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By R. W. Fenn, H. A. Lepper, W. R. Hibbard

THIS paper reports the results of static tension and torsion tests made on single crystals of alpha brass for the purpose of determining its elastic coefficients. 70-30 alpha brass was chosen because it has been used extensively in the study of the plastic deformation and because it has the following desirable characteristics: (1) face-centered cubic structure, (2) marked elastic anistropy, (3) low elastic modulus. In 1928 Masima and Sachs' using static methods reported the following values for the elastic coefficients of 72-28 pct alpha brass: S11 = 19.4 X 10-13' cm2 per dyne S12 = —8.35 X 10"' cm2 per dyne S44 = 13.9 X 10-13= cm2 per dyne These values were obtained from the measurements shown in fig. 1. The experimental points for both tension and torsion lie consistently below the lines drawn to represent them. Fig. 2 shows the stress-strain curves for their specimens. Only a few points in the elastic range of these curves were available to obtain their values for Young's modulus. Therefore, it was considered that a re-evaluation of these data was desirable. In addition a variation of from 1.13 to 1.485 kg per mm2 was found in the values of the critical resolved shear stress for 70-30 alpha brass reported by Burghoff,² Treuting and Brick: Martin,4 Maddin, Mathewson and Hibbard5,6 and von Goler and Sachs.' Therefore, it was desired to evaluate the conclusion of Boas and Schmid8 that a constant resolved shear stress and not a constant elastic shear initiates plastic deformation. Theoretical Considerations*: The elastic deformation of cubic crystals may be defined by three elastic coefficients (S11, S12, S44,) or three elastic parameters (C,,, C,, C,,). These coefficients or parameters are sufficient to define the stress and strain relations for cubic crystals in the generalized form of Hooke's law referred to Cartesian coordinates. Elastic parameters and coefficients in the cubic system are related by the expressions: C11 —S11+S12/(S11-S12)(S11+2 S12) C12=-S12/(S11-S12)(S11+ 2 S12) (S11 — S12) (S11 + 2 S12) [2] C44 =1/S44 PI It is possible to determine all the elastic coefficients for a cubic metal by measuring two of the three elastic constants: Young's modulus (E), torsion modulus (G), or compressibility (S). The following relations exist between crystallographic orientation and E, G and S for cylindrical crystals of the cubic system: 1/E = S11 — 2 [(S11 - S12) — Su] (?1² ?2² + ?2²?83 + ?3² ?1²) [4]

Jan 1, 1951

Beverley S. Randolph, Frostburg, Md. (communication to the Secretary): It has always appeared to me that each coalseam has its peculiar character or habit, due to the conditions of its formation, by virtue of which it is either persistent or variable in its section over extended areas. One seam will hold its thickness, chemical character, number and position of partings, beds of slate, etc., over a large area, while another will be found to vary in some of these characteristics every few feet. As the position of the outcrop is an accident of the topography, depending on folding and erosion which have taken place since the bed was formed, no one opening in the outcrop, or, in fact, anywhere else, can supply reliable evidence as to the general character of the seam. To determine the character of an untried seam, a number of sections are necessary from widely separated points, in order to show such variations as may exist. Should material variations be developed, more numerous sections are necessary, in

Jan 1, 1901

By P. Shahinian, M. R. Achter

P. Shahinian and M. R. Achter (U.S. Naval Research Laboratory)—We should like to point out another instance where concentration of impurities in grain boundaries led to an embrittlement. In this case an impure nickel (99.8 pct) developed many more in-tergranular cracks during creep in a nitrogen atmosphere than in vacuum.5 In comparison high-purity nickel (99.99 pct) exhibited a much smaller atmosphere effect. We concluded that the interartion of the nitrogen with nitride-forming impurities concentrated at grain boundaries promoted inter-granular cracking.

