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By M. M. Singh, H. L. Hartman

This paper reports on the results of a fundamental investigation of the behavior of rock under impact of a chisel-shaped bit. Drop-tester studies were conducted with strain gauges attached to the rock and striking bit-edge. It was established that rock behaves viscoelastically. Little correlation was found to exist between the strain waveforms detected on the rock surface and in the bit; thus, strain-time curves obtained with transducers mounted on the bit cannot be used to explain the sequence of events in rock breakage. It is estimated that nearly 1 per cent of the total energy of the blow is expended in permanent deformation of the rock. The strain- energy distribution on a rock surface as a result of chisel impact, which follows a simple law, is presented graphically. Experiments also were conducted with gauges embedded in the rock vertically below the line of impact and at an angle of approximately 45' to the vertical. No essential difference was observed in the type of wave obtained with embedded gauges and with gauges on the surface, as may have been anticipated from theory. INTRODUCTION Through the ages great strides have been taken towards improvement of the various techniques applied in the breakage of rock. Indeed, numerous applications of the rock-failure process are an integral part of present-day industry, including oil well drilling. Yet, astonishingly, little is known regarding the behavior of rock under dynamic loading or the mechanism of rock failure. The value of impact loading studies from the point of view of drilling is evident, however, and requires little elaboration because impact of a chisel edge on rock forms the basic action constituting most common methods of drilling. RELATED STUDIES Impact studies of communition and fragmentation conducted by Fahrenwald, et a1,8 Poncelet,l7 Axelson, et a1,2 Piret,16 Hartman and pfleider,ll Charles and deBruyn,5 and others have been of considerable help in understanding rock-breakage phenomena. Further insight into the basic action of drilling and penetration has been obtained by the work of Irving,13 Cherkasov and Shlyapin,6 BOrcherdt,3 Shepherd,19 Shreiner and Pavlova,20 Drilling Research Inc.7 Hartman,10 Appl and Gatley1 and several other investigators. However, knowledge concerning the stresses and strains induced in the rock and bit during impact remains scant. Recent photoelastic studies by Tandanand and Hartman (1961. 1962)22, 23 have shed light on stress distributions and Fracturing produced in plastics by chisel-shaped bits. In the field of transient strain Pulses and their role in rock drilling, the only extensive work has been performed by Drilling Research Inc. (DRI). They attached strain gauges to the shank of a bit and conducted drop-tester studies, using a die-shaped bit to obtain force-time diagrams. Their work led to the conclusion that, for a given rock type, the first peak of force occurs at a fixed level regardless of the total energy in the system, provided it exceeds a certain minimum threshold level. Further, on this basis an explanation was offered for the sequence of events in crater formation as the result of a single blow on rock. PURPOSE OF PRESENT STUDY The investigations reported in this paper were conducted in a manner similar to the DRI approach, but with the objective of determining the strain distribution in the rock around the area of bit impact and, to a limited extent, the strain in the chisel-shaped bit itself. It was expected that a knowledge of the disposition of these strains, along with the rate of attenuation of strain energy in the rock

By Henry Wurtz

HERACLITUS, a sage of antiquity, called the dark philosopher, who refused a throne, preferring a hermit's cell, propounded, twenty-four centuries since, the maxim : [ ] War (or strife) engenders all things. This, though probably intended by Heraclitus to apply especially to the internal forces of nature, is often said, with equal reason, of the affairs of men. Controversial strife, whether fortunately or unfortunately, is a crucible through which all new discoveries in science, and all technical applications of science must pass-a test which they must all endure before they can become so vitalized as to germinate, so to speak, take root in the human mind, grow tip, and overspread the earth. The greater the number and the power of the elements arrayed against such a growth, and of the influences hostile thereto, the greater should be the inherent vitality of the germ, the more strenuous, skilful, and persistent its cultivators and upholders. During the decade last past we have had, in spite of the severe stringency of the times, an active growth of this kind in progress, whose prospective importance it would now be difficult to overrate. This is the movement which has for its motive the idea that, generally speaking, fuel should be gaseous in form, and which has for its goal the introduction into general public use of gaseous products, made by cheap and rapid processes and on a gigantic scale, distributed throughout our cities and towns in distribution-systems which shall be proportionately gigantic, and sold at prices which will bring such fuel within the means of the poorest householders. Personally, for ten years past, the writer has never failed, on occasions public or private, to urge his belief that the realization of this idea, deemed by him a certainty of the future, will bring about

