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By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

MINING AND METALLURGICAL SOCIETY OF AMERICA San Francisco Section The San Francisco Section of the Mining and Metallurgical Society of America held a joint meeting with the local section of the American Institute of Mining Engineers at the Engineers' Club, San Francisco, on Tuesday, Apr. 16, 1918. The meeting was preceded by a dinner. Letters from the parent body in NewYork asking for the consideration of the proposed bill before Congress, and an expression of opinion relative to the appointment of a Federal Administrator of Mines justified the joint meeting of the local sections of the two mining societies, in that a more representative opinion of the engineers of California could he obtained. The meeting was called to order at 7:15 P.M. by Mr. Frank H. Probert acting as Chairman. About thirty engineers were present. Mr. Probert read a letter of March 14, from Secretary Huntoon, asking that the meeting be called. He read excerpts from Bulletin 117 of February 28, 1918, of the Mining and Metallurgical Society containing a copy of the proposed bill, so that all present might be advised of its essential contents. He briefly commented on the urgent need of such legislation and invited discussion of the subject. After long and thorough discussion on the part of the members present, Professor Lawson made the following motion: I move that a resolution expressing the sense of the joint meeting of the local sections of the American Institute of Mining Engineers and Mining and Metallurgical Society of America be forwarded to the secretaries of the two societies to the effect that we heartily approve of the purpose and intention of the bill designed to promote and stimulate the production of minerals necessary for the successful prosecution of the war; and that we suggest prices should be fixed for the period of the war and two years thereafter, and that these prices, guaranteed by the Government, should apply at the nearest shipping point to place of production of the minerals. This motion was carried. The meeting then adjourned, and a telegram was sent by Mr. Probert, the Chairman, to Mr. Huntoon, notifying him of the motion that had been carried at the meeting.

Jan 7, 1918

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W. FRANCIS, Chairman, WILLARD S. MORSE, Vice-Chairman. THOMAS -T. READ, Secretary, Woolworth Bldg., New York: N. Y. P. A. MOSMAN, Treasurer. LOUIS D: HUNTOON. Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY, S. H. RICHARDSON.

Jan 10, 1914

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,' and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6'7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.' EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.' Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

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Jan 1, 1907

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

The temperature, orientation, and strain-rate dependence of tensile flow in single-crystal NiA1 of equiatomic composition have been investigated up to 800°C. Compression tests at room temperature have also been carried out. Optical and replica electron microscopy and X-ray diffraction methods were used to investigate the slip mechanisms. NiAl exhibits {110)(001) slip and cube slip {l00)(010) was also observed. This results in very high strength of single crystals in cube orientation. The implications of this slip mode, with the resultant small number of possible slip systems and three mutually perpendicular slip vectors, are discussed. ThE CsCl structure compounds represent a class related to the bcc elements, but their behavior is affected by three additional variables: composition (within the stability range of the compound), extent of long-range order perfection, and bonding energy. Very little data are available on the effects of these variables on mechanical properties. Rachinger and ~ottrell' suggested slip to occur along (111) in compounds of low ordering energy; in compounds of higher bond strength (>0.06 ev), they observed (110) (001) slip. As pointed out by copley,' only three in- dependent slip systems are available in the latter case; hence general deformation is impossible. Brown3 carried out a theoretical calculation of the yield-point variation with the degree of long-range order in the CsCl structure, based on the assumption of superdislocations. More general approaches, based on considerations of superlattice dislocations and antiphase domain boundaries in ordered structures, were carried out by Flinn~ and by Vidoz and Brown.' These, however, give no information on changes in the slip structure—if any—between the ordered and the disordered compounds. This aspect was investigated experimentally and theoretically by Stoloff and Davies' and by Marcinkowski and chessin7 in FeCo. The latter workers proposed the deformation behavior of the ordered FeCo to be essentially the same as that in many other bcc metals. Investigations of polycrystalline A~M~'-'O indicate considerable variation in mechanical properties with composition and test temperature. The existence of {123)(111) slip was reported in AgMg.'9'9'0 (The formation energy of this compound, presumed to be ordered at all temperatures below melting, is 4.38 cal per g-atom," i.e., 0.024 ev per bond.) The yield strength has been reported as relatively independent of temperature below 0.45 T, (where T, is the absolute melting temperature). Tensile deformation of single-crystal AgMg was also investigated by Kurf-man," who observed marked tendency to single glide on{112}(111) and {110)(111). From observations of slip lines in deformed poly-crystalline NiA1, Westbrook et a1.I3 suggested the