Jan 1, 1965

The serious shortage of eastern gas coal and of coke for gas-making in Illinois and adjoining states during the winter of 1917-1918 was emphasized at the meeting of the Illinois Gas Association, March, 1918. The seriousness of the situation was of concern not merely to private interests but to the general public, which consumes gas for heating, lighting, and for important industrial uses. Some relief was thought possible if central district coals from Illinois, Indiana, and western Kentucky could be used generally as a substitute for eastern coal and coke in the manufacture of retort gas and water-gas. Already a little Illinois and Indiana coal was being used under special circumstances in Illinois retort plants and successful experiments with mixtures of Illinois coal and eastern coal had been conducted at the Decatur retort-gas plant by F. K. Ovitz of the U. S. Bureau of Mines and the Illinois Mining Investigations, with the advice and cooperation of a committee of the Illinois Gas Association. Consequently, it seemed desirable to continue experiments with central district coal in gas retorts, and with coal as a substitute for coke in water-gas generators, and to give publicity to the results and technical assistance to companies desiring to use central district coal. Other matters, of national importance were the prospective shortage of toluol and of ammonia for the manufacture of explosives, and the possibility of encouraging recovery of additional amounts from some of the plants in central states that were not contributing these substances. Results of work done by the Gas Section, Illinois Mining Investigations, under the advice of the Technical Committee, were pushed to early publication until the signing of the armistice lessened the importance of speed as a war measure. The first two publications listed below were distributed by the Regional Director of the U. S. Fuel Administration, through the Bureau of Gas. By-products and Public Utilities. The others were distributed by the Geological Survey. Bulletin 21. The Manufacture of Retort Coal-gas in the Central States Using Low-sulphur Coal, from Illinois, Indiana, and, Western Kentucky. Bulletin 22. Water-gas Manufacture with Central District Bituminous Coals as Generator Fuel

Jan 8, 1919

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,' has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-' in fcc metals, vary from 1 to 10~6 sq cm sec-'. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"' content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By C. W. Volek, J. E. Chappelear

The injection of a hot liquid into initially cool porous media, saturated with the same liquid and surrounded by two impermeable but heat conducting media (cap and base rock), has been studied both experimentally and theoretically. The temperature dependence of the viscosity was included in the theoretical model, but it was assumed that the specilic heats and densities of the various materials were independent of the temperature. Solutions to the theoretical model were approximated by numerical methods. Both theoretical and experimental results indicate that center-line temperatures are significantly higher than boundary temperatures. Comparison of experimental and theoretical results with a cold/hot viscosity ratio 01 19:1 were in reasonable agreement. Theoretical calculations show that the effect of the temperature dependence of viscosity was very significant at ratios of 100:l to 1000:1, which are typical of those that occur when injecting hot water to flood heavy oil reservoirs. INTRODUCTION We consider the problem of prediction of fluid flow and temperature distribution in an initially cold-fluid-filled reservoir on the injection of the same hot liquid by the use of mathematical and physical models. The results reported are for a two-dimensional rectangular section of the reservoir, as shown in Fig. 1. The injection and withdrawal faces are assumed to be equipotentials for fluid flow. The ultimate purpose of such models would be to predict hot-water injection performance. However, we note that in the work presented here, one of the most significant aspects of the problem — the instabilities resulting from two-phase, water and oil flow — is not included. We will not give a historical review, but refer instead to the paper of Spillette and Nielsen,1 which contains a rather complete bibliography and critical discussion. The physical problem is exactly the same as Spillette and Nielsen, except for certain simplifications in our assumptions. The mathematical details are somewhat different, and we will present the details of our method here. The mass flow equation, which is elliptic in character, is handled by successive overrelaxation. The heat flow equation, which is parabolic in character, is handled by a straightforward explicit approximation. Some difficulty arose in the over-all heat balance due to small errors in the solution of the mass flow equation, and we feel that a different formulation of the heat flow equation would be desirable for future work. In addition to the mathematical solutions for the temperature distributions in a porous medium due to the injection of hot liquids, experimental data are presented to check the validity of these solutions. A schematic diagram of the model is shown in Fig. 2. Certain qualitative physical conclusions were obtained from our numerical and experimental results. These are: 1. Assuming high (infinite) conductivity normal to the bedding plane in the reservoir is a poor approximation, and may lead to overestimates of the total heat losses (to cap and base rock) of as much as 50 percent. 2. More heat is retained in the reservoir (per unit of heat injected) for higher viscosity changes. 3. Any particular temperature isotherm moves more rapidly along the center line for higher viscosity changes. Consequently, the approximation of temperature independent viscosity is not suitable for obtaining quantitatively correct results. MATHEMATICAL MODEL Our mathematical model is that of a reservoir of thickness 2h. The problem is idealized from that of a linear hot-water drive, and we imagine that the input face is sufficiently far away from the injection wells that the stream lines enter it normally. Similarly the production wells are far enough from the outflow face that the flow lines leave it normally. The reservoir and surrounding cap and base rock

