Search Documents

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite, with length-to-diameter (LID) ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite), were broken in axial compression to determine to what extent an increase in end constraint increased compressive strength. Radial end constraints of 13 to 23% of the average axial stress in the pillar, produced by solid steel rings bonded with epoxy to the ends of dogbone-shaped specimens, increased compressive strength somewhat above that of cylindrical pillars without ring constraint. However, when the results were compared with those obtained by other investigators for straight specimens of several rock types taken collectively, with LID ratios greater than 0.5, the resulting strengths were not significantly different. Thus, the amount of end constraint produced by the solid steel rings was about the same as that produced by the friction from the steel end plates. In other tests, a radial prestress of 3000 or 5000 psi was applied prior to axial loading by adjustable hardened steel rings to increase the constraint above that obtained for the solid rings. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 3000 psi prestress, was 54.3% for limestone, 40.3% for marble, 44.7% for sandstone, and 23.4% for granite. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 5000 psi prestress, was 74.2% for limestone, 51.2% for marble, 61.6% for sandstone, and 29.7% for granite. These constraints increased the compressive strength significantly above the strength of straight specimens and solid-ring constrained specimens. These results suggest that large horizontal stresses in orebodies mined by the room-and-pillar method should increase the strength of the pillars and allow an increase in ore recovery by a reduction of pillar size when major structural defects are absent. One important objective of the U.S. Bureau of Mines (USBM) mining research program is the rational design of mining systems. In the design of room-and-pillar mining operations, pillar strength is a fundamental variable. It is customary to estimate this strength from uniaxial compression tests of rock samples and to correct this value for the length-to-diameter (LID) ratio of the in-situ pillar. This method of estimating pillar strength corrects for pillar shape but does not consider the effect of a large horizontal in-situ stress field that sometimes exists in underground formations. The purpose of the work covered in this report was to determine to what extent the compressive strengths of model pillars of relatively brittle rock loaded in axial compression were affected by lateral end constraint. In previous work, Obert l used solid steel rings bonded to the ends of dogbone-shaped specimens to study the creep behavior of three quasi-plastic rocks -salt, trona, and potash ore - during a test period of 1000 hr. These rings provided radial constraint during the loading cycle of 20 to 50% of the axial stress for specimens with LID ratios of 2, 0.5, and 0.25. He concluded that (1) "for a quasi-plastic material the end constraint strongly affects the specimen strength, and (2) as D/L increases (length-to-diameter decreases), the specimens lose their brittle characteristics and tend to flow rather than fracture." He also concluded that model pillars constrained by rings were better for use in predicting the strength of mine pillars than either cylindrical or prismatic specimens. This conclusion appears to be valid where mine pillars, roof, and floor are a single structural element. In the present study, 460 specimens of four relatively brittle rocks — limestone, marble, sandstone, and granite - were tested to failure. The study consisted of two parts: (1) the effect on the compressive strength of end constraint produced during the axial loading cycle by solid steel rings bonded with epoxy to the ends of the specimens, and (2) the effect on the compressive strength of increased end constraint produced in part by a prestress applied prior to axial loading and in part by lateral expansion of the specimen during the loading cycle. The first part of this study was reported in some detail earlier.2 EXPERIMENTAL PROCEDURE AND EQUIPMENT Model rock pillars of the sizes and shapes shown in Fig. 1 were broken in axial compression when the ends were constrained as shown in Fig. 2. he straight specimens were broken without ring constraint. The specimens of dogbone shape were broken with (1) solid

