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By P. R. Sahm, T. V. Pruss, D. A. Gandolfo

Cb 3 Sn powders were hot-pressed to estahlish densi-fication conditions and assess the possible use of such compacts in multiphase structures with ceramic or magnetic inclusions. Superconducting transition temperatures, Tc, were measured as a function of powder particle size, pressing temperature, and second-phase admixtures. The highest transition temperatures were found in coarse powder (5 to 500 u) compacts and were only weakly depended on pressing temperatures up to 1200°C. Fine powders (below 5 p), however, both single-phase CbsSn and Cb3 Sn-composites, showed a stronger dependence on hot-pressing temperatures. While Al2 O3 phase admixtures did not affect T, much more, a Pronounced T, degradation was observed upon the addition of ferrimagnetic Fe2 Mno. 5 Zno.5 O4 powders. Likewise, critical current densities, Jc, at 4.2° K were lowered appreciably in the ferrite doped samples, whereas the neutral A1203 inclusiow gave slightly improved Jc values. MULTIPHASE structures in electronically active materials have recently gained in interest as pointed out by Galasso in a review article.' In superconductors the most widely reported group are eutectic alloys which have been mostly investigated with respect to the proximity effect.2"4 In addition, "artificial eu-tectics", for example in the form of mercury-vycor glass sponge5 or fine niobium wires imbedded in a copper matrix,= have been prepared to attain higher critical fields and critical current densities. The idea was to enhance flux pinning phenomena by second-phase inclusions or ho1es. 7 Flux pinning should also be possible by the introduction of insulator inclusions into a superconducting matrix. Ceramic-metal combinations are most easily produced by hot pressing (= pressure sintering), as it permits an almost unlimited selection of material combinations. Cb 3 Sn has been prepared by vapor phase growths or in the form of thin films. Large compacts must be sintered,1° however, and normally present difficulties. At temperatures below 1350°C insufficient densities are obtained and at higher temperatures the loss of tin due to dissociation upsets the stoichiometry. Hot pressing is a natural approach to circumvent the problems, since one can obtain satisfactory densities despite low sintering temperatures. This work was mostly concerned with establishing conditions to hot press Cb3 Sn and Cb3 Sn multiphase structures (= composites), because no data are presently available, and to evaluate these with respect to their transition temperatures. However, a few measurements on critical current densities were also carried out, in particular to assess the value of ferrimagnetic inclusions. I) EXPERIMENTAL PROCEDURE The experimental procedure involved the preparation of feed material and powders, hot pressing, and evaluation of the resulting ingots. As no attempts were made to synthesize Cb3Sn from the elements during hot pressing, feed material had to be produced. For this purpose, a stoichiometric Cb-Sn powder mixture was compacted into a 3-cm-diam ingot (80,000 psi) and then inserted into a quartz tube and evacuated. Rf heating was employed. Above the tin melting point (230°C) liquid tin was forced out of the ingot, but was pulled back by capillary action after approximately 0.5 hr of continuous pumping at 700°C. Thus, it appears that evacuation at this temperature caused desorption of impurity gas creating wetting surfaces which, later on, favored alloying at relatively low temperatures. After a presintering period of 17 hr at 800°C, the quartz tube was tipped off and sealed into another such larger-diameter tube which, in turn, was connected to a pump system. This configuration permitted a temperature treatment at 1400°C, carried out for 65 hr, without collapsing of the glass walls or unfavorable chemical interaction of Cb3Sn with the quartz. The resulting material was

Jan 1, 1969

Jan 1, 1967

By R. E. McNulty, R. D. Heidenreich, C. H. Gerould

TIIE electron microscope techniques and their application to magnesium alloys that are to be discussed in this paper are the result of research at The Dow Chemical Co. over the past three years. The view- point underlying the work is not wholly metallurgical, but has evolved through a variety of problems related to the physics and chemistry of surfaces. It can be said that the interest and stimulus were closely associated with a desire to employ effectively the electron microscope in research concerning the properties of solids as related to their physical structure. Only a portion of this work will be described here, and, consequently, many points of interest and debate are of necessity either only briefly recognized or are completely omitted. As has been pointed out by Desch,1 a great deal of the knowledge of the structure of metals has been obtained through microscopic studies of the surfaces of metallic specimens prepared in a particular manner. This information, when added to that obtained by means of thermal, electrical, X-ray, dilatometric and other methods, has been of great value both from a theoretical and a practical view- point. With the introduction of new instruments such as the electron diffraction camera and the electron microscope, it would be expected that still more information could be obtained. These two instruments have in many instances been very effective when directed toward the investigation of metallic surfaces, provided the proper methods of surface preparation were employed. Experience shows that the problems of surface preparation greatly limit the general application of these instruments to metallographic studies. It was found necessary to discard the standard metallographic procedures in applying the electron microscope to magnesium alloys and to work out new methods, which were required to satisfy certain conditions. These methods are unique to magnesium only in the specific chemical reactions occurring during etching. The presentation of the methods and results will be ordered as follows: I. Electron Microscopy of Surfaces. 2. Surface Preparation of Magnesium Alloys. 3. Discussion of Microstructures. a. Pure Magnesium and Single-crystal Studies. b. Types of Precipitation. c. Some Common Structures. d. Special Micrographs and Techniques. e. Structure of Mg-A1 Solid Solutions. 4. Correlation of "Fine Structure" with Corrosion Behavior of Magnesium Alloys.