Jan 1, 1970

By P. H. Royster

SOMETHING of a mystery has attached itself to the production of ferromanganese in the blast furnace. This alloy has been produced on the Continent almost continuously since 1876 and in very considerable tonnages, but little definite information concerning the practice is to he found in technical literature, and almost nothing in the way of a theory of the manganese furnace. In this country prior to 1904, bit one company had attempted its production in a serious way, and none of the operating data or other information from this company has been, or is, available to the public. In the last 5 years, as a result of the restriction of imports, a number of furnaces have been blown in on this alloy, with the result that in 1918 as many, as 18 furnaces were in blast. The majority of the men in charge of these furnaces had had little previous experience in such operations. Realizing the advantages both to the country and to the industry from a pooling of operating data and experiences, the Bureau of Mines, in the summer of 1918, undertook the collection of data from ferromanganese furnaces. Although the results of this investigation have already been reported to the companies cooperating, they may he of permanent metallurgical interest, so this paper attempts to give, briefly, the more important points brought out in the investigations. OPERATING DATA IN FERROMANGANESE PRACTICE Operating data were collected by the Bureau from 11 ferromanganese furnaces, which will be referred to throughout this paper as furnaces A, B, C, F, G, I, J, K, L, M, and P. The dimensions, of seven of the furnaces are given in Table 1. The companies from whom this infor-

Jan 2, 1919

By August Wendel

It is a well-known fact to all Bessemer steel manufacturers using a blooming mill, that ingots show large cracks in the first few passes of the rolls, which, in the following ones, do not always roll up satisfactorily. This deficiency in the quality of the product is generally called "red-shortness," though, in the writer's opinion, mostly unjustly so. Different explanations for the said peculiarity are given by the leading authorities, each works selecting one element as a special scapegoat for the inferior quality of the ingot. The sulphur is generally first charged as being the principal cause of all mischief in this direction ; then, after ascertaining that sulphur is not higher than the average, and sometimes lower in the very worst heats, silicon has to bear its share of abuse. How and why silicon should affect the working qualities of the metal, the writer could never precisely learn, but is convinced that the doctrine of its pernicious influence is an established one with many. In cases where silicon failed to explain everything, resort was taken to calcium, aluminum, and some other known or unknown elements, without settling the difficulty; and lastly, when the skill of the chemist became exhausted, " practical men " came to the same conclusion, which many leading blast-furnace managers had arrived

