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By LESTER H. WOOLSEY

IT IS doubtful whether anything new can be said upon this subject and, therefore, it is with considerable hesitation that l prepare this paper. On account of my recent connection with the Department of State as its law- officer, perhaps I will be pardoned if I discuss this subject briefly from the point of view of that branch of the Government. , I cannot, of course, speak for that department, since I have-no connection with it at-present, but it may be helpful if I set down certain* of the factors which in my opinion and from my experience have a bearing on this international problem. With oil-burning ships, motor vessels, motor vehicles, airplanes-all consuming, astonishing quantities of petroleum or petroleum products; with the United States having within its borders only 12 per cent. of the petroleum resources of the world, and consuming about 70 per cent. of the world's output; with the more enterprising nations wide awake to the necessity ; of obtaining and preserving as large a share as possible of the oil resources extant ; the 'problem is peculiarly and in a, very practical sense an international one.

Jan 1, 1921

By Robert F. Brindisi

There are approximately thirty to forty operating mills in the United States which are currently producing uranium yellow cake. This figure includes a significant number of in situ and by-product operations however the conventional acid leach flowsheet depicted in Figure 1 is the most common process used by domes- tic yellow cake producers. Ground ore is leached with sulphuric acid and the solids are separated from the pregnant liquor and washed in a series of counter- current decantation thickeners. After clarification of the pregnant liquor, uranium is recovered from the solvent extraction/stripping circuit by the addition of ammonia with precipitation of ammonium diuranate, or simply yellow cake. The yellow cake precipitate is then thickened in a conventional thickener before re- porting to the dewatering/washing unit operation. De- watered solids subsequently report to thermal drying, and clarified liquor from the dewatering/washing step is recycled to the yellow cake thickener. The yellow cake dewatering/washing unit operation is generally accomplished using either a solid bowl centrifuge or a rotary vacuum drum filter. In most cases the underflow from the yellow cake thickener is pumped to the dewatering/washing unit operation at approximately fifteen to twenty percent solids. For the purpose of this discussion ammonium diuranate, the product of ammonia precipitation from a conventional acid-leach uranium mill flow sheet, as discussed earlier, will be considered. With only slight adjustment this discussion will be equally applicable to sodium diuranate or uranium perioxide precipitates and to either in situ or by-product operations where such precipitates are generated. Some of the domestic uranium mills which have selected solid bowl centrifuges instead of vacuum drum filters for the dewatering/washing unit operations are listed in Figure 2. Why have these uranium mills, as well as others not listed, chosen to use the solid bowl centrifuge for this particular application? It is simply a matter of performance, reliability and economics. In the remainder of this paper the performance, initial cost, installation cost, maintenance and power consumption of both the solid bowl centrifuge and the rotary vacuum drum filter will be com- pared. In order to provide a consistent basis for comparison the appropriate sized (centrifuge or filter) unit for the dewatering/washing of 400 to 500 pounds per hour of yellow cake solids will be considered. Such a flow will usually be generated by a typical 3,000 ton per day (acid-leach) uranium mill.

Jan 1, 1980

By Albert Hoskinson

PROGRESS on the earth depends to a large extent upon the rapid inter-change of ideas and commodities between the various nations of the world. The smooth flow of commerce, by which these ideas and com-modities move, is accelerated by accurate and complete maps of the various land and water areas of the earth, The production of accurate maps depends upon a complete knowledge of the figure and dimensions of the object to be charted, therefore a knowledge of the shape of the earth is a prime necessity for accurate charting purposes. Gravity observa-tions were first undertaken to aid in determining the shape of the earth so that the geodetic surveys of its land and water areas might be more accurately connected to form an undistorted map. A large part of the earth's surface is water and it is therefore necessary to get gravity values at sea as well as on land before a complete and accurate figure of the earth can be determined. Dr. F. A. Vening Meinesz, of Holland, was the first scientist to perfect a pendulum instrument that would accurately measure gravity at sea. He had previously developed a multiple pendulum apparatus for measur-ing gravity upon swampy and unstable land areas in Holland and it was therefore quite natural that he should adapt the instrument to give accurate results upon a still more unstable support, the surface of the sea. His instrument as perfected gives satisfactory results when mounted in gimbals on any vessel where the roll and pitch are not more than about 5° and where the vibrations from rotating machinery and wave action are not large enough to cause the pendulums to shift on the knife-edges. This degree of stability can be obtained on surface craft only in protected waters or on very calm days. Therefore, Dr. Meinesz mounted his instrument in a. submarine so that he could submerge below the disturbed surface waters and get the desired stability in nearly any kind of weather by simply diving to greater depths. Most of the gravity-at-sea work has been done with a Meinesz instrument and a very large number of the observations have been made by Dr. Meinesz himself. He has occupied nearly 1000 sea stations and probably has traveled as many miles by