Jan 1, 1968

By Herbert J. French

Herbert 1. French (Member 1934), vice president of the International Nickel Co. Inc., assistant vice president of the International Nickel Co. of Canada Ltd., and AIME Howe Memorial Lecturer for 1956, died in Rochester, Minn. on Aug. 17, 1955, after a long illness. Before his death, Mr. French had laid the foundation of research on which the Howe Memorial Lecture (p. 770) was based. His associates at Inco, 0. 0. Miller and J. W. Sands, were able to complete the project, present the lecture, and prepare it for publication, following Mr. French's general outline. Born in New York on May 27, 1893, he graduated from the School of Mines, Columbia University, with a degree in metallurgical engineering in 1915. Mr. French gained his early engineering experience with the American Smelting and Refining Co., serving as a chemist and as-sayer at the company's Murray, Utah, installations. He later returned east and became a metallurgical engineer for the General Vehicle Co., Long Island City, IT. Y., a subsidiary of the General Electric Co. In 1917 Mr. French was appointed civilian inspector of materials for the U.S. Army Signal Corps, and continued this work when it was later absorbed into the Bureau of Aircraft Production. Subsequently he was appointed district inspector in Philadelphia for the Pittsburgh (Ordnance Metallurgical) office, later transferring to Pittsburgh. After World War I Mr. French became an assistant physicist on the metallurgical staff, U. S. Bureau of Standards, Washington, D. C. During his years with the Bureau, he was successively associate physicist, metallurgist, senior metallurgist, and assistant chief, division of metallurgy. In 1929 Mr. French joined International Nickel as a metallurgist at the company's Bay-onne, N. J., research laboratory. Transferring to the development and research division, New York, in 1931, he took charge of alloy steel and iron development, becoming assistant manager of this division in 1943. Mr. French's appointment as an Inco vice president came in March 1947. Previously, he was appointed assistant vice president of the International Nickel Co. of Canada Ltd. in January 1947. Mr. French served the War Production Board during World War II as senior technical consultant in charge of the metallurgical and specifications section of the iron and steel branch. When this section of the WPB was organized into the steel division, he was appointed chief of the metallurgical branch. From March 1944 to September 1945 Mr. French served as assistant director. Herbert French was well known not only for his prolific contribution to the metallurgical literature, for which he received numerous awards, but also for his prolonged service to the profession through its technical societies. He was a past president of ASM, and was the Campbell Memorial Lecturer for that group in 1933. Mr. French was honored by the American Society for Steel Treating in 1931 when he was awarded the Henry Marion Howe Medal. A series of lectures he gave in 1941 before the Fourth Western Metal Congress in Los Angeles was later published in book form under the title Alloy Constructional Steels.

Jan 1, 1957

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By F. R. Morral

INDUSTRY has yet to find a universal solution to the problem of engineer personnel selection. Today, the choice of the right man for the right job is even more pressing than ever before. The age of the hard apprenticeship seems to have passed. In its place one finds the interviewer who must determine through personal contact and evaluation of college grades whether a graduate engineer will fit into his company's scheme. The problem, as it is constituted today, may be broken into four parts: Need for better use of human resources (there is a shortage of engineers, scientists, and skilled workers), productivity with higher efficiency, encouragement of personal pride in work performed, and employee's happiness on the job and away from it.