Jan 1, 1880

By Paul M. Tyler

DOES mining pay? Inasmuch as the whining of minerals from Nature is one of the world's principal sources of new wealth, this question is of general economic interest but it is obviously of even more vital concern to investors and those engaged in mining. In a previous article on "Wage Costs in the Mineral Industries,' published in the November issue, I attempted to show that wages paid workers on the job accounted for, roughly, 50 per cent of the mine dollar. Salaries normally range over 5 per cent - lower for large metal mines but higher in stone quarries and minor nonmetallic min. in, industries. Purchases of supplies, materials. fuel, and power generally aggregate within the range of 15 to 25 per cent of total receipts, with the average well under 20 per cent. The total of all such specified expenditures which may he loosely described as

Jan 1, 1934

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,&apos; and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,&apos; the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,&apos; who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder&apos;s equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET&apos;s and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.&apos; More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET&apos;s. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET&apos;s with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By R. L. Dietrich

Magnesium alloy sheet has less ability to accept bending at room temperature than most of the heavier metals. In work designed to improve the bend properties, the preferred orientation of the sheet is of major importance as it is in all studies of the properties of wrought magnesium products. When rolled into sheet, all of the common magnesium alloys form an orientation texture having the basal (002) planes approaching parallel to the surface of the sheet. This texture is only slightly affected by annealing. Magnesium single crystals are highly anisotropic, and, as might be expected, so are magnesium alloy wrought products in which a strong preferred orientation is developed. It is therefore not surprising that bend properties are affected by orientation. Ansel and Betterton1 reported that the orientation of AZ3lXt sheet varies from surface to center and that bend properties are improved by etching away the sharply oriented material at the surface of the sheet to reach the more broadly oriented structure below. This paper covers a study of that orientation, either during the rolling process or by treatment of the finished sheet, in an effort to improve the bend properties and toughness of sheet. Literature The orientation texture of magnesium and magnesium alloy sheet has been studied extensively. Early determinations2 showed that pure magnesium sheet has a preferred orientation in which the basal planes are parallel to the sheet surface within very narrow limits. J. C. hIcDonald3 and J. D. Hanawalt4 reported that sheet containing a small amount of calcium develops a "double" texture, that is, the majority of the basal planes are a few degrees from parallel to the surface and there is a noticeable vacancy at the parallel position. Bakarian5 made careful quantitative pole figures of both pure magnesium sheet and MI alloy SEPTEMBER 1949 sheet which show these features. In all of these studies, however, the orientation was determined by transmission methods in which the resulting pattern is an average through the thickness of the sheet. The tendency of wrought metal to exhibit a different orientation at the surface from that in the center has been reported by many investigators. G. von Vargha and G. Wasserman6 found that with copper, aluminum, iron, and brass the textures of rolled compared to drawn wires were the same at the center but differed markedly at the surface. It was also reported by investigators7 that the orientation of rolled aluminum varies from surface to center. Har-greaves8 found that the surface texture of AM503 (magnesium alloy similar to MI) sheet was different from the center texture. It is reported by Edmunds and Fuller9 that zinc alloy sheet sometimes had a thin layer at the surface with a strong orientation of the basal planes parallel to the surface, which, if present, impaired the bend properties of the sheet. Part1 Surface Orientation ofMag- nesium Alloy Sheet and the Effect on Properties Attempts to correlate the bend properties of magnesium alloy sheet with tension ductility over short gauge lengths proved unsuccessful and the subsequent investigation showed that nonuniformity in orientation is a con- tributing factor as the properties of the surface material have a much more important effect in bending than in tension. A program to study the relationship between surface orientation at the surface and bend properties was then undertaken. First, the effect of etching away the surface of sheet on the bend properties and the orientations at the various depths were studied. Sheet samples of M1, AZ31X, and AZ61X were etched in dilute nitric acid to remove the surface material for various depths to 0.015 in. As may be seen in Table 1, the minimum bend radius improved considerably as the surface layers were etched away but it was necessary to etch the sheet quite deeply, much more so than was found necessary by Edmunds and Fuller9 on zinc sheet. It is also apparent that the amount of etching required is a function of the sheet thickness. In all of this work, radii were measured as R/t, the radius divided by the sheet thickness, in order to eliminate the effect of the reduction in sheet thickness produced by the etching. To determine the orientation texture of the sheet, X ray reflection patterns were taken using copper radiation with the bearn striking the specimen at an angle of 17&apos; to the surface, which is the Bragg angle for the (002) planes of magnesium. Two exposures were made of each specimen, one with the beam perpendicular to the rolling direction and the other with the beam parallel to the rolling direction. The symmetry of the preferred orientation in magnesium sheet is such that these two photographs gave an approximation of the pole figure sufficiently accurate for qualitative work and it was not thought worthwhile to make complete pole figures. These X ray patterns show that the orientation has a much narrower spread at the original surface of the sheet than below the surface. The narrow spread is found in sheet having the majority of the basal planes (002) parallel to the surface, and since this is an unfavorable position for slip, it is