By R. A. Garling

INTRODUCTION Since the infancy of in situ uranium mining, a growing number of hydrometallurgical processes have been incorporated into pilot and commercial scale flowsheets. Although initial design efforts were geared toward maximizing uranium recovery and minimizing plant and wellfield flow circuit maintenance, recent emphasis has shifted to improved means of water conservation and aquifer restoration. As mining units approached depletion, evaporation ponds reached minimum freeboard, and state and federal agencies demanded proof of groundwater restoration, processes including mixed bed and conventional ion exchange, reverse osmosis and electrodialysis were adopted by the industry. These units served the additional function of reducing process bleed flows during mining in states where the deep disposal well permitting ice remains unbroken. This report concerns the use of electrodialysis as an alternative to the more conventional processes used in in situ mining. In addition to a brief history and description of the process, a comparison to reverse osmosis and operational data derived from testing an Ionics, Inc. 1.31 x 10-3 m /s (30,000 gallon/day) unit at the Teton-Nedco Leuenberger Research and Development pilot will be presented. HISTORY Commercially practicable electrodialysis was contingent upon the development of synthetic ion exchange membranes in 1940's. In 1952, Ionics Inc. demonstrated that the process was amenable to the treatment of salt and brackish water and, in 1954, made their first commercial sale. The following decade saw several major electrodialysis unit sales which were generally targeted for use on private or municipal potable water treatment. Major increases in membrane desalting unit capacities, facilitated by technological advances in the reserve osmosis industry, were noted during the 1970's. The development of polarity reversing electrodialysis equipment which reduced feed pretreatment requirements, increased water recovery rates, and simplified unit operation, kept Ionics Inc. competetive in the water treatment industry. Engineering advances which incorporated automated equipment, non-corrosive construction materials, and improved ion exchange membranes allowed the electrodialysis process to compete in industrial waste treatment among other commercial markets. PROCESS AND APPARATUS DESCRIPTION The electrodialysis process utilizes direct electrical current passed across a stack of alternating cation and anion selective membranes in order to achieve an electrochemical separation of ionized materials in an aqueous solution. The membrane stack has the appearance of a plate and frame filter press and auxilliary equipment includes solution pumps, electrically actuated valves, filters, piping and a direct current power source. The ion separation membranes are thin sheets of synthetic cation or anion selective resins. Attaching sulfonate or quaternary ammonium groups to the cross linked copolymer structure determines the ion selectivity of the membrane. The membranes are separated from each other in the stack by non-conductive spacers that house flow channels which route the flow tortuously and parallel to the membranes. Direct electrical current passing perpendicularly to the membranes and solution passages attracts cations toward the cathode and anions toward the anode (Figure 1). As the ions from the feed stream pass through the ion selective membranes, they become concentrated in the adjacent brine channel and are retained there by the combined attractive force of the electrode and the repelling force of the next membrane toward the electrode. Limiting factors on the degree of demineralization possible include chemical solubilities in the brine flow and the current density that will produce an unacceptable degree of polarization (Figure 1). Feed or brine solution treatment with complexing agents or acids has been successfully applied to prevent membrane scaling. Polarization can occur when sufficient current density is applied to dissociate water in the ion depleted region of the diluting compartments near the membrane surfaces. Significant polarization is evidenced by large electrical resistances across cell pairs and notable pH differences between diluting and concentrating streams. Limiting current densities have been increased in U.S. manufactured equipment by utilizing tortuous flow paths of relatively high linear velocities thereby promoting continous solution mixing. Energy consumption is due to separating electrolytes and solutions, oxidation and reduction reactions occurring in electrode compartments, overcoming electrical resistance, conversion from AC to DC power, solution pumping and auxiliary equipment actuation. A major improvement to the basic electrodialysis process was applied in 1970 which resulted in frequent, automatic cleaning and descaling of membrane surfaces. The process, polarity reversal, incorporates alternating the cathode and anode on a periodic basis while exchanging product and brine flow channels via electrically actuated values. The reversal reduces the potential of stack plugging with CaCO3 (calcite), CaSO4 (gypsum), and colloidal materials and, in most waters, eliminates feed pre-treatment requirements. For approximately two minutes during and following the reversal, off spec. water is flushed to waste or reintroduced to the feed supply. The usual feed treatment on polarity reversing electro-

Jan 1, 1982

By P. E. Landolt

BEFORE World War I, and even prior to World War II, lithium was considered among the rare elements. Mining was limited to exploitation of a few well selected sources of rich minerals recoverable by hand cobbing methods. Within the past five years the situation has changed radically. Many new sources have been explored and developed, principally in Canada, North Carolina, and Southern Rhodesia. The prime raw material for lithium recovery is spodumene. In Southern Rhodesia, however, both petalite, a modified spodumene, and lepidolite, a lithium mica, are being mined in quantity.

Jan 4, 1957

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By F. Weinberg, E. H. McLaren

