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By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.' ' Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.'" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By W. A. Klikoff, I. Fatt

The concept of fractional wet wattability is examined. Fractional water wettability of a reservoir rock is defined as the fraction of the internal surface urea that is in contact with water. Capillary pressure and relalive permeability of unconsolidated sand are shown to be functions of fractional wettability. INTRODUCTION The petroleum industry has long recognized that wettability of reservoir rock has an important effect on multiphase flow of oil, water and gas through reservoirs. As early as 1928 the American Petroleum Institute sponsored a study of wettability as part of API Project 27 at the U. of Michigan.' Despite 30 years of research, there is still little exact knowledge of the wettability of reservoir rocks. There are two parts to the wettability problem. After agreeing to a uniform nomenclature in regard to wettability,' the first question to be answered is, "What is the in situ wettability of a given reservoir rock?" If this can he answered the next question is, "What part does wettability play in determining the characteristics of multiphase fluid flow through the rock?" This paper represents an oblique attack on the problem of wettability. No attempt is made here to answer the basic question of wettability in situ. instead the consequences of the concept of fractional wettability are examined. Multiphase flow in sandpacks is shown to he highly influenced by fractional wettability. Jennings' has given 3 definition of wettability and the other terms used in discussing wettability. These terms must be applied to the physical situation existing In reservoir rock. A survey of the pertinent literature from 1928 to 1956 indicates that the concept of a contact angle was applied to reservoir rock in the same way it would be applied to a flat, homogeneous surface. Attempts were made to state quantitatively the wettability of a reservoir rock in terms of a contact angle which was presumably constant at all points on the very rough and heterogeneous interior surface of a porous rock. Calhoun, et al,3-6 prepared synthetic consolidated and un-consolidated porous media in which they claimed there was a known uniform contact angle. They then showed the effects on the capillary pressure and relative permeability characteristics of varying this angle. The API Project 47 at the U. of Texas' and others' have made extensive studies of an indirect approach to the contact angle through the use of heat of wetting data. Even if successful. however, this approach also states the wettability of porous rock in terms of a contact angle which is uniform over the entirc surface. If the angle varies from one part to another on the internal surface, there is no way of determining from the measurements the area distribution of contact angles. In 1956 Brown and Fatt5 suggested that the concept of a contact angle, as applied to reservoir rock, be abandoned. This suggestion was made because it is known that the internal surface of most reservoir rocks is composed of many different minerals, cach with a different surface chemistry and a different capacity to adsorh surface active materials from reservoir fluids. Furthermore, the operation of a contact angle in determining the form of a fluid-fluid interface is difficult to picture in the very complex geometry of a pore. Brown and Fatt proposed that the wettability of reservoir rock be stated in terms of the fractional internal surface area that is in contact with water or oil. All surfaces on which there is water are called water-wet; surfaces on which there is oil are called oil-wet. The fractional water wettability is then stated as a number which represents the fraction of the internal surface that is in contact with water. A symmetrical statement can be made for the fractional oil wettability. The concept of a fractional wettability as previously stated has in its favor the recognition of the heterogeneous mineral composition of most reservoir rocks. Another point in its favor is that fractional wettability can be measured quantitatively with relative ease. Hol-brook and Bernard10 se a simple dye adsorption test to obtain fractional wettability of reservoir rocks. Amott11 uses a combination of imbibition and displacement to arrive at a wettability index of reservoir rocks which seems related to fractional wettability in the range 0.25 to 0.75 fractional water wettability. Jennings" has shown the changes in relative permeability that take place when a porous material is changed from unity to zero fractional water wettability. He also shows that reservoir rocks in their natural state, but at room temperature and atmospheric pressure, have relative permeability characteristics which would indi-

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions'-' are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4'5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall's determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,' sulfur in iron, cobalt, and nickel; Cheng and ~lcock,' sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.' Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry's law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By T. H. Alden