Jan 1, 1950

By K. P. Mukherjee, K. P. Gupta, J. Bandyopadhyaya

Even though a lot of work has been done in the past to establish phase equilibrium in the Cu-Si system a re cent investigation casts some doubt about the existence and crystal structure of some of the phases that form in the composition range of 15 to 25 at. pct Si in Cu. The present investigation was carried out using high temperature X-ray diffraction technique along with other standard techniques to study the phases in this composition range. The high temperature 6 phase appears to be tetragonal with parameters a,, = 8.815A, c, = 7.903A, and co/ao = 0.896. The reported bcc E phase exists at room temperature and at least up to 780°C and appears to undergo a transformation near 600°C. The phase appears to be cubic but not of the bcc type. The ? phase appears to undergo a transformation, as has been indicated by earlier investigators, and the low temperature form of .? phase is tetragonal with parameters a, = 7.267A, co = 7.8924, and co/ao = 1.086. THE Cu-Si binary system has been investigated by several investigators1" and several intermediate phases,?,e,?&apos; at lower temperatures and ?,ß,0,e, and ? at higher temperatures, were observed between terminal solid solutions of copper and silicon. Even though the existence of the e phase and the transformation in the ? phase were reported in many early works, in a recent study of this system Nowotny and Bittner6 doubted the existence of the e phase and phase at 550°C. Among the high temperature phases, the 6 phase was reported to have a complex cubic structure with parameter a, = 8.805A.7 Nowotny and Bittner, however, suggested that the structure of the 6 phase might be of CsCl type. In order to check these contradictory reports the present study was taken up to investigate the Cu-Si binary system in the composition range of 17 to 25 at. pct Si. EXPERIMENTAL PROCEDURE Weighed amounts of copper (99.99 pct) and silicon (99.9 pct) were induction melted in recrystallized alumina crucibles under argon gas atmosphere. The alloys containing 17, 18, 20, 21, 21.2, 22, and 24 at. pct Si were annealed in evacuated and sealed quartz capsules at 700°C for 3 days and subsequently water quenched. Other than this annealing, the 21.2 at. pct Si and 24 at. pct Si alloys were annealed at 550°C for 10 days, the 17 at. pct Si alloy was annealed at 750°C for 3 days, and the 22 and 24 at. pct Si alloys were annealed at 780°C for 2 days. All annealing temperatures were controlled to within *l°C. Alloys after quenching were subjected to metallographic and X-ray diffraction investigation. A solution containing 5 g FeC13 + 10 cc HCl + 120 cc H2O diluted with six times its volume with water was used as etching reagent. A 114.6 mm diam Debye Scherrer camera was used for obtaining diffraction patterns. The 17, 21.2, and 24 at. pct Si alloys were subjected to high temperature diffractometry using a Tempress Research High temperature attachment and a GEXRD VI diffractometer. For the 6 phase (17 at. pct Si alloy) powder specimen from a 750°C annealed alloy was reheated to 750°C in the high temperature attachment for 1½ hr before taking a diffraction trace. A 550°C annealed and slowly cooled phase (24 at. pct Si) alloy was first reheated to 550°C. a diffraction trace was made after annealing it for 2 hr, and subsequently it was heated to 716OC and kept at this temperature for 2 hr before taking a diffraction trace. For the e phase (21.2 at. pct Si alloy) a 550°C annealed and slowly cooled specimen was heated first to 425°C and annealed at this temperature for 2 hr before taking a diffraction trace. Subsequently, the specimen temperature was raised to 495", 540°, 603", 635", 682", 720°, and 748°C and homogenized at each temperature for 1 hr before taking diffraction traces. The powder specimen temperature was controlled to within +2oC at each temperature and argon gas, purified by passing it at slow rate through a fused CaC12 column, hot (800°C) copper and titanium chips and finally through a P2O5 column, was used to prevent oxidation of the powder. For all X-ray work copper-radiations at 25 kv, 15 ma (for Debye Scherrer technique), and 40 kv, 20 ma (for diffractometer tech-nique) were used. RESULTS AND DISCUSSION At 700°C the alloys containing 17 to 21 at. pct Si showed two phases while the 21.2 at. pct Si alloy was found to be single phase. The X-ray diffraction patterns of the two-phase alloys were consistent with the phase (ßP-Mn type structure) and the phase (21.2 at. pct Si) patterns. The diffraction patterns of the 17 at. pct Si alloy quenched from 750" and 700°C were identical. According to the accepted Cu-Si phase dia-gram4,5,10 the 17 at. pct Si alloy at 750°C should be in the (k + 6) two-phase region and very close to the -phase boundary. The identical patterns possibly resulted from the decomposition of the 6 phase on