Dilute binary alloys have been solidified under controlled thermal conditions, and solute distributions, temperatures during freezing and melting, and the position and morphology of the solid-liquid interfaces have been examined. Binary Zn, Sn, and Pb based alloys were investigated with solute additions of AgU°, AU°, Sb'24, TlZo4, snH3, and Zns5. Approximately 150 cc of metal was used in each ingot. Appreciable solute segregation occurred in most of the ingots, depending on the solute concentrations, distribution coefficients. and freezing conditions of the alloys. Measurements were made of the general solute distribution by sectioning layers of material from the ingot circumference and counting the activity of each layer. Local segregation was detected by autoradiographic techniques. Freezing and melting curves for the same alloys were obtained by precision resistance thermometry. These curves are related to the corresponding measured solute distribution curves and those calculated from theoretical expressions. The position and morphology of solid-liquid interfaces during freezing were determined by both decanting and quenching techniques. The results indicate the manner in which freezing and remelting occurred under the conditions investigated. If an isomorphous dilute binary alloy is solidified or melted under equilibrium conditions, the concentration of solute in both solid and liquid would be uniform at all stages in the freezing process. The solute concentrations during freezing could be determined from the phase diagram of the alloy, and the freezing curves would have an alloy slope defined by the solidus and liquidus points. In practice, however, solidification under equilibrium conditions rarely, if ever, occurs, primarily because of low rates of diffusion in the solid and incomplete mixing in the liquid. As a result, the solute distribution and the shape of the freezing and melting curves obtained in a given system depends on a number of factors. These include, in addition to the extent of diffusion and mixing, the initial solute distribution and concentration, the distribution coefficient, the rate of freezing or melting, supercooling of the liquid, the morphology of the solid-liquid interface, and the effect of annealing. The purpose of the present investigation was to determine, experimentally, actual solute distributions and thermal curves for a series of dilute binary alloys, using tracer techniques to determine the solute distributions and precision resistance thermometry for the temperature measurements. In addition, observations were made of the positions and morphologies of the solid-liquid interfaces during freezing and remelting. The distribution of solute in a dilute alloy, assuming complete mixing in the liquid, and negligible diffusion in the solid, is given by1 where Co is the mean solute concentration of the alloy, C, is the solute concentration in the solidg is the fraction of the ingot solidified, and ko is the equilibrium solute distribution coefficient (assumed to be independent of concentration for dilute alloys). For the case of partial mixing, ko can be replaced by an effective distribution coefficient k. If solute transport in the liquid is assumed to be entirely due to diffusion, with negligible diffusion in the solid, then the solute distribution in the solid is given by Tiller et a1.' as where R is the rate of advance of the solid-liquid interface, D is the solute diffusion coefficient in the liquid, and x is the position of the interface from the start of freezing. The temperature at the interface TI is related to the solute concentration of the solid at the interface C, by the expression where Tm is the freezing temperature of the pure solvent and ml is the slope of the liquidus for the binary alloy being considered. Accordingly, by relating TL to the actual temperatures measured in the present experiments, solute distributions can be deduced from the temperature measurements. Using the above expressions, the measured solute distribution of a given alloy may be compared to the theoretical distributions, as well as to the distribution calculated from the observed freezing curve. EXPERIMENTAL The solvent materials used in making up the binary alloys were C. P. New Jersey zinc (99.999 pct), Vulcan Extra Pure Tin (99.999 pet), and Tadanac lead (99.998 pct). The solute elements were of 99.99 pct purity or better, and were activated in the

Jan 1, 1963

By D. J. Carney, J. Chipman, N. J. Grant

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some remaining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

By Jerome Strauss, Carl L. Shapiro

THIS is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years,, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I INFLUENCE OF BODY-CENTERED CUBIC ELEMENTS The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tantalum) are reviewed individually. Iron-carbon-chromium System.-In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts' concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.-Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. a; these results have received general approval. Iron-carbon-molybdenum System.-In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and Reed,8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-

Jan 1, 1943

By Carl L. Shapiro, Jerome and Strauss

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By Jerome and Strauss, Carl L. Shapiro

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By David Donoghue

THE. years 1901, 1910, and 1924 may be considered as the beginning of new eras in the history of the oil industry of the Gulf Coast of Texas and Louisiana. Spindletop, in 1901, with its enormous cap-rock production revealed the possibilities of the salt domes. The lateral sand development at Vinton, in 1910, renewed interest in the then known domes which were non-producing, or were producing from the cap rock or from sands above the cap rock. The discovery of three domes, Nash, Orchard and Long Point, in the year 1924, by means of the torsion balance and the seismograph, is the beginning of intensive explorations of the Gulf coastal plain by geophysical methods. Domes other than those mentioned have no doubt been found during the last few months of the year but tests have not been drilled to confirm the evidence of the instruments. DISCOVERY OF DOMES BY GEOPHYSICAL METHODS The Rycade Oil Corpn. operated the first torsion balance on the Gulf Coast in October, 1922, and the Roxana Petroleum Corpn. brought in one of these instruments and began work in December, 1922. The U. S. Coast and Geodetic Survey made some gravity observations at Damon Mound, in 1923, with a pendulum apparatus. In March, 1924, the Marland Oil Co. placed the first seismograph on the Gulf Coast and the Gulf Production Co. followed with one in May. In June, 1924, the Gulf Production Co. began operations with a torsion balance. The Atlantic Oil Producing Co., The Texas Co., and others have experimented with several types of instruments involving various principles. During the next few years, a great advance in geophysical methods may be expected, especially if one of the newly discovered domes should be productive. The first dome discovered was the Nash, in Fort Bend County, Tex., about 6 mi. east of Damon Mound. A slight elevation and two shallow wells containing sulfurous waters made the locality somewhat interesting from the standpoint of surface indications, and the torsion-balance measurements indicated the presence of a dome. On July 20, 1924, the Rycade Oil Corpn. No. 1 Wisdom encountered lime at a depth of 634 ft. and anhydrite at 639 ft. The hole was abandoned on Sept. 8, 1924, at 769 ft. in anhydrite. A cavity in the anhydrite caused much delay and the final abandonment of this test.