Jan 1, 1938

By AIME AIME

I N JUNE, 1918, at a meeting of the American Society of Mechanical Engineers in Worcester, Mass;, a resolution was adopted for a committee to investigate the aims and organization of that society. This was followed subsequently by similar independent action on the part of the Society of Civil Engineers. The other two Founder Societies were approached and requested to appoint similar committees, the four committees to combine as a .Joint Development Committee, later called the Joint Conference Committee, to investigate what might be done in the way of coordinating those activities of the Founder Societies which ape of common interest, and which were then being pursued separately. The Joint Conference committee worked diligently -for almost. two years and. brought forth a tentative as outlined in its report which was published in full in MINING AND. METALLURGY, December, 1919. It recommended the formation of a nation-wide organization to be composed of representatives' of all of -the engineering societies, local, state, regional, or national, the object to be to further the interest of the public through the use of technical knowledge and engineering experience, and to consider and act upon matters common to the engineering and allied technical professions. Whereas the technical societies have large fields of endeavor in welfare work, and their prime. efforts are 'still in technical lines, this new organization was to be devoted entirely to service, looking to the welfare of the nation and the engineering profession, and to service for the public in local and state affairs.

Jan 1, 1920

By H. E. Nold

THIS paper is an effort to explain in a simple manner the fundamental principles involved in examining a clay deposit for both quantity and quality and in operating a clay mine, either open-pit or underground, so that the best quality of finished material can be made from the raw material available. The writer is aware that what is recommended in this paper is everyday practice in many refractories plants and in some other heavy-clay products plants, but observations made while visiting practically every clay mine in Ohio have convinced him that the practices herein discussed are not as widely used as their importance warrants. It is true that the problem of mining for quality is more acute in refractories plants than in most heavy-clay products plants, yet some of the latter are finding it profitable to pay more than ordinary attention to the selection and blending of their raw materials. It is hoped that this short paper may prove helpful to some who are now finding it difficult to produce a uniform product of as high quality as their clay deposit seems to warrant. The coordination of the work of the clay mine or pit with the manufacturing plant, to the end that the best product possible be made from the raw material available, presupposes a rather intimate knowledge of the clay deposit. The knowledge must include not only information of the amount of clay-available but also rather detailed information about both vertical and horizontal variations in quality of the clay. This information should cover three things: quality, quantity, and location.

Jan 1, 1929

By R. Stefanko, Y. J. Wang, H. R. Hardy, R. Y. Kim

Since 1964, the Dept. of Mining at The Pennsylvania State University has been carrying out extensive studies associated with the phenomena of microseismic activity and inelastic behavior in geologic materials. Briefly, the program to date has involved the following stages 1) Study of the microseismic noise and energy rates for selected geologic materials under incremental, uniaxial tension.1,2 2) Investigation of the frequency spectra of microseismic activity of selected geologic materials under incremental, uniaxial tension.3,4 3) Investigation of the time-dependent inelastic deformation of geologic materials and the analysis of such deformation in terms of mechanical models.5, 6 4) Simultaneous study of microseismic activity and time-dependent inelastic deformation in geologic materials under incremental, uniaxial compression.7,8 Details of the research involved in stage 4 of the program constitute the subject of this chapter. It should be noted that the majority of the experimental data quoted in this chapter forms part of a thesis to be presented by one of the authors (Kim) in partial fulfillment of the requirements for the Ph.D. degree in mining engineering at The Pennsylvania State University. During the last two or three years, a number of important papers have been published which deal primarily with the fundamental structure and mechanical behavior of geologic materials. Recent papers 9,10 have provided research workers in the rock mechanics field with a meaningful overall picture of rock as a structural material. The concept that many

Jan 1, 1970

By John A. THOMPSON, Pazcl D. Torrey, Frank Breayster

DISCOVERY of natural gas in the Dundee field of New York in February, 1930, and the subsequent discovery in Tioga in September of that year, focused the attention of the natural-gas industry on the enormous possibilities of production and distribution in - the most populous area of the United States-New York and New England. Prior to 1926 the natural-gas industry in New York State had settled into a definite and limited policy, with the distributing companies controlling the output from its discovery to the ultimate consumer. Production amounted to between G and 7 thousand mil- lion cubic feet a year, with another 10,000 million feet imported from Pennsylvania for distribution in New York State. This gas was primarily from the Medina sand stone in. the western part of the state.

