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The Nominating Committee desire to submit the following nominations. President and Director: SIDNEY J. JENNINGS District 0 Vice-President and Director: H. S. DRINKER District 2 R. M. RAYMOND District 0 Directors: G. C. STONE District 0 HENNEN JENNINGS District 9 S. A. TAYLOR District 2 F. G. COTTRELL District 6 ARTHUR THACHER District 3 These nominations were unanimous. By order of the Committee J. V. N. DORR, Chairman. Oct. 10. 1917.

Jan 12, 1917

By J. P. Newell, R. W. Storey

AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery .augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120 This head design proved to be very satis-

Jan 1, 1952

By P. Schwarzkopf, J. H. Brophy, J. Wulff

A constitutional diagram has been proposed for the tantalum-rhenium alloy system. Rhenium dissolved in tantalum up to 48 wt pct, and the maximum solubility of tantalum in rhenium is 5 wt pct. Intermediate x and s phases were found. X-ray diffraction, metallography and melting points were employed. SEVERAL investigators have described the phases present in the tantalum-rhenium alloy system, but no detailed account of the phase diagram prior to the present investigation appears to be available. Greenfield and Beck' reported the solubility of 48 to 54 at. pct Re in tantalum, a s phase at 41 at. pct Ta, and x phase isomorphous with a Mn from 37 at. pct Ta to less than 25 at. pct. They employed as-arc melted specimens and heat treatments at 1200 °C lasting 72 hr.2 Duwez3 reported the existence of a a phase at the composition Re3Ta2. Niemiec and Trzebiatowski4 observed a lattice parameter a = 9.69A, for the x phase at a composition Ta7Re22, but no s phase. Savitiski and Tylkina5 have shown a hardness maximum at the composition 40 at, pct Ta and a somewhat lower plateau from 35 to 10 at. pct. Knapton6 indicated results similar to those of Greenfield and Beck.' The present investigation describes the phase relationships in the tantalum-rhenium alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURE Commercial 99.7 pct Ta powder from Fansteel Metallurgical Corp. and 99.9 pct Re powder from Chase Brass and Copper Co. were used for alloy preparation. The powders were weighed to desired nominal compositions and then pressed without binder into compacts weighing 5 or 10 g. The compacts were arc-melted six times on alternate sides on a water-cooled copper hearth using a nonconsumable tungsten electrode in an atmosphere of titanium gettered helium, at a pressure of 500 mm Hg. In most cases this procedure yielded alloy buttons of satisfactory homogeneity. A series of alloy specimens were analyzed wet chemically for use as standards for X-ray fluorescence. All specimens were analyzed by fluorescence and the results showed that the compositions differed by less than 3 pct Re from the original as-weighed nominal composition.* On the basis of self-

Jan 1, 1961

By Edward Hart

Having occasion several years since to make ferrous sulphide, I attempted to do so by fusing a mixture of coal-brasses (FeS2) and dried ferrous sulphate. A very nice-looking sulphide was obtained; but on attempting to use it, I found that it was insoluble in dilute hydrochloric and sulphuric acids. The subject was laid aside at the time, but has since been taken up; and some curious results have been obtained, which I believe are new. I have made the material by all of the following methods and the product seems to be pretty much the same, however obtained : (a) FeS2 heated to fusion. (b) FeS2, and FeSO4 heated to fusion. (c) FeS2, and Fe2O3 heated to fusion. (d) FeS2, and FeCO3, heated to fusion. (e) FeSO4, and S heated to fusion. (f) Fe2O3 and S heated to fusion. Obtained in this way the mass after cooling breaks easily and is very nearly black in color. On the upper surface of the fused cake the color is generally reddish or brownish black. When this is treated with dilute sulphuric or hydrochloric acid, it refuses to dissolve; but if touched with the point of a file or any piece of wrought-iron, solution of the sulphide takes place with the evolution of sulphuretted hydrogen. If the iron is removed the evolution of gas ceases, and only begins again when the iron is again brought into contact with the fused sulphide. The same thing happens if the iron is connected with the sulphide by means of a platinum wire. But in all the samples of fused sulphide I have obtained, if the iron is allowed to remain in contact with the sulphide for a certain time (which varies with different samples of the fused sulphide) and is then removed, solution of the sulphide continues. Zinc, tin, and magnesium have the same effect as iron. In hydrochloric acid aluminium acts more rapidly even than iron. In sulphuric acid it has little if any effect. Copper in HCl, when brought in contact with the fused sulphide, dissolves quietly without evolution of gas. The solution of copper chloride formed becomes,as it flows down over the sulphide, converted into copper sulphide.