Jan 3, 1925

The Committee submits the following report: The General Committee met in the Treasury Building at Washington on Oct. 6 and 7, 1919. At the first meeting, Cornelius P. Kelley was appointed chairman, and Paul Armitage, secretary of the Committee. Subcommittees were appointed on Invested Capital, on Mine Valuation, and on Depletion and Depreciation. These subcommittees were directed to meet separately and to report on Oct. 7 to the General Committee. On Oct. 7, the reports of these committees were submitted to the General Committee and on motion were received and referred to the Executive Committee for its information to be used as it deemed wise. A motion was carried that the Executive Committee be constituted a permanent committee to continue the work of the Committee, with full power to add to and increase its membership; that as thus increased it should constitute a permanent organization to act and cooperate with the Treasury Department in matters of mining taxation under the Federal Income and Excess Profits Tax Laws. Thereafter the Executive Committee met and formed a permanent committee as follows: Cornelius F. Kelley, chairman, 42 Broadway, New York City. J. L. Darnell, Office of the Commissioner of Internal Revenue, Washington, D. C. J. Parke Channing, 61 Broadway, New York City. Walter Douglas, 99 John St. New York City. R. V. Norris, 542 Second National Bank Bldg., Wilkes-Barre, Pa. J. E. Spurr, care of Engineering & Mining Journal, 10th Ave. and 36th St., New York City. W. G. Swart, 808 Selwood Bldg., Duluth, Minn. J. P. Finley, 45 Cedar St., New York City. W. A. Williams, Bartlesville, Okla. F. S. Peabody, care of Peabody Coal Co., McCormick Building, Chicago, Ill. Matthew C. Fleming, 71 Broadway, New York City. H. B. Fernald, 54 Wall St., New York City.

Jan 1, 1923

The Committee submits the following report: The General Committee met in the Treasury Building at Washington on Oct. 6 and 7, 1919. At the first meeting, Cornelius P. Kelley was appointed chairman, and Paul Armitage, secretary of the Committee. Subcommittees were appointed on Invested Capital, on Mine Valuation, and on Depletion and Depreciation. These subcommittees were directed to meet separately and to report on Oct. 7 to the General Committee. On Oct. 7, the reports of these committees were submitted to the General Committee and on motion were received and referred to the Executive Committee for its information to be used as it deemed wise. A motion was carried that the Executive Committee be constituted a permanent committee to continue the work of the Committee, with full power to add to and increase its membership; that as thus increased it should constitute a permanent organization to act and cooperate with the Treasury Department in matters of mining taxation under the Federal Income and Excess Profits Tax Laws. Thereafter the Executive Committee met and formed a permanent committee as follows: Cornelius F. Kelley, chairman, 42 Broadway, New York City. J. L. Darnell, Office of the Commissioner of Internal Revenue, Washington, D. C. J. Parke Channing, 61 Broadway, New York City. Walter Douglas, 99 John St. New York City. R. V. Norris, 542 Second National Bank Bldg., Wilkes-Barre, Pa. J. E. Spurr, care of Engineering & Mining Journal, 10th Ave. and 36th St., New York City. W. G. Swart, 808 Selwood Bldg., Duluth, Minn. J. P. Finley, 45 Cedar St., New York City. W. A. Williams, Bartlesville, Okla. F. S. Peabody, care of Peabody Coal Co., McCormick Building, Chicago, Ill. Matthew C. Fleming, 71 Broadway, New York City. H. B. Fernald, 54 Wall St., New York City.

Jan 1, 1923

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10' v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969