Jan 4, 1953

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W. FRANCIS, Chairman. WILLARD S. MORSE, Vice-Chairman. . THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN, Treasurer. LOUIS D. HUNTOON, Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY, S. H. RICHARDSON.

Jan 6, 1914

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W. FRANCIS, Chairman, WILLARD S. MORSE,. Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN, Treasurer. LOUIS D. HUNTOON. Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY, S. H. RICHARDSON.

Jan 8, 1914

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W, FRANCIS, Chairman, WILLARD S. MORSE, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN, Treasurer. LOUIS D. HUNTOON. Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W..RODDEWIG, Vice-Chairman. LYNDON K, ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY, S. H. RICHARDSON.

Jan 7, 1914

By John B. Dilworth

In September, 1930, H. N. Eavenson, then Chairman of the Coal Division, appointed a Committee on Methods of valuing Coal Propelvties, with John B. Dilworth as chairman. The latter prepared a schedule' of features for consideration under the general headings of Undeveloped and Developed Coal Properties. These subjects were divided among the members of the committee and during the next year written discussions of his allotted subjects were received from each member. Mr. Grimes and Mr. Eavenson discussed the entire list,. These discussions were mimeographed and a set sent to each member before the meeting of the Institute in February, 1932. There was a general discussion at that meeting. At the meeting in February, 1934, Mr. Dilworth submitted a report12 which summarized the accumulated opinions and data and presented the conclusions of the committee as a whole on the subjects embraced in it's schedule. Members of the committee expressed the desire that some of the individual opinions be published for reference. Mr. R. Damon Hall's abstracts of these papers arc therefore presentrd herewith.3 Personnel of Committee John B. Dilworth (Chairman), Consulting Mining Engineer, Edward V. D'Invilliers Engineering Co., Philadelphia, Pa. Eli T. Conner, Consulting Mining Engineer, Seranton, Pa. W. G. Duncan, Jr., Superintendent, W. G. Duncan CoaI Co., Greenville, Ky. Howard N. EAveNson, Consulting Mining Engineer; Eavenson, Alford & Hicks. Pittshurgh, Pa. George Watkin Evans, Consulting Mining Engineer, Seattle, Wash. J. A. Garcia, Consulting And Constructing Engineer, Allen & Garcia Co., Chicatgo. III. John Alden Grimes, Valuation Engineer, Bureau of Internal Revenue, Washington, D. C. Otto Herres, Assistant Manager, United States Fue1 Co., Salt Lake City, Utah. J. R. Hicks, Consulting Mining Engineer, Eavensorl, Alford & Hicks, Pittsburgh, Pa. Robert D. Reeder, Mining Engineer, U. S. Bureau of Mines, Washington, D. C. Samuel, A. Taylor, Consulting Engineer, Pittsburgh, Pa. Bleeckee L.. WHeeler, Mining Engineer, Ford, Bacon & Davis, New York, N. Y.

Jan 1, 1934

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.'-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels' have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,'' using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson's experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970

By John V. Beall

Let's start at the beginning, Mr. Turner. Where and when were you born? In Lansing, Mich., on July 31, 1880. And what was your education? I went to the University of Michigan, where I got an A.B. degree in 1902; then to the Michigan College of Mines at Houghton, graduating from there in 1904 with a B.S. and an E.M. What was your first job in the mining industry, Mr. Turner, and what were you paid? In the summer of 1902, 1 was a field assistant for the U. S. Geological Survey in southwestern Idaho and southeastern Oregon, working under Israel C. Russell, professor of geology at the University of Michigan, who incidentally, had just returned from an expedition to study the effects of the eruption of Mt. Pelee, on Martinique. I was paid $60 a month and found; in addition to doing geologic and hydrographic work, I cooked many of the meals for a party of four, and wrangled four horses. I slept for four months under the stars, without a tent.

Jan 1, 1949