Jan 1, 1946

By T. F. Witheree

The Fletcherville Furnace was built in 1864 and 1865, making its first blast from August until October of the latter year, when it was blown out to prevent its " bunging-up." Repairs were made in time to enable it to be blown in again December 12th, 1865, the blast ending October 7th, 1866. Total product 1921.15 tons iron, an average of 6.8.2.5 tons per day, from ores yielding 44.8 per cent. Consumption of charcoal 223.2 bushels per ton of iron. The furnace journal up to this time shows no record of furnace dimensions, or temperature of the blast, but as near as can be ascertained, they were as follows, viz.: Height of stack, 42 feet. Diameter of bosh, 11 feet. Angle of bosh, 71/2 inches to 12 inches rise, about 58°. Diameter of open tunnel head, 42 inches. Number of tuyeres 3 ; each 3 inches in diameter. Dam 15 inches high. Tuyeres 24 inches high. Tymp 224 inches high. Diameter of steam cylinder, 20) inches. } Diameter of blast cylinder, 64 inches. } Stroke 5 feet. The engine is direct-acting horizontal non-condensing. December 26th, 1866, the furnace was again put in blast, having been considerably altered in the crucible; the height of stack, bosh, and tunnel head remaining as before. Six tuyeres were put in, three in each of the side arches. The hearth or crucible was rectangular in form, 3 feet wide x 31/2 feet long x 64 feet high. Inclination of bosh 58°. Height of tuyeres 26 inches; nozzles 21/4 inches diameter. Temperature of blast estimated to be about 500°.

Jan 1, 1967

Jan 1, 1968

Jan 1, 1944

Jan 1, 1944

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these' the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert's law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957

By L. V. Wade

Abstract-US Bureau of Mines efforts under longwall research programs to develop the capability to predict support requirements for longwall/shortwall support systems are discussed. Ground control studies are being conducted in conjunction with several longwall/shortwall demonstration projects. Geologic, support performance, and strata behavior are being documented on these projects. A hypothesis is presented for the prediction of support requirements.

Jan 11, 1978

By R. Moldenke

The presence of nickel-chromium in pig iron made fro111 Cuban oles is so well known that the word "Mayari" is unconsciously associated with it. Since 1904, when exploration of the Mayari deposits of iron ore in northeastern Cuba was undertaken, there llas been increasing interest in these ores. Tlie Transactions contain numerous references to t1ieln.l This iron ore, which is shipped to the Tinited States in the nodulizecl state, has been thoroughly tested and found very valuable; the deposit covers over 25,000 acres and there is in sight over 500,000,000 tons of ore that, by systematic mining, runs practically constant in composition. With nickel and chromium present, also titanium in sufficient quantities to attract attention, as well as extremely low phosphorus and sulfur contents, the iron founder is naturally interested in the utilization of RInpari ore for pig iron for the better grades of finishrtl iron products. The present point of coilsn~iil)tion ol ILlapri ore is at Sparrow's Poi111, where hlayari pig iron of ally desiretl coml>osition is made. The composition of the dried ore is about as follows: Iron -29 per cent., silica 3 pc.r cent., nickel 1 per cciit., chroiniun~ 1.5 per cent., alumina 11 per cent., ant1 coinbined water 13 per cent. When nodulized, the iron runs up to nearly 56 per cent., the silic:~, :tlumi~i:i, nickel, and c~llromiurn are slightly highr than the arno~l~its just given. Practically all the, combined wntcr is driven off aild the iiodulizccl ore carries only a few- tenths per cent. of 1 C. M. Weld: Residual Rrolvn Iron Ores of Cuba. Tmns, (1909) 40, 299. C. K. Leitll nnd If'. J. Mcncl: Origin of Iron Ores of Central and Northeostr~n rlbn. Trans (1911) 42, 00. C. W. Hayes: May:~ri and Mos Iron-ore Deposits in Cuba. Idem, 109. J. E. Little: Maynri lron Mincs, as Developed by the Spanish-American Iron ('0. Idem, 152. J. F. Iie~np: M'ryari Iron-ore Dcposi(s. Trans. (1915) 61, 3. C. K. Leith 2nd N. J. Mead: Additional Data on Origin of Lateritic Iron 01cs or Eastern Cubn. Tmns. (1916) 63, 75.