Using alternating tension-compression straining, the hardening of magnesium oxide single crystals was studied up to large stresses and strains. At 0.25 pct plastic strain amplitude, the hardening curve is approximately linear with slope 25,000 psi from the shear yield stress, 7 to 8000 psi, to 35,000psi. Above this stress, the slope decreases. The strain hardening behavior of MgO is considered qualitatively similar to that of metal single crystals. The relatively high stress attainable by strain hardening is associated apparently with the high yield stress on the cross-slip system, (001) <110>. Cleavage fracture during testing is uncommon. It is argued that the centers of high internal stress at glide band intersections, at which cracks tend to nucleate, are dispersed by cyclic strain. Special features of the glide band structure produced by cyclic strain and revealed by dislocation etch pits, support this view. Strain hardened MgO has mechanical properties greatly superior to the as-received material: yield stress, greater than 100,000 psi; elongation to fracture about 1 pct. A material is said to strain harden if the yield stress increases with an increment of plastic strain. This definition is usually applied for straining done in one direction, but is also applicable when the strain direction is periodically reversed, Fig. 1. For certain metal single crystals, data are available which permit a comparison of the hardening behavior for cyclic straining and for tension straining.&apos;-4 With certain qualifications, these data show that the same processes of hardening are operative in each type of test.5 Despite this fact, the importance of the technique is not immediately evident, although tension-compression studies of the common metals appear to suggest some deficiencies in theories of strain hardening developed exclusively on the basis of tensile tests. However, a recent observation suggests that the cyclic straining method may be very useful for studying semibrittle crystals in which large plastic strains are not accessible in unidirectional testing. The observation is that zinc crystals, when strained in tension-compression at -52°C, do not fail by cleavage at low stress (-500 psi)6 as they do in tension, but harden to a limiting stress of more than 5000 psi over a total plastic strain of about 600 pct.2 An important characteristic of the behavior of zinc crystals is the high stress, relative to the yield stress, attainable by strain hardening. By comparison, the hardening of aluminum single crystals tested by an identical technique saturates at 1100 psi. This difference is best explained by the cross-slip hypothesis of dynamic recovery.7,8 In zinc, cross slip is difficult because of the high yield stress for glide on planes other than the basal plane in the < 1120 > zone. The present work was undertaken in order to test whether these methods and ideas are applicable to other materials. Magnesium oxide single crystals, in common with most crystals of the rock-salt structure, deform plastically but fail by cleavage after a small strain when tested in tension. It was hoped that larger strains would be attained using tension-compression. There is, in addition, evidence 8a which shows that slip on the probable cross system, (001) < 110>, is difficult in magnesium oxide; it may therefore be possible to attain high stresses by strain hardening. 1) EXPERIMENTAL PROCEDURE Experimental methods used in this study were based in part on techniques reported in papers of Stokes, Johnston, and Li.&apos; MgO blocks, purchased from Norton Co., were used without further annealing. Specimens were cleaved to dimensions approximately 0.125 in. sq and 1 in. in length. The gage section, formed by chemical polishing, was sprinkled with 280 mesh silicon carbide particles in order to introduce fresh dislocations. The crystals were then cemented into cylindrical aluminum adapters and clamped in an Instron testing machine. One of two alternating straining programs was used. In the first, total cross-head travel was established and increased in steps after various numbers of cycles. In the second, a capacitance gage was used to directly measure the elongation of the specimen and the crosshead was controlled so as to keep the plastic strain amplitude constant. The straining was always symmetrical with respect to the initial, zero strain condition. While both procedures produce strain hardening, only the latter permits a measure of the total plastic strain so that hardening curves may be drawn. Constant plastic strain amplitude tests were done

Jan 1, 1963

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)&apos; molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),&apos; which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.&apos; This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.&apos; These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar&apos;s cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.&apos; Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2&apos;3&apos;4&apos;5&apos;6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made&apos; and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."&apos; The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.&apos; Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2&apos;3&apos;4&apos;5&apos;6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made&apos; and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."&apos; The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel&apos;d and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

