A and placing the whole in a temperature gradient such that the temperature of the layer is above the lowest melting temperature of the system. Surrounded by an excess of A, the layer will dissolve A, becoming molten, and expand in length." As so- lution of A continues, at both interfaces, the mean solute concentration in the zone will move to the right in Fig. la, until at temperature T, the liquid at the cooler interface reaches the liquidus concentration C,. Solution of A thereupon ceases because the liquid T1 is saturated with A. The liquid at the hotter end of the zone, being at temperature T2, is not saturated with A at concentration C1. Hence solution of A continues there and concentration C2 is approached. A concentration gradient therefore is set up in the zone, causing A to diffuse toward the cool end and B toward the hot end. As a result, the liquid at the cool interface becomes supersaturated and a layer of crystalline A containing concentration kc, of B in solid solution freezes. Since a source of A

Jan 1, 1956

By R. F. Krueger, L. C. Vogel

A design is presented for an electrical analog computer which can solve non-steady state heat transfer problems in an extensive radial forrnation containing a moving cylindrical source. The computer is used to simulate a .simplified thermal oil recovery process in which heat transfer from a moving, constant temperature source takes place radially by conduction only. Temperature distribution curves are .shown for several different assumed modes of travel for the heat source. The data are used to estimate the residual fuel requirements necessary to maintain a self-propagating isotherma1 front for the particular system being studied. Although the computer is designed to represent an unique system. conversion factors can he adjusted to show the effects of changing the assumed values of system constants, such as thermal conductivity of the formation and temperature of the source isotherm. Examples are given to illustrate the relative influence the assumed values of these variab1es will have upon the quantity of fuel required to maintain the source. The maximum effect of heat transfer by the flowing air stream is estimated mathematically, and full requirements for this system are shown to he markedly reduced. Inasmuch as the examples discussrd refer to a simplified process, the results are not directly applicable to a practical field operation. It is believed, however, that the data il1ustr-ate some general trends which are important in thermal recovery processes. Data from laboratory and field experimentation can he used to modify the computer to take into account the influence of heat transfer by various mechanisms, for example, by injected air and by fluids ahead of the hot zone. With .such refinements it would be possible to estimate more accurately the limiting values for the rate of travel of the high temperature front and for the required air- injection rates. Use of this computer should aid in evaluating the economic feasibility of oil recovery by various thermal processes. It is hoped this paper will stimulate further work by others to help accomplish this objective. As the costs of exploration for and development of new oil fields rise. increasing the recovery of oil from established fields becomes more and more important. In fields containing low gravity crude oil, ultimate recoveries by primary means are sometimes less than 10 per cent and often total only 10 to 20 per cent of the oil in place. Conventional secondary recovery methods are not always effective in increasing this total. Methods which have been proposed for increasing the recovery of viscous oils include thermal processes for increasing the mobility of the oil. One method is to provide a moving heat source generated within the formation to heat the oil and a flowing gaseous medium (for example, air) to sweep the oil to the producing wells. The possibility of such a process has intrigued engineers for many years.&apos;. &apos;." but little or no information has been available in the literature relative to the technical or economic feasibility of this method. Recently, however, interest has been revived by publication of laboratory and field test results indicating the feasibility of maintaining

Jan 1, 1956

By John F. Haberer

DURING the twentieth century Canadians have been steadily improving their standard of living. Originally, this improvement depended almost entirely upon the export of basic raw materials and a triangular system of trade with Great Britain and the United States. However, since the Second World War, Canadian living standards have improved still further because of the very rapid d0evelopment of secondary industries. As a result of this development, the present demand for scientists and engineers exceeds the supply, and interest in scientific research has never been greater. It is the purpose of this paper to discuss the professional and economic status of Canadian scientists and engineers over the past half century. GROWTH OF RESEARCH It is difficult to determine accurately the amount of scientific research conducted in Canada since 1900. However, ?prior to World War I, it was limited and was connected mainly with primary industries and health. Government departments did some; university science faculties, overloaded with teaching responsibilities, did a little; and industry, which consisted mainly of subsidiaries of American and British firms, depended chiefy upon foreign sources for new information.

Jan 1, 1956