Jan 1, 1923

By R. Moldenke

The presence of nickel-chromium in pig iron made fro111 Cuban oles is so well known that the word "Mayari" is unconsciously associated with it. Since 1904, when exploration of the Mayari deposits of iron ore in northeastern Cuba was undertaken, there llas been increasing interest in these ores. Tlie Transactions contain numerous references to t1ieln.l This iron ore, which is shipped to the Tinited States in the nodulizecl state, has been thoroughly tested and found very valuable; the deposit covers over 25,000 acres and there is in sight over 500,000,000 tons of ore that, by systematic mining, runs practically constant in composition. With nickel and chromium present, also titanium in sufficient quantities to attract attention, as well as extremely low phosphorus and sulfur contents, the iron founder is naturally interested in the utilization of RInpari ore for pig iron for the better grades of finishrtl iron products. The present point of coilsn~iil)tion ol ILlapri ore is at Sparrow's Poi111, where hlayari pig iron of ally desiretl coml>osition is made. The composition of the dried ore is about as follows: Iron -29 per cent., silica 3 pc.r cent., nickel 1 per cciit., chroiniun~ 1.5 per cent., alumina 11 per cent., ant1 coinbined water 13 per cent. When nodulized, the iron runs up to nearly 56 per cent., the silic:~, :tlumi~i:i, nickel, and c~llromiurn are slightly highr than the arno~l~its just given. Practically all the, combined wntcr is driven off aild the iiodulizccl ore carries only a few- tenths per cent. of 1 C. M. Weld: Residual Rrolvn Iron Ores of Cuba. Tmns, (1909) 40, 299. C. K. Leitll nnd If'. J. Mcncl: Origin of Iron Ores of Central and Northeostr~n rlbn. Trans (1911) 42, 00. C. W. Hayes: May:~ri and Mos Iron-ore Deposits in Cuba. Idem, 109. J. E. Little: Maynri lron Mincs, as Developed by the Spanish-American Iron ('0. Idem, 152. J. F. Iie~np: M'ryari Iron-ore Dcposi(s. Trans. (1915) 61, 3. C. K. Leith 2nd N. J. Mead: Additional Data on Origin of Lateritic Iron 01cs or Eastern Cubn. Tmns. (1916) 63, 75.

Jan 1, 1923

By C. W. Spencer, F. N. Rhines, R. J. Knight

Ametallographic study has been made of the peritectoid transformation as it occurs in two Ag-A1 alloys, containing 6.0 and 6.9 wt pct Al, respectively. After equilibrating at 475°C, these alloys were transformed isothermally just below the peritectoid temperature which lies at about 450°C.1-3 Peritectoid transformation in this alloy system consists in the reaction of a and 5 to form µ. The crystal structures of the a, µ, and 5 phases have been determined as face-centered-cubic, 6 manganese, and hexagonal-close-packed, respectively. At the peritectoid temperature their equilibrium compositions are approximately 5.85, 7.02, and 7.24 wt pct (19.92, 23.2, and 23.8 atomic pct) aluminum."" The transformation might be expected to occur principally at the interface between the a and 5, but such is not the case. Instead, the major part of the transformation occurs by the direct (and perhaps initially diffusionless) conversion of 5 to µ. The composition range of the forming µ nearly overlaps that of the parent at the temperature of transformation" so that little, if any, composition change is required. Transformation proceeds by the nucleation of µ at points upon the external surface of the sample and sweeps through the 5 phase, leaving the a initially almost undisturbed. Subsequently, the a phase participates in the transformation by being partly or totally converted to µ. Specimens approximately 1/4 x 1/4 x 1/16 in. were cut from cast ingots, previously equilibrated 68 hr at 588°C. The specimens were held for 3 hr at

Jan 1, 1958

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By H. B. Menardi

The history, geology, ore deposits and current mining operations of the Huitzuco district have been described by C. W. Vaupelll and the current mill operations by David Segura.2 This paper completes the story of Huitzuco with a description of the reduction of the flotation concentrates. The predominant ore mineral in the Huitzuco deposit is livingstonite, a rare, mercury-antimony sulphide (HgS.2Sb2S3). Other associated minerals include cinnabar, stibnite and elemental sulphur. The gangue is largely limestone and gypsum. Former operators mined a selected grade of ore, from which the mercury was recovered by an expensive, inefficient operation. A considerable tonnage of rejects and fills, carrying mercury and antimony, was left in the mine. In order to recover both mercury and antimony from these fills and also from newly developed ore, a combination method has been developed, by means of which the livingstonite is concentrated by flotation and the flotation concentrates subsequently reduced to metallic mercury and antimony. An essential part of the flotation treatment, as developed by Segura, is the use of copper sulphate as an activating agent. A typical analysis of concentrates now being produced at the property is as follows: Hg, 7.73 per cent; Sb, 26.40; Fe, 1.20; S, 29.68; CaO, 11.50; MgO, 7.25; SiOz, 1.63; A1203, 0.65. PRocess foR Treatment op Concentrates In the development of a process for treatment of these concentrates, three different methods were investigated: (1) roasting in a Dwight-Lloyd sintering machine with an excess of air; (2) separation of mercury and antimony by distillation in a reducing atmosphere; (3) a third method, which ultimately developed into the present process. The third method involved a slow calcination at a closely regulated temperature with a limited admission of air, which separated the mercury and antimony, the raeroury passing out of the kiln with the furnace gases and the antimony remaining in the calcine or "sinter."

