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[James C. Gray, President W. B. Stephenson, President-Elect A. B. Cummins, Past-President E. G. Fox, Eastern Regional Vice-President H. C. Weed, Western Regional Vice-President Donald W. Scott, Central Regional Vice-President John Cameron Fox, Secretary 29 W. 39 Street New York 18, N. Y. After September 7, 1961 345 East 47 Street, New York 17, N. Y. D. R. Tone, Assistant Secretary Nathaniel Arbiter, Treasurer]

Jan 1, 1961

Jan 1, 1968

Redetermination of the Chromium and Nickel Solvuses in the Chromium-Nickel System by C. J. Bechtold and H. C. Vacher, p. 14 The text of pages 16 and 17 is in improper sequence. The correct version will appear in the bound volume.

Jan 1, 1962

By W. G. Woolf, E. R. Crutcher

The electrolytic zinc plant of the Sullivan Mining Co. is in Government Gulch, at Silver King, Shoshone County, Idaho, in the Coeur d'Alene mining district, about one mile from the Bunker Hill smelter and about three miles from Kellogg. The Sullivan Mining Co., which owns both the zinc plant and the Star mine, is itself owned jointly by the Bunker Hill & Sullivan Mining & Concentrating Co, and the Hecla Mining Company. The Tainton high-density, high-acid process is used at this plant, therefore some parts of its flowsheet differ markedly from those of electrolytic plants using the low-density process. While it is a custom plant and has treated a variety of zinc concentrates originating from various sources in a number of states, it has obtained its main supply of zinc concentrates chiefly from the zinc-bearing ores of the Coeur d'A1ene mining district, of which the principal important sources have been the Bunker Hill and Star mines. Thus the main feed has been zinc concentrates obtained from complex lead-zinc-silver ores. For the year of 1935 the concentrates had the following composition: water, 9.5 per cent; Zn, 50.6; Pb, 3.3; Fe, 9.4; S, 31.0; Cu, 0.2; insoluble, 2.9. Flowsheet The concentrates are delivered to the plant in railroad cars, which discharge into storage bins directly under the track. Bottom-dump cars are dropped directly into the bins while a slip scraper, pulled by an air tugger hoist, is used to empty box cars. There are five storage bins for concentrates, each of approximately 300 tons capacity. At the bottom of each bin there are individual belt feeders that discharge onto a common conveyor belt, which in turn discharges to another belt that carries the concentrate onto a weightometer belt for weighing. Immediately after the weighing, the crushed oversize return from the roasters is added to the load on the belt and then the ground-up sweepings, lumps and roaster cleanings. An electromagnet at the end of this conveyor removes tramp iron from the feed. The belt discharges to a set of 30 by 12-in. rolls, which break up lumps or frozen chunks of concentrate, etc. Beneath the rolls there is a screw conveyor, which conveys the roll discharge to a

Jan 1, 1937

E. G. Spilsbury, Trenton, N. J.: Mr. Case's paper possesses much interest for me, because my attention was called many years ago (early in the seventies) to the deposit he describes, and his explorations seem to have confirmed the predictions I then made as to the form of the deposit, namely, that the ore would be found to occur, not, as was then imagined, in loose boulders, distribnted

Jan 1, 1894

Society of Chemical Industry (London), American Section. Foster D. Shell, Secretary, 130 Clinton St., Brooklyn, N. Y. Publications of this Society are not of direct interest in this directory but the address of the Society is listed that the reader may have it on record for reference. Subscription to the Journal (A the Society costs £ 2 10s, or $12.50 at the normal rate of exchange. Individual copies are is 9d, postage extra.

Jan 1, 1933

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of' carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,'-' it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;' the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By A. F. Melcher

THE present paper is a progress report. on an investigation of the physical factors of oil and gas and especially of their sands, I such as-pore space, size of pores or permeability, retentivity, viscosity of the oil, temperature, pressure, thickness and area of the pay sand, water relations, and capillarity. The purpose is to determine as many of these physical factors as possible, and to ascertain the relations existing, directly or indirectly, between these physical factors and the production of oil and gas. As yet only pore space2 and size of grains of pay sands have, been investigated, although an apparatus has been designed to determine the permeability of a sand to oil, water, or gas under definite drops of pressure between the entrance face and exit face of the sample. Messrs. E. W. Shaw, R. Van A. Mills, D. Dale Condit, G. B. Richardson, G. C. Matson, and C. H. Wegemann collected the samples upon which the physical determinations were made. Acknowledgment is made to my colleagues of the United States Geological Survey for many suggestions and criticisms; to Mr. Mills for the production data given of the oil wells from which some of the samples were collected; to Mr. A. W. McCoy of the Empire Gas and Fuel Co., Bartlesville, Okla., for many ideas.