Jan 1, 1970

By E. Gybbon Spilsbury

(Pittsburg meeting, March, 1910.) THE recovery of gold and silver from their ores by means of the cyanide process has been so successful in the last few years that any radical improvement would seem impossible; yet the appliance to which I wish to call attention in this paper is really a radical departure from the methods now in general use. The most modern and approved of these, known as the all-sliming method, depends for its success on the grinding of the. ore so fine that practically 90 per cent. of it will pass through a 200-mesh screen. The slimes thus produced are then agitated and aerated in tanks of various types. The main object of this treatment is to insure such a thorough admixture of the pulp and solution that every particle of the ore is surrounded by a volume of solution sufficient to insure the dissolving of the whole of the gold- and silver-content. In addition, in order to expedite the action of the cyanide, and to oxidize such elements as would, if left in their active state, become cyanicides, air is blown in under pressure. In the Pachuca tank, this air is the active and sole means of agitation. The chief objections to all the methods off agitation used heretofore are the expense of operating and maintaining the mechanical devices for keeping the pulp in suspension, and the length of time required to obtain a fairly complete extraction. of the values. These objections are inherent to any method of agitation effecting a circulation of the pulp and the solution together, by giving the whole mass a circular movement, as in the low-tank system, or a vertical circulation, as in the Pachuca-tank system. In both methods, the particles of ore are kept traveling in the same direction as the solution, and with very little difference of speed; so that, while the whole mass is in

May 1, 1910

By Charles S. Barrett

THE experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal&apos;s capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientations resulting from recrystallization and is being extended to other metals and other types of deformation. PREVIOUS WORK The previous experiments are few and have given confusing results. Ono1 compressed a polycrystalline alpha-iron specimen between two flat plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a. double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1938

By B. Tani, K. Anderson, I. Johnson, R. Schablaske

INVESTIGATION of the various rare earth-cadmium binary systems discloses the existence of a compound corresponding to the composition MCd6 in all systems save the La-Cd system. Lattice constants for all of the MCde compounds, except LaCd6 which apparently does not form, and PmCd6 whose synthesis was not attempted, are also recorded herein. Iandelli and Ferro 1 report the existence of the compound CeCd6. No additional information, structural details, and so forth are given. Elliott and Lemons2,3&apos; have measured the vapor pressure of cadmium over CeCd6 and have calculated the activity of cadmium in solid CeCd6. These authors find that CeCd6 exists over a composition range from 5.967 to 6.098 (Cd:Ce ratio) at 584oC, and from 5.971 to 6.118 at 639°C. The following is an excerpt from the paper by Elliott and Lemons: 2 "Recently Mr. F. H. Ellinger of this laboratory has indexed an X-ray diffraction powder pattern of CeCd6.00 which we had prepared by gas phase reaction. The compound has a primitive cubic unit cell with a = 15.783 + 0.001A Based on the volume of the cubes surrounding an elemental cerium or an elemental cadmium atom, Mr. Ellinger finds room for 24.10 CeCd6 formula units in the CeCd6 unit cell; similar calculations based on CeCd2 and CeCd11 yield 24.18 formula units per unit cell. The presence of 24 CeCd6 units per unit cell seems probable with an X-ray density of 8.255 grams per cubic centimeter. The most one can say about in-terstitial~ is that there appears to be room in the crystal even at room temperature." Measurements of the solubility of the rare earths in liquid cadmium4 led to the discovery of GdCd6,

Jan 1, 1964

By William H. Spice

Drilling activities in South Central Texas for the year 1945 continued the steady increase over the past two years, while new fields discovered for the year included four new gas fields and one field extension. In the 30 counties included in this area, which comprises district No. 1, Oil and Gas Division, Railroad Commission of Texas, 141 exploratory wells were completed, compared with 61 drilled in 1944 and 29 drilled in 1943. Of these 141 tests, 55 were field well and 86 were wildcats; 38 were completed as oil wells, S as gas and gas-distillate producers, and 95 were abandoned as dry. Atascosa and McMullen Counties were the most active in the district, accounting for 73 of the wells drilled.

Jan 1, 1946

By Robert F. Mehl

EXTENSION of physical and chemical methods of research in the study of metallic behavior continues rapidly, particularly in the correlation of behavior with crystal structure, and in the analysis of elastic and plastic properties. The growth of the science of metals during 1933 calls for special comment; the need for special reviews and for textbooks and monographs is now acute, as might he supposed from the number of references appended to this article, a list which is much abbreviated.

Jan 1, 1934

By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y&apos; phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS&apos; showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939