Jan 1, 1932

By C. E. LAWAL

WITH the object of adapting high-school vocational courses to the industrial needs of the community, a few high-school officials in West -Virginia working with the School of Mines of the State university decided to try an innovation this year. The purpose of this experiment was to teach coal mining in two high schools situated in mining communities. We thought that if a course in coal mining would be included in the list of optional courses offered in the high school, it might interest some of the boys, and if the course were properly taught it would undoubtedly be of inestimable value to those boys who later decided to take up mining work as their vocation. This coal-mining course was started last September in the Berwind and Gary high schools in West Virginia. The high-school officials in their conferences with' us decided that we should work up the outline of this course and they would assign the science teachers of the schools as instructors, with ,the understanding that we would help 'these instructors with this work. We consented to all this and submitted -an outline to the school officials which they are following this year.

Jan 1, 1929

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p' which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß' was determined. X-ray diffraction studies indicate that 4' has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner' neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0' + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß'/ß' + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B' phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.' Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,' potentiometric3 and scaled flow models' were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy's law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.'5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By D. Turnbull, J. H. Hollomon, J. C. Fisher

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,&apos; in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but &apos;grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil&apos;s classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965

By Rodney P. Smith

The diffusivity of carbon (0.1 wt pct C) in Fe-Nz alloys (0 to 100 pct Ni) has been determined for the temperature range 860° to 1100°C. As a function of nickel content, the diffusivity has a maximum near 60 pct Ni (the maximum diffusivity being about 1.3 times that in the absence of nickel); the activation energy has a maximum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The difference between the minimum activation energy and that in iron is about 3000 cal pev g-atom; Do has a minimum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The results cannot be rationalized by an approximate thermodynamic treatment. THE diffusivity of carbon has been determined in a number of iron alloys over a limited concentration range. It seemed desirable to investigate a system which allows an extended range of alloy composition within a single-phase region. The Fe-Ni system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are fee in a convenient temperature range.&apos; The carbon diffusivity was determined by a decar-burization method. The experimental procedure was identical with that used to determine the diffusivity of carbon in y Fe-Co alloys.2 The experimental data are given in Table I. A small correction (order of a few percent) has been made to the measured carbon loss to correct for the carbon lost from the ends of the cylinders.&apos; Since the diffusivity of carbon varies with carbon content the measured diffusivity is an average value for a carbon content between zero (surface) and that at the center of the sample at the end of the decarburization periods. In making the correction in D to 0.1 wt pct C it is assumed that the measured D corresponds to the arithmetical mean of the carbon content at the surface and at the center of the sample at the end of the decarburization period.3 Since this correction is small (<4 pct in D) and since for our decarburization times the changes in carbon content at the center of the sample was small the mean carbon content could have been taken as half the initial value. It is further assumed that the change in D with carbon content for the alloys is the same as that for the diffusion of carbon in iron. From the data of Wells, Batz, and Mehl4 and of smith5 the correction of D from the mean carbon content to 0.1 wt pct C is 0.3 (0.1 - mean wt pct C). The results for iron are given in Ref. 2. Within the experimental error log Do.l%C for each alloy is a linear function of 1/T; the constants for the equation determined by the method of least squares are given in Table I. The deviations of the experimental points from the least-squares line are of the order of 2 pct in D. A comparison of our results for the diffusivity of carbon in nickel with those of other investigations is shown in Fig. 1. The lower curve in Fig. 1 is a linear extrapolation of values calculated* from the equation of Diamond6 for the relaxation time (temperature range 100° to 500°C). The results indicate a small increase in the activation energy over the temperature range 100° to 1400°C; however, it is difficult to say whether the change in Q is real or experimental error. Certainly the change in Q is less than the variation of 5 kcal per g-atom in the diffusivity of carbon in a iron.6 The experimental data for all the alloys are plotted in Fig. 2. As a function of nickel content the diffusivity has a maximum near 60 wt pct Ni at all temperatures investigated and possibly a minimum between 80 and 90 wt pct Ni for temperatures below 1000°C. The activation energy, Q, and log Do are plotted as a function of the nickel content in Fig. 3. Due to the limited temperature range of our experiments neither Q nor Do can be determined precisely; the activation energies appear to be consistent to ±0.3 kcal per g-atom; however the deviation from the absolute values may be considerably larger, see Table II. The Do values probably have little significance. The solid line for Do in Fig. 3 represents the values required to reproduce the experimental values for D when Q has values represented by the upper solid line The diffusivity of carbon may be expressed in terms of the mobility B22, the activity coefficient r2,