Jan 4, 1920

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By P. G. Winchell, M. Cohen, J. Woodilla

The kinetics of stabilization have been studied with respect to the isothermal component of the martensitic reaction in ivon-nickel alloys. Although the carbun (or nit-vogen) content may be very low in these alloys, it plays an important vole in the stabilization phenomenon. In fact, if these interstitial elements are removed by moist-hydrogen treatment, no evidence of stabilization is found. In the pvesence of 0.007 wt pct C, the activation energy for the stabilization process is comparable to that -for the diffusion of carbon (or nitrogen) in ferrite) rather than in austenitc. This suggests that the interstitial diffiision controlling the stabilization occurs within the martensitic embryos rather than in the matrix of the parent phase. The kinetics furthev indicate that the interstitial atoms tend to diffuse -from the embryos toward the suvroundings, thereby immobilizing the interface. This appears to be the origin of the stabilizing effect -found in these alloys. PHILIBERT' has shown recently that interstitial elements play an important role in the stabilization of martensitic transformations in iron-base alloys. However, determination of the temperature dependence for this stabilization process has produced values (- 11,000 cal per mol) that cannot be readily identified with the activation energy for diffusion of carbon (or nitrogen) in either ferrite or austenite. In the present work, the isothermal mode of the martensitic reaction was employed to derive the activation energy for stabilization, and this was found to agree fairly well with that for diffusion of carbon (or nitrogen) in ferrite. An iron-nickel alloy with 30.8 wt pct Ni and 0.007 wt pct C was used in these experiments, the specimens being in the form of rods 0.074 in. in diam and 2 1/2 in. long. The specimens were sealed in evacuated vycor tubes and austenitized at 1100°C for 1/2 hr prior to quenching in water. A second series of specimens was decarburized (and denitrogenized) prior to the above austenitizing treatment by annealing in moist hydrogen for 182 hr at 1215°C. In order to achieve a "standard" condition in the austenitic state, all the specimens were transformed to martensite by cooling to - 195°C before the final austenitizing. Both the 0.007 pct C and the decarburized series then had an Mi temperature of about - 30°C. The isothermal martensitic transformation was carried out at a reference temperature of -88"C, and was traced by means of electrical resistance measurements. Each resistance value was normalized by dividing by the resistance of the austenitic specimen at O°C, thus giving a resist- ance ratio R. The rate of decrease of the resistance ratio (-dR/dt) provided a measure of the transformation rate. It was found that a plot of R vs log t at the reference temperature resulted in a slightly curved line which could be closely approximated by two straight lines intersecting at a time of 10 min, as shown in Fig. 1. If G = dR/dlogt is the linear slope of either straight segment, the rate of transformation at any given time is: The ratio of G for 1 less than 10 min to that for t greater than 10 min was 1.19 for the 0.007 pct C series and 1.24 for the decarburized series. These ratios made it possible to compute the transformation rate at any time greater than 10 min, knowing the transformation kinetics prior to 10 min. The stabilization treatment was introduced by up-quenching from the reference temperature, usually after 10 min of isothermal transformation: to one of four stabilizing temperatures between 0" and 22"C. After holding for various times, the specimens were down-quenched to the reference temperature for additional isothermal transformation. In this way, it was possible to compare the transformation rate (- dR/dt), immediately after stabilization with the transformation rate (- dR/dt)U in the unstabilized condition. The degree of stabilization was defined as: Ordinarily, Gs and Gu would be measured after the same time of prim isothermal transformation.

Jan 1, 1960

By E. A. Devuyst, M. A. Mosoiu, V. A. Ettel

Nickelic hydroxide is an important metallurgical reagent used for precipitating cobalt from nickel sulfate solutions. Existing methods of preparation of nickelic hydroxide involve electrolytic oxidation of Ni(OH)2 or the use of strong oxidizing agents such as chlorine, ozone and persulfate. Although the oxidizing properties of the SO2 + O2 system have been known for some time, e.g., detection of SO2 and oxidation on iron in acidic solution, the application of this system for the preparation of nickelic hydroxide as a process was not considered in the past. The present paper describes a new method for chemical preparation of nickelic hydroxide which has been developed in INCO laboratories. The technique consists of reacting nickelous hydroxide suspensions with a slurry of calcium sulfite in the presence of air or oxygen. The main advantage of the process is the cost of reagents and an absence of soluble by-products (e.g., C1-). The chemistry of this process is unusual since the redox potential obtained during the reaction exceeds that of the oxygen electrode. Therefore, the effect of CaS03 is not just a catalytic acceleration of the reaction NI(OH)~ + 02. The so3= must be involved in the stoichiometry of the overall reaction producing in the initla1 phase some strongly oxidizing intermediate species.