By L. T. Lloyd, H. H. Chiswik

The operative deformation elements in a-uranium single crystals under compression at room temperature have been determined as a function of the compression directions. The deformation mechanisms noted may be arranged with respect to their frequency of occurrence and ease of operation in the following order: 1 — (010)-[I001 slip, 2—{130} twinning, 3—{~172} twinning, and 4bunder special conditions of stress application, kinking, cross-slip, {.-176) twinning, and (011) slip. The composition planes of the (172) and (176) systems were found to be irrational. Cross-slip was shown to be associated with the major (010) slip system, coupled with localized interaction of slip on the (001) planes. The mechanism of kinking was found to be similar to that observed in other metals in that it occurred chiefly when the compression direction was, nearly parallel to the principal slip direction [loo] and was associated with a lattice rotation about an axis contained in the slip plane and normal to the slip direction: the [001] in the uranium lattice. The resolved critical shear stress for slip on the (010)-[100] system was found to be 0.34 kg per mm2 In a single test it was shown that under compression in suitable directions twinning on the (130) also occurs at 600°C. DEFORMATION mechanisms of large grained polycrystalline orthorhombic a-uranium have been studied by Cahn.1 A major slip system identified as the (010) with a probable [loo] slip direction and a minor slip system on the (110) planes were reported; the slip direction of the minor system was not determined. The twinning systems that were identified experimentally included the (130) and the irrational (172) composition planes; observations of other traces which were not as frequent and which did not lend themselves to positive experimental identification led Cahn to postulate on the basis of indirect evidence that twinning also occurred on (112) and (121) planes. In addition to the foregoing slip and twinning mechanisms, Cahn also observed kinking and cross-slip in conjunction with the major (010) system; the cooperative cross-slip plane was not identified. The availability of single crystals to the present authors has enabled them to check these results, particularly with reference to the doubtful mechanisms and the preference of operation of any one mechanism in relation to the direction of stress application. The tests were confined to compression only, primarily because of experimental limitations imposed by the size and shape of the available crystals. The tests were performed at room temperature except for one crystal compressed at 600°C. The compression directions were chosen to obtain a representative coverage of one quadrant of the stereo-graphic projection. To test the existence of some of the deformation elements that were reported by Cahn, but were not found in the present study, several additional crystals were compressed in specifically chosen directions considered most ideal for their operation. Experimental Techniques The single crystals were obtained by the grain coarsening technique described by Fisher? They grinding and polishing on rotating laps, with final surface preparation performed in a H3PO4-HNO3 electropolishing bath. A typical crystal readied for compression is shown in Fig. 1; their dimensions were rather small and depended upon the testing direction. Crystals isolated for compression in a direction close to the [010] axis, which lay roughly parallel to the longitudinal axis of the polycrystalline rod, were about 3 to 4 mm long and 5 mm2 in cross-section, while those prepared for compression in other directions were smaller. Most of the crystals were free from twin markings and showed no evidence of Laue asterism. Several crystals, however, contained twin traces prior to compression; these were identified prior to compression so as to clearly distinguish them from those initiated during deformation. The origin of the twin markings prior to deformation may be ascribed to two sources: thermal stresses and specimen handling during isolation and preparation. Two other types of imperfections in the crystals should be mentioned: inclusions, which were probably oxides or carbides. and three of the crystals contained a small number of spherical included grains (<0.01 mm diam), which were remnants of unabsorbed grains from the coarsening treatment. The volume represented by these imperfections was small, and their presence presented no difficulties in the interpretation of the macrodeformation processes during subsequent compression. Two compression fixtures were employed: crystals A, B, C, E, and G were compressed in a hand-operated screw-driven jig whose compression platens were designed to minimize axial rotation;

Jan 1, 1956

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By Colin Baker, G. C. Smith

Investigation of the initiation and propagation of ductile failure in OFHC copper was undertaken to determine the role of nonmetallic inclusions. The effect of inclusion initiated voids on the formation of the internal cavity and the final shear separation was studied by metallographic eranzination of strained test pieces. A strain anneal technique was used to enlarge the voids under uniaxial stress conditions to elinzinate triaxial stress effects. Measurements of void size us stress and strain were made to show the point at which void im&apos;tiation begins and becomes an important factor in the deformation process. The work of separation of copper-cuprous oxide was determined to attempt to correlate the breakdown of the matrix inclusion interface with void initiation and propagation. The zloid shape and position relative to the tensile axis suggested an interface breakdown mechanisnz of initiation. Evidence is presented that shows a basic similarity between the central cavity propagation and the 45-deg shear portions of the failure. DUCTILE fracture has been studied by a number of workers1-lo and attention drawn to the importance of hard second phase particles in the initiation of the failure. Holes formed at the matrix-particle interface can elongate by plastic deformation and then subsequently expand sideways to link up and produce a major crack. This is usually observed first in the center of the macroscopically necked region of a test-piece where the hydrostatic stresses are at a maximum. As the crack spreads sideways towards the free surface of the specimen, well defined shear zones develop from the crack tip and the final separation is along a direction at approximately 45 deg to the stress axis. This shear failure may also be associated with voids formed adjacent to second phase particles. In this way a cup and cone type fracture is produced. The stage at which separation takes place between particles and the surrounding matrix has not been clearly identified. In addition, although researchers have dealt with anisotropy of tensile behavior" as a result of material fabrication variables, not much is known about the microstructural features of aniso-tropic behavior. In the present work evidence on these points is presented in relation to the behavior of copper containing second phase particles of cuprous oxide. I. MATERIALS AND PROCEDURES EMPLOYED The material used was +-in. diam or 2-in. sq cold-drawn OFHC copper bar which contained 0.6 pct by volume of cuprous oxide inclusions. These ranged in COLIN BAKER, Junior Member AIME, formerly at -mnF of Metallurgy, University of Cambridge, Cambridge, England, is presently Research Scientist Reynolds Metals Co., Richrnand, Va. G. C. SMITH, Member AIME, is Senior Lecturer, Department of Metallurgy, University of Cambridge. Manuscript submitted June 20, 1967. IMD size from approximately 1 to 6 p in length and 1 to 4 p in width. The shape was generally slightly ovoid. Tensile tests were made on specimens having a gage length of 2.5 cm and diameter of 0.643 cm. Metallographic examination was carried out by sectioning deformed and fractured specimens; in addition fracture surfaces were examined optically and with a scanning electron microscope. Some measurements of the work of separation between copper and cuprous oxide were made, using a sessile drop technique which was a modification of that used by Kingery and umenick." The best metallographic results were obtained by using a vibratory polisher, which minimized smearing of the surface. 11. RESULTS A) Initial Experiments. Specimens from the +-in. diam rod were annealed for 2 hr at 650°C in uacuo, at which temperature complete recrystallization occurred without any change in the form of the inclusion. They were then fractured at temperatures from -190" to 600°C. Cup and cone fractures were obtained at all temperatures from -196" to 400°C. With increase in temperature there was, however, a continuous increase in the extent of the central transverse area and a corresponding decrease in the shear portion of the fracture. Above 400°C, the fractures became intergranular. Sections of specimens tested below 400°C revealed extensive small voids which were always associated with inclusions. However, the voids only reached dimensions greater than the inclusion size in the region of the macroscopic neck, where they were many times longer. Lateral expansion was found only near the fracture surface of the test pieces. As observed by Puttick, the voids were either (a) triangular holes initiated in the direction of the tensile axis and elon-