Jan 1, 1967

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.&apos;-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young&apos;s equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young&apos;s equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young&apos;s equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of&apos; analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,&apos; the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS&apos; A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto&apos; proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer&apos;s analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

By ED. E. Furman, R. H. Atkinson

HITHERTO the practical creep testing of precious metals has received little or no attention. The only previous creep tests of precious metals have been made with wires under conditions such as to yield much more rapid rates of creep than in engineering tests.&apos;, &apos; Up to the present time the value of creep bars of adequate size, in the absence of real need for engineering data, has deterred investigators. However, the increasing use of platinum at high temperatures has demonstrated the need for reliable creep data for the guidance of engineers, especially those engaged in designing certain specialized chemical plant equipment. In order to supply this need, creep tests were conducted at 1382°F (750°C) on 0.290 in. diam specimens of platinum, 90 pct Pt, 10 pct Rh and palladium. The platinum was high purity, nominally 99.95 pct Pt. The 90 pct Pt, 10 pct Rh was of the same high quality as is used for making gauzes for the catalytic oxidation of ammonia. The palladium was also of high purity; two batches of palladium bars were tested, one deoxidized with calcium boride and the other with aluminum. Spectrographic examination of the palladium confirmed its good quality; the only significant impurities apart from the residual deoxidizers were traces of silicon and lead. Procedure The creep bars, which were furnished by Baker and Co. to our specification, were 6 ¾ in. in overall length with a 4½ in. (4 in. gage length) reduced section 0.290 in. in diam and had the ends threaded (?-NC16). It may be of interest that the bars were valued at up to $600 each. The specimens were supplied in a 50 pct cold-worked condition to facilitate attachment of the creep extensometer, which was of the push rod type. Because of the softness of the platinum and palladium, the extensometer rings were secured to the test section by means of circular knife edges instead of the usual pointed set screws. The extensometer rods extended through the bottom of the furnace and readings were taken with a 0.0001 in. "Last Word" dial gage fastened to the rods for the duration of the test. The bars were directly loaded by hanging weights from the lower specimen grip. All tests were conducted at 1382°F ± 2°F, and an effort was made to maintain the temperature gradient over the test section within 2°F. The ends of the furnace tube were packed with asbestos wool, which allowed a very slow circulation of air through the tube. Annealing was accomplished in the creep furnace before the load was applied. The platinum and palladium specimens were annealed at the test tem- perature for about 17 and 24 hr respectively; in the case of the rhodioplatinum it was found expedient to anneal for 1 hr at 1922°F (1050°C). Pilot samples cut from the same stock as the bars were used to check annealing procedures. Pertinent measurements of grain size and hardness were recorded. Results and Discussion The creep data obtained are given in Table I and the creep curves are plotted in Figs. 1, 2, and 3. Two platinum specimens, tested under a stress of 250 psi, had almost identical creep rates at 2000 hr, namely 0.000008 and 0.000009 pct per hr. A third platinum specimen, stressed at 400 psi, had a creep rate at 2000 hr of 0.000026 pct per hr; the reason for a rather sharp decrease in creep rate during the period from 1200 to 1600 hr is unknown. As it was thought that 90 pct Pt, 10 pct Rh would have a lower creep rate than platinum, the first sample was tested at 400 psi; however, the creep rate was approximately 50 pct greater. Microex-amination revealed that differences in grain size might be responsible for the unexpected result, as annealing at 1382°F developed an average grain diameter of 0.0021 in. in the rhodioplatinum specimen compared with 0.004 in. in the platinum bar. Annealing the alloy for 1 hr at 1922°F (1050°C) increased the average grain diameter to 0.0032 in. and materially improved the creep resistance, making it much better than platinum. A second specimen annealed at 1922°F (1050°C) and tested under a stress of 550 psi had a creep rate of 0.000022 pct per hr at 2000 hr, which was still substantially lower than that shown by the specimen annealed at 1382°F (750°C) and stressed at only 400 psi. In contrast to the creep behavior of the platinum and rhodioplatinum specimens, the palladium bars, whether deoxidized with calcium boride or aluminum, were characterized by high first stages of creep. However, after about 1200 hr of test, the creep

Jan 1, 1952