Jan 1, 1981

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949

By AIME AIME

Report of Committee 24, of the International Association for Testing Materials, presented at the Brussels Congress, 1906. Republished for use at the 94th Meeting of the American Institute of Mining Engineers, New York, N. Y., February, 1908. Discussion by letter is requested by the Secretary of the Institute. The Committee appointed for the solution of Problem 24 consisted of the following members Prof. H. M. Howe, New York, N. Y. (Chairman); L. Levy, Paris, France (Vice-Chairman) ; Prof. D. Tschernoff, St. Petersburg, Russia (Vice-Chairman) ; Prof. Albert Sauveur, Cambridge, Mass. (Secretary) ; Van Drunen, Ixelles, Belgium; Lieut.-Col. H. Tusen, Copenhagen, Denmark ; E. P. Martin, Abergavenny, England ; A. Pourcel, Paris, France ; H. Brauer, Dortmund, Germany ; Dr. Prof. H. Wedding, Berlin, Germany; P. Verole, Milan, Italy ; A. Baalsrud, Christiania, Norway ; A. R. v. Dormus, Vienna, Austria ; A. Sailler, Vienna, Austria; Bureau des Forges, St. Petersburg, Russia; Prof. N. Belelub-sky, St. Petersburg, Russia ; N. Jossa, St. Petersburg, Russia ; Maj.-Gen. M. Korobkoff, St. Petersburg, Russia ; S. Smirnoff, St. Petersburg, Russia ;.Ladislaus v. Tetmajer, Budapest, Hungary ; H. H. Campbell, Steelton, Pa. Early in February, 1905, a list of species and varieties of iron and steel, with definitions, drawn by the Chairman and Secretary of Committee 24, was sent to every member of this Committee with a request for comments and suggestions. A special request was sent to the following gentlemen . for the equivalents in their several languages of these species and varieties : A. , Pourcel, Paris, France; Prof. H. Wedding, Berlin, Germany ; J. A. Brinell, Stockholm, Sweden ; Prof. H. I. Hannover, Copenhagen, Denmark; Prof. P. Kley, Delft, Holland; P. Verole, Milan, Italy; Col. Cubillo, Trubia, Spain. This present report, which is based upon our original list and definitions, and upon the replies to these requests, consists of four parts I. A polyglot, which gives the names of the chief classes of iron and steel in English, French, German, Swedish, Danish and Dutch. We .regret that we have failed to get the Italian and Spanish names. II. English definitions of principal classes of iron and steel. III. A glossary of special sizes and shapes of iron and steel. IV. A note on the boundary between steel and cast-iron. I. POLYGLOT, IN ENGLISH, FRENCH, GERMAN, SWEDISH, DANISH AND DUTCH, OF THE CHIEF CLASSES OF IRON AND STEEL, AND OF THE APPARATUS IN WHICH THEY ARE MADE. This list is not intended to be complete, but rather to include only those varieties which are of interest to the Association.

Mar 1, 1908

PRESIDENT AND DIRECTOR R. C. ALLEN . CLEVELAND, OHIO PAST PRESIDENTS AND DIRECTORS H. A. BUEHLER ROLLA, Mo. JOHN M. LOVEJOY NEW YORK, N. Y. VICE-PRESIDENT, TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y. VICE-PRESIDENTS AND DIRECTORS HENRY KRUMB NEW YORK, N. Y. PAUL D. MERICA NEW YORK, N. Y. H. G. MOULTON NEW YORK, N. Y. HARVEY S. MUDD Los ANGELES, CALIF. WILFRED SYKES CHICAGO, ILL..

Jan 1, 1937

Upper Peninsula W. O. HOTCHKISS, Chairman C. H. BAXTER, Secretary-Treasurer, Michigan College of Mining and Technology, Houghton, Mich. S. R. ELLIOTT RUDOLPH ERICSON W. H. SCHACHT Utah Meets second Thursday of each month, October to May, inclusive B. L. SACKETT, Chairman C. T. VAN WINKLE, Vice-chairman G. L. OLDRIGHT, Secretary-Treasurer, U. S. Bureau of Mines, Salt Lake City, Utah A. E. RING L. A. WALKER

Jan 1, 1932

By D. Walton, W. C. Winegard, W. A. Tiller, J. W. Rutter

It is shown that the cellular substructure observed in binary alloy crystals grown from a melt of known concentration can be eliminated by the proper choice of growth conditions. For a given solute concentration, there exists a critical ratio of temperature gradient G in the melt to the rate of solidification R of the crystal, i.e., of G/R, which must be exceeded before the cellular structure can be eliminated. A secondary substructure is observed which is related to the cellular substructure. IN crystals grown from the melt, a prismatic substructure has been observed by Buerger,1 Pond and Kessler,2 and Rutter and Chalmers." This structure is columnar in the direction of growth and appears as a network of hexagonal cells in the plane of the solid-liquid interface. Rutter and Chalmers3 have shown that this substructure occurs as a result of the presence of a layer of high impurity concentration in the melt adjacent to the solid-liquid interface. The formation of the substructure is accompanied by a redistribution of this impurity in the neighborhood of the interface. The structure can be controlled by proper adjustment of the variables in the solidification process such as a rate of solidification and the temperature gradient in the liquid. The redistribution of solute during the solidification of metal crystals has been treated theoretically

Jan 1, 1956

By C. G., Fink

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution.

Jan 1, 1950

By Pierre R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,1 and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.2-4

Jan 2, 1959

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963