Jan 1, 1887

By R. G. Davies

WeERTMANI has shown that the high temperature steady state creep rate, i, in lead and indium-base alloys obeys an equation of the form where AH is the activation energy, o the applied stress, n the stress exponent, and R and T have their usual meanings. He observed a variation in n from 4.5 for pure metals to 3 for concentrated alloys, which he interpreted as due to Change in creep mechanism from the climb of dislocations in pure metals to a micro-creep mechanism in the alloys. The Cottrell-Jaswon microcreep mechanism of the moving dislocation taking its impurity atmosphere with it was considered to be the most likely process, although short-range order and the segregation of solute atoms to a stacking fault will also give a stress exponent of 3. Steady state creep has been investigated in a Au - 27 at. pct Cu alloy at temperatures above 1/2 TIM where TIM the absolute melting temperature. As the oxidation resistance of this alloy is excellent all tests were carried out in air with a furnace built to give a temperature variation of less than 1°C along the 60 mm gage length. A lever-arm arrangement applied the stress with a load being adjusted between each creep test to maintain a constant stress. As each test produced less than 0.5 pct creep strain, the variation in stress during the test was negligible. The creep strain was measured by a transducer at the end of one of the alloy-steel grips, with the out of balance potential being finally recorded on a variable speed chart recorder. A typical creep curve is shown in Fig. 1. The results, Fig. 2, confirm that n is nearer to 3 than to 4.5; the creep mechanism could be any of those given above. The activation energy, AH, which is independent of stress, is consistent with a diffusion controlled process; the activation energies for the self-diffusion of gold and for the diffusion of gold into Copper are both -45 kcal per ml., There is now considerable evidence, that, when the steady state creep is dependent upon diffusion, irrespective of the actual creep mechanism, the activation energy is independent of the stress. The author would like to acknowledge the financial assistance provided by the International Atomic Energy Agency, Vienna, and the Argentine Atomic Energy Commission.

Jan 1, 1962

By R. Kossowsky

BRIDGMAN has listed five possible transitions in bismuth at 25°C which were observed as volume changes. He was unable however to detect the last three transitions by electrical-resistivity changes. Kennedy and LaMori have verified the pressures at the Bi 1-11 and Bi 11-111 transitions. They suggested however that the 125-kbar transition previously reported by Bundy3 actually corresponds to the 90,000 kg per sq cm transition observed by Bridgman.1 Jura4 reported a well-defined drop in resistivity at 92 kbar obtained by a four-lead method. The Bi 111-IV and Bi IV-V transitions have not been reported in any of the above-mentioned references.'-' Bundy3 observed a small dent in the low-temperature boundary of the Bi Vll region which is consistent with the presence of a 111-IV boundary. Zeitlin and Bray-man5 were the only ones to report small but well-defined drops in resistance of bismuth at 44.0 and 63.8 kbar, corresponding to Bridgman's 111-IV and IV-V transitions, respectively. High-purity (99.99 pct) 0.020-in.-diam 0.5-in.-long bismuth wire was used to calibrate the Uniram tetra-hedral high-pressure apparatus used in the present work. The bismuth phase changes at 25°C were correlated with changes in electrical resistance as a function of pressure. The output of a sensitive bridge constructed of carbon resistors and kept at a constant temperature of ±°C during the measurements was fed to the Y axis of a MoseleyX-Y recorder and the X axis was used for time scans. Specimens were pressurized using a hydraulic press with maximum capacity of 200,000 lb. Load was applied in increments of 2000 lb and held for about 3 min. The resistance was recorded at the end of this time period. Good contact was established below 20,000 lb. Typical recorder charts are reproduced in Figs. 1 and 2 which show that resistance fluctuations were practically nil during each time scan. Well-defined discontinuities in resistance were observed at 58,000 and 82,000 lb, Fig. 1. Two small but definite "blips" are noticed at 92,000 and 122,000 lb, Fig. 2. At 156,000 lb another drop is observed which

Jan 1, 1967

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2 that galena freed of surface oxidation products and lead carbonate ("clean" galena) is waterrepellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. Of 1.18 sp. gr hydrochloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (x) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table x.