Jan 1, 1944

By W. A. McCurdy, Joseph W. Leonard, William F. Lawrence

INTRODUCTION Utilization from the Point of View of the Preparation Engineer The primary interest of the coal preparation engineer is in process design, operation, and maintenance to produce an acceptable product that can be sold at the greatest possible profit. Because of emphasis upon these interests, attention to other potential values of coal is sometimes neglected. The intent of this chapter is to alert the preparation engineer to the utilization possibilities of the product as well as the tributary coal flow moving through a modern coal preparation plant. The basis for any unrealized potential derives directly from the coal seam itself. Most coal seams consist of coal bands and benches sandwiched together in layers that differ visually from each other in physical structure and luster. Randomly selected physical and chemical ranges determined from layers of coal in a single seam can easily differ by as much as 30 Hardgrove grindability indices, 0.30 of a specific gravity point, 20 percentage points of ash, 6 percentage points of dry volatile matter, and 10 percentage points of total su1fur.l Similar wide variations exist for calorific value, seam moisture content, and, undoubtedly, for any other conceivable coal test parameter that might be used for comparative purposes. These observations all point to the long-established fact that coal is not homogeneous, as conventional analytical methods might tend to indicate, but is instead a highly heterogeneous substance.

Jan 1, 1979

ON Oct. 5, 1926, the day before the general ses-sions of the fall meeting of the American Insti-tute of Mining and Metallurgical Engineers at Pittsburgh, a round table conference on the combus-tibility and testing of coke was held at the Bureau of Mines Experiment Station. There were about fifty present, with A. C. Fieldner, chief chemist of the Bureau of Mines, as chairman. The following organi-zations were represented: American Institute of Min-ing and Metallurgical Engineers, American Society for Testing Materials, American Gas Association, Eastern States Blast Furnace and Coke Oven Association, Gas and Fuel Division of, American Chemical Society, and Southern Ohio Pig Iron and Coke Association. In opening the proceedings, Mr. Fieldner explained that the meeting had been called at the suggestion of several members of the Institute and members of other organizations. The subject is of interest to the pro-ducer and the user of coke whether it be in a blast furnace, cupola furnace, house-heating furnace, open grate, gas producer, or in a water-gas generator. There has been much confusion on this subject largely because there is no common definition of combustibility. Does the blast-furnace superintendent, the coke-oven operator, and the fuel engineer have the same under-standing of the term "combustibility"? If a common understanding can be reached, many differences of opinion will disappear. COMBUSTIBILITY OF COKE R. H. Sweetser of Columbus, Ohio, disagreed with the statement of P. H. Royster, T. L. Joseph, and S. P. Kinney in Reports of Investigations, Serial No. 2524, of the Bureau of Mines, in which it was stated that the coke-oven op-erator cannot change coke combustibility by modifying oven practice. Mr. Sweetser held that the coke-oven man can change the combustibility of coke. Blast-furnace men know that coke that will burn easily with low pressure and will. come down in the regular way in the furnace can be pro-duced from a given mixture of coal. His idea of the combustibility of coke is the rate of flow through the com-bustion zone of the blast furnace. If the coke does not pass through in normal manner it is highly incombustible. H. J. Rose of the Koppers Co., Pittsburgh, objected to being pinned down so closely on this phase of the com-bustibility and incombustibility of coke. Coke-oven men are frequently obliged to change oven conditions to make a coke which gives blast-furnace men what they want. The size of the coke and the screening have an important bear-ing on combustibility, and there are many cases on record where by simply changing the different sizes of the coke, everything worked smoothly, and that is a much more combustible coke.

Jan 1, 1927

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

Mining and oil industry representatives are scheduled to testify May 15 at hearings on the Simpson bill to extend the Reciprocal Trade Agreements Act, Several Congressmen have introduced bills to extend present trade agreements without modification. Price of copper appears to be stabilizing at 30[] per lb, after a period where market price ranged from 27 to 34[]. Copper offerings from abroad were finding no takers at 30.24[] per lb late in April.

Jan 5, 1953