Jan 1, 1969

By Hollis L. Caswell

The present status of integrated circuits utilizing. superconductive switching. elements is reviewed with special attention given to fabrication techniques, methods for interconnecting completed circuits, and refrigeration requirements. Cryoelectronics has been largely an "inte- grated-circuit" technology since its conception because the switching speed of superconductive devices is attractive only when these devices are fabricated with thin-film techniques. It is true that cryotron circuits can be constructed from wires of appropriate materials (as indeed was done by Dudley Buck 1 in his early investigations) but these circuits will switch in times characteristic of milliseconds whereas similar circuits fabricated by thin-film methods have potential switching times of nanoseconds. Furthermore, cryo-electronic devices such as the cryotron lend themselves readily to fabrication by thin-film techniques since these components may be made from polycrys-talline thin films and are relatively insensitive to the presence of impurities (as measured by semiconductor standards). Therefore, during the past decade considerable effort has been devoted to developing techniques for batch fabricating circuit arrays containing superconductive switching elements. Technology had developed to the point several years ago that fabrication of cryoelectronic arrays containing up to one hundred devices was rather straightforward. However, larger arrays containing between lo4 and 106 components which are required for commercial development of cryoelectronics still pose very severe yield problems. Thus in a sense cryoelectronics found itself in 1962 at the point semiconductor technology finds itself today; namely, individual devices and small groups of integrated devices could be fabricated with acceptable yield and the outlook for building larger integrated-circuit arrays was bright. Unfortunately, problems associated largely with yield have made fabrication of these larger arrays difficult. Unlike semiconductor technology, cryoelectronics had to solve the problems of large-scale integration before it could become economically attractive. This has proven to be a sizable burden to bear. Since several reviews exist on superconductivity,2 superconductive devices,3 and cryoelectronic technology, no attempt will be made in this paper to summarize these areas. Instead a few specific topics will be dealt with in more detail. First, a brief description is given of selected superconducting switching and storage devices with special attention to several metallurgical techniques which improve the performance of these devices. Second, techniques used to fabricate cryoelectronic devices are described with emphasis on problems affecting yield. Third, techniques for interconnecting a number of cryoelectronic planes are described. And last, refrigeration of cryoelectronic components is discussed briefly since the low operating temperature of superconductive devices is an important consideration in this technology. SUPERCONDUCTING STORAGE AND SWITCHING DEVICES The basic superconductive switching device is the thin-film cryotron. The geometry of this device is attractively simple, since it involves only the intersection of two lines that are electrically insulated from each other. The switching element (gate) and control element (control) of a crossed-film cryotron are arranged as illustrated in Fig. 1. The material for the gate is selected to permit the gate to be switched from the superconducting to the normal (resistive) state by the application of a control current. Tin, which has a critical temperature (T,) of 3.7°K, is commonly used for the gate and the cryotron is operated at a temperature just below T, (for example, 3.5°K). The control material (normally lead, with T, = 7.2°K) is chosen so that the control is never driven normal during circuit operation. To improve cryotron operation, a ground plane, also of lead, is placed under all of the circuitry to act as a diamagnetic shield and improve the current-density uniformity across the width of various thin-film elements. Normally, line widths vary from 0.005 to ^ 0.020 in. and film thicknesses from 300 to 10,000A, although new fabrication techniques make narrower lines feasible. In fabricating cryotrons it is important that the edges of the gate elements be geometrically sharp to avoid undesirable switching characteristics associated with a thinner edge region, Fig. 2. One technique which has been used extensively to form patterns consists of placing a physical mask containing the film pattern between the evaporation source and the substrate and depositing through the mask. Film strips formed in this manner possess a penumbra at the film edges due to shadowing of the evapor-ant under the mask. Several techniques have been proposed for minimizing effects due to this penumbra. One of the more promising metallurgical techniques