Jan 1, 1970

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

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

Jan 1, 1962

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970

By J. R. Szedon, T. L. Chu, G. A. Gruber

Amorphous adherent filnzs of silicon dioxide have been deposited on silicon substrates by the oxidation of silane at temperatures ranging from 650 to 1050C. Various diluents (argon, nitrogen, hydrogen) were used to suppress the formation of SiO2 in the gas phase. Deposition rates of the oxide were determined over the temperature range in question as functions of' re-actant flow rates. Etch rate studies were used for a cursory comparison of structural properties of deposited and thermally grown oxides. From electrical evaluation of metal-insulator-silicon capacitors it was determined that the interface charge density of deposited films is similar go that of dry-oxygen-grown films in the 850° to 1050 C temperature range. Deposited films exhibit several ionic instability effects which differ in detail from those reported for thermal oxides. Stable passivating films of silicon nitride over deposited oxides appear to be practical for use in silicon planar device fabrication. Such films can be prepared under temperature conditions which have less effect on substrate impurity distributions than in the case of grown oxides. AMORPHOUS silicon dioxide (silica) is compatible with silicon in electrical properties and is the most widely used dielectric in silicon devices at present. Silica films can be prepared by the oxidation of silicon or deposited on silicon or other substrate surfaces by chemical reactions or vacuum techniques. The ability of thermally grown silicon dioxide films to passivate silicon surfaces forms one of the practical bases of the planar device technology. Properly produced and treated films of grown SiO 2 can have low densities of interface charge (-1 X 10" charges per sq cm) and can be stable as regards fast migrating ionic sgecies. 1 To maintain these properties, even with an otherwise hermetically sealed ambient, the Sia layers must be at least l000 A thick. Such thicknesses require oxidation in dry oxygen for periods of 7.8 hr at 900°C or 2 hr at 1000°C. Although oxidation in steam or wet oxygen can reduce these times to 17 and 5 min, the resulting oxides must be annealed to produce acceptable levels of interface charge., Oxidation or annealing involving moderate to high temperatures for extended periods of time can be undesirable. Under some conditions, there can be changes in the distribution of impurities within the underlying substrate. A chemical deposition technique using gaseous am-bients is particularly attractive and flexible for preparing oxide films. With a wide range of deposition rates available, films can be produced under condi- tions of time and temperature less detrimental to impurity distributions in the silicon than in the case of thermal oxidation. The pyrolysis of alkoxysilanes, the hydrolysis of silicon halides, and various modifications of these reactions are most commonly used for the deposition of silica films.3 Silica films obtained in this manner are likely to be contaminated by the by-products of the reaction, organic impurities, or hydrogen halides. The use of the oxidation of silane for the deposition process has been reported recently.4 The deposition of silica films on single-crystal silicon substrates by the oxidation of silane in a gas flow system has been studied in this work. The deposition variables studied were the crystallographic orientation of the substrate surface, the substrate temperature, and the nature of the diluent gas. The electrical charge behavior of Si-SiO2-A1 structures prepared under various conditions was investigated by capacitance-voltage (C-V) measurements of metal-insulator-semiconductor (MIS) capacitors. The experimental approaches and results are discussed in this paper. 1) DEPOSITION OF SILICA FILMS The overall reaction for the oxidation of silane is: The equilibrium constants of this reaction in the temperature range 500° to 1500°K, calculated from the JANAF thermochemical data,= are shown in Fig. 1. In addition to the large equilibrium constants, the oxidation of silane is also kinetically feasible at room temperature and above. However, the strong reactivity of silane toward oxygen tends to promote the nucleation of silica in the gas phase through homogeneous reactions, and the deposition of this silica on the substrate would yield nonadherent material. The formation of silica in the gas phase can be reduced by using low partial pressures of the reactants. Argon, hydrogen, and nitrogen were used as diluents in this work. 1.1) Experimental. The deposition of silica films by the oxidation of silane was carried out in a gas flow system using an apparatus shown schematically in Fig. 2. Appropriate flow meters and valves were used to control the flow of various reactants, i.e., argon, hydrogen, nitrogen, oxygen, and silane. Semiconductor-grade silane, argon of 99.999 pct minimum purity, oxygen of 99.95 pct minimum purity, and nitrogen of 99.997 pct minimum purity, all purchased from the Matheson Co., were used without further purification. In several instances, a silicon nitride film was deposited over the silica film. This was achieved by the nitridation of silane with ammonia using anhydrous ammonia of better than 99.99 pct purity supplied by the Matheson CO.' The reactant mixture of the desired composition was passed through a Millipore filter into a horizontal water-cooled fused silica tube of 55 mm

Jan 1, 1969

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By Malcolm McColl, C. A. Mead

Thin films (of mica have unique attributes that are exceptionally good for studies of high-field conduction mechamisms in thin-film insulators and the quantum mechanical tunneling of electrons from metal to metal. The principal advantages of using mica films are that the films are crystalline and the cleavage planes occur every 10Å. This property results in films whose thicknesses are integral multiples of 10Å and whose surfaces are uniformly parallel over sizable areas. Hence, very well-defined metal -mica-metal structures are possible. Furthermore, the fact that the insulator is split fro??! a bulk sample allows the index of refraction, dielectric constant, forbidden energy gap, and trapping levels and their density- to be obtained directly from measurements performed on thick samples Of mica rather than requiring that these properties be interred from the conduction characterrsties alone. In the work to he described, all the cleaving was done in a high vacuum just prior to the evaporation of metal elertrodes so as to avoid air contamination at the interfaces. Results of these studies indicate that the current through the 30 and 40Å films exhibited quantitative agreement with the theoretical voltage and temperature dependence derived by Strallon for the tunneling of electrons directly from metal to metal. Thicker films at room temperature exhibited volt-ampere curves suggesting Schottky emission of electrons from the cathode into the conduction band of mica. However, the thermal activation energy was smaller than that found from other measurements, and the experimsntal Schottky dielectric constant was larger than the square of the index of refraction. These facts would indicate that the electrons were being injected into polaron stales ill the iusulator. At low temperatures and high fields, the current through the thicker films did not exhibit the Fowler -Nordheim dependence as would be predicted by a simple extention of the theory of field emission into a vacuum. THE mechanism of electrons tunneling through insulating films has received considerable attention in the last few years due to the devices possible utilizing tunneling'-4 and the success of tunneling in the study of superconductivity.5,6 Until the recent paper by Hartman and chivian7 on the study of aluminum oxide, there had been no reported successful quantitative experimental fit to the theory. Their method of fabrication necessarily results in a polycrystalline insulator, the stoichiometry of which is nonuniform from one side to the other. This structure also introduces complications to the shape of the barrier which is set up by the insulator since the insulator possesses a spatially nonuniform band structure and dielectric constant. Due to these facts an analysis of the data in terms of a pviori barrier shape is of questionable validity. The use of muscovite mica not only overcomes these disadvantages but, as an insulating thin film, provides physical properties (dielectric constant. trapping levels and their densities, forbidden energy gap, and so forth) that are identical to the easily measured values of the bulk sample. Furthermore, it is a single-crystal insulator whose cleavage planes (10Å apart8,9) provide uniformly parallel surfaces of well-known separation. This material is therefore ideally suited to the study of electron-transport phenomena. Von Hippel10 using a 6.5-µ-thick sample was the first to observe the high-field conductivity (=5 x l06 v per cm) of mica. No attempt was made to develop an empirical formula, but Von Hippel concluded from intuitive arguments that the current was being space-charge limited by trapped electrons. Mal'tsev11 in a more recent investigation at high fields observed a dependence of the conductivity a on the field F of the form exp(ßF1/2). This dependence was attributed to the Frenkel effect,12,13 a Schottky type of emission from filled traps. No mention in the English abstract was made of the thicknesses of his samples or, and more important, of how well the value of ß fit Frenkel's theory. In 1962 Foote and Kazan14 developed a technique for splitting mica to a