Jan 1, 1941

By S. Shapiro, G. Krauss

We will reply to Dr. Pitsch's discussion by 1) presenting in greater detail the single surface trace analysis which we performed on the reversed austenite plates in a single parent plate of martensite of known orientation, 2) relating the results of our analysis to the conclusions which Dr. Pitsch makes on the basis of our data, and 3) examining the validity of our selection of twenty-nine individual traces from the over 200 austenite plates which were observed in a surface of this single martensite plate. Fig. 7 shows a standard (001) projection of the martensite plate from which the austenite-martensite interface traces were taken. The traces are plotted on the projection as the small solid circles, and the great circles corresponding to the loci of plane normals which could contain each trace or could intersect the surface plane along the measured directions are also plotted. It can be seen that these great circles intersect at a point which corresponds to the normal of the surface plane on which the traces were observed. Also rate which occurred only at particularly low heating rates, see Figs. 1 and 3 in the paper.2 Since in this case the interpretation of Jana and Wayman is plausible and since we have no alternative to this interpretation, we would like to state only that the existence of a diffusion-controlled reversal at low temperatures seems to be not yet proved beyond any doubt. The author wishes to thank Professor G. Krauss for making available his manuscript prior to publication. It is also a pleasure to acknowledge the lively written discussions, which the author has had with Professors G. Krauss and C. M. Wayman prior to this communication. The financial support of the Deutsche For-schungsgemeinschaft for the work on which this communication is based is also gratefully acknowledged. plotted within small dotted circles which represent a i3 deg scatter in each of the twenty-four unit stereo-graphic triangles are our A and B poles7 and the pole P determined by Kessler and itsch.' The data presented in Fig. 7 permit a direct association of the measured traces and the various proposed habit plane poles for the reversed austenite plates in the martensite crystal. If the sample measurements do in fact

Jan 1, 1969

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2. that galena freed of surface oxidation products and lead carbonate ("clean" galena) is water-repellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. of 1.18 sp. gr. hydro chloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (I) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table I.

Jan 1, 1941

By G. Sandoz, C. A. Siebert

OIL quenching of steel, in good commercial practice, is carried out using a great deal of agitation in the quenching bath. Many of the tests reported in the literature represent the results obtained on steels quenched into still oil. Scott1 describes three stages of cooling in liquid quenching baths, namely: "State `A'-Vapor Blanket Cooling-In this, the first stage, a thin stable vapor film surrounds the hot metal. Cooling is by conduction and radiation through the gaseous film and is therefore relatively slow. "Stage `B'-Vapor Transport Cooling- Termination of the `A' stage is marked by wetting of the metal surface. Vapor forms copiously in bubbles and is carried away by gravity and convection currents to condense in cooler surrounding liquid. This is the fastest stage of cooling. "Stage `C'-Liquid Cooling--The `B' stage ends as the surface temperature of the metal approaches the boiling point of the quenching liquid. Vapor no longer forms, so cooling is by conduction and convection and the temperature difference is greatly decreased. This mode of cooling is slower than that of the `B' stage." Mechanical agitation of the quenching medium will accelerate all three stages of cooling. The greatest effect, however, will be noted on stage `B' because the removal of the bubbles from the surface of the steel will not be entirely dependent upon gravity and natural convection currents. The method employed in this investigation for evaluating the oils was the end quench test. The various oils were substituted for water as the quenching liquid and hardness determinations were made at various distances from the quenched end. Most of the tests were run using a 3/8-in. orifice with a 2 ½ -in. stream height. However, to check the effect of other velocities two additional conditions were used, namely: (I) A 3/8-in. orifice and 1-in. stream height, and (2) a ½ -in. orifice and a 3 ½ -in. stream height. In all cases the samples were suspended so that the quenched end was ½ -in. above the orifice. The steel used was an NE 9450 having the following analysis: [ ] Some tests were run on an NE 8740, 3312, and a 4340 steel. The results obtained on these steels confirmed those obtained on the NE 9450 and have therefore been omitted' from this paper. The test bars were machined from 1 1/8 -in. stock to 1-in. diam by 4 in. long.