Jan 1, 1967

By Robert E. Green, Kenneth Reifsnider

Several experiments have been performed in order to illustrate the application of a recently developed X-ray image intensifier system to metallurgical investigations. In the present work the system has been used to study the instantaneous alterations in Laue transmission X-ray diffraction patterns during tensile deformation of aluminum single crystals. Expem&apos;mental results are presented which demonstrate the capability of the system for crystal orientation, for following orientation changes due to lattice rotation during tensile deformation, and for showing changes in the homogeneity of the lattice planes along the specimen length as a function of strain rate. RECENTLY, a new X-ray system has been developed which incorporates a cascaded image intensifier and permits direct viewing and recording of X-ray diffraction patterns produced on a fluorescent screen.1"3 In the present work the results of several experiments are presented which demonstrate the usefulness of this system for metallurgical applications. EXPERIMENTAL PROCEDURE A schematic diagram of the experimental arrangement is shown in Fig. 1. In this system a Machlett AEG-50-S tungsten target X-ray tube, normally operated at 50 kv and 40 ma, serves as the X-ray source. The X-ray tube is placed in direct contact with a 10-in.-long collimator, which transforms the X-ray beam from one with a circular cross section to one with a rectangular cross section 3 in. high and 1/6in. wide. By blocking off all but a small portion of the rectangular slit, it is possible to work with the more conventional "pinhole" collimated X-ray beam commonly used for obtaining Laue diffraction patterns. In the present work the test specimens were 99.99+ pct aluminum single crystal wires & in. in diam and 3 in. long. For the deformation tests the wire crystals were mounted in a special set of grips in a table model Instron machine so that diffraction patterns could be recorded during specimen deformation. For the orientation tests the wire crystals were mounted in a rotating goniometer so that diffraction patterns could be recorded during specimen rotation. At a distance of 3 cm from the specimen axis, a 6 in. diam DuPont CB-2 fluorescent screen is positioned to transform the X-ray image to a visible one. A Super Farron f/0.87 72 mm coupling lens, corrected for 4 to 1 demagnification, transmits the visible image to the image tube. The image intensifier used is a three-stage magnetically focused RCA type C70021A with an S-20 input photocathode and a P-20 output phosphor. The tube has unity magnification and useful input and output screen diameters of 1.5 in. The image on the output phosphor is of sufficient intensity to be viewed directly, to be recorded cine-matographically, or to be displayed by vidicon pick-up on a television monitor. The recording device most commonly used is a 16 mm Bolex motion picture camera fitted with a Canon f/0.95, 50 mm lens. The overall gain of the system is 16,000 for direct viewing and 2240 for recording on 16 mm movie film. The resolution of the system is limited to 1 line pair per mm which is approximately that of the fluorescent screen. This system has been used for cine recording of transmission Laue X-ray diffraction patterns with exposure times as short as 1/220 sec and for vidicon television pick-up and display at a scan time of 1/30 sec. Quantitative information may be obtained from each frame of the movie film, by either stopping the vertical slit down to a point source in order to obtain a conventional Laue photograph or else by retaining the linear beam and introducing fiducial marks as described in a previous paper.4 In either case, each frame may be enlarged to appropriate size for analysis by either using a photographic enlarger and making prints of the desired frames, or, more conveniently, by using a microfilm reader. EXPERIMENTAL RESULTS The first series of photographs which are presented in Fig. 2 serves to demonstrate the usefulness of the system for crystallographic orientation determination. This series of prints, made from enlargements of a 16 mm movie film, shows the dynamic Laue transmission patterns produced by an aluminum single crystal wire which was rotating about the wire axis when the patterns were recorded. The movie films were taken at 16 frames per sec and the crystal was rotated at a rate of 15 rpm.

Jan 1, 1970

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub&apos;s data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.&apos; Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200&apos; and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963