Jan 1, 1948

By L. Zwell, H. A. Wriedt

In describing their procedure for measuring the lattice parameters of solid solutions, Abrahamson and Lopata report (p. 77) the final heat treatment of their alloy specimens as "700°C for 100 hr, followed by a furnace cool". The isothermal part of this treatment may be expected to precipitate solute in excess of the stable a solid-solution limit at 700°C; the subsequent slow cooling is likely to reduce the dissolved solute still further. Fig. 1 (upper) presents the data for titanium alloys so he;rt-treated and shows the lattice parameters of solid solutions containing up to 3.5 at. pct Ti; Fig. 17 (lower) shows 2 at. pct Ti as the solubility limit in a iron at 700°C. Figs. 1 and 17 are thus incompatible. The paper contains comparable incon~patibilities for zirconium alloys, for niobium alloys, and for tantalum alloys. The final heat treatment at 700°C may also be responsible for the anomalous "knee" in the lattice-parameter data for nickel alloys, Fig. 3. The "knee" composition is located near the 700°C limit of the stable a solid-solution field;37 alloys of the experimental composition range with more nickel than the "knee" composition are two-phase at 700 C and prolonged heat treatment of them at 700°C would tend to produce inhomogeneity rather than homogeneity. In Figs. 4 and 7, the composition ranges of the zirconium, hafnium, and niobium alloys examined terminate at alloy concentrations of 0.1 to 0.2 at. pct. These metals form very stable oxides and their partial removal from solid solution in iron by impurity oxygen may be expected. We believe that the authors should have reported the procedure by which they distinguished the amounts of alloying elements in solution and in oxide. The diagrams pertaining to copper in Figs. 3 and 18 (lower) are almost certainly incorrect. Three recent investigations of this system38-40 all substantially agree on the solubility of copper in a iron, finding it to be much larger than that reported by Abrahamson and Lopata. The change of the lattice parameter with composition reported by Abrahamson and Lopata is too large by a factor of three to five, as seen by comparison with the findings of other investigators.41738 Moreover, the authors violate, in Fig. 18, the accepted Fe-Cu constitution diagram37 by ignoring the eutectoid at about 850°C.

Jan 1, 1967

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.'-' While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood' has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3'4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968

By G. R. Speich, Morris Cohen

The growth rate of bainite has been determined by hot-stage metallography in five hypereutectoid high-purity iron-carbon, iron-carbon-chromium, and iron-carbon-nickel alloys. The studies have been confined essentially to lower bainite. The growth rate is independent of time at constant temperature, but both the edgewise and sidewise growth rates increase with increasing temperature. Increasing the carbon content, or adding chromium or nickel, decreases the growth rate without greatly affecting the temperature dependence. The results lead to separate diffusion-controlled models for the edgewise and sidewise growth rates. ALTHOUGH bainite has been subject of many detailed investigations,1,2 the growth mechanism of this intermediate transformation product of steel remains unclear. One difficulty has been that practically all the kinetic measurements have been restricted to studies of the overall reaction rate. Only a limited amount of information3, 4-6 is available on the growth process itself. The purpose of the present work was to investigate the effect of time, temperature and composition on the growth rate of bainite using hot-stage metallography. This method makes it possible to observe continuously the isothermal growth of individual bainitic units because of the surface upheavals accompanying their formation.3 This information is needed to test the existing growth models and to obtain a better understanding of the factors controlling the bainitic transformation. EXPERIMENTAL PROCEDURE Alloys—The compositions of the alloys used in the present work are shown in Table I. The five alloys were vacuum-melted and cast, and were prepared from high-purity materials. The three iron-carbon alloys were available from the work of Roberts et al.7 in the form of 3/8-in. diam rods.* To facilitate machining, the rods were ing. The rods were then tempered for 3 hr at 650°C to allow machining. The iron-carbon alloys in Table I were selected for investigating the effect of carbon on the bainitic growth rate. Due to the rapidity of the transformations involved, it was not feasible to measure the growth rates in iron-carbon alloys having carbon contents much less than 0.9 pct C. The iron-carbon-chromium and iron-carbon-nickel alloys were selected to study the influence of chromium and nickel on the growth rate at a carbon level of about 1.1 pct C, since this carbon content was intermediate among the iron-carbon alloys. The concentrations of chromium and nickel were chosen to match isothermal trans formation diagrams in the literature.8'9 Hot-Stage—Since the iron-carbon alloys had such low hardenabilities, it was necessary to quench the hot-stage specimens drastically from the austentiz-ing temperature to the isothermal transformation temperature to prevent the formation of pearlite or proeutectoid constituents. A rapid-quenching metal-lographic hot-stage was built for this purpose. A maximum temperature of about 1100°C and quenching rates up to 500°C per sec could be attained with this equipment. The details of the apparatus are described in a recent publication. After being polished and mounted on the hot-stage, the specimen (0.020 in. thick) was protected from oxidation and decarburization during austenitizing by a vacuum of 10-4 to 10-5 mm. The quench to the reaction temperature was accomplished with a helium blast, and the isothermal run at this temperature was conducted in a helium atmosphere. A fine-wire thermocouple spot-welded to the sample and a high-speed

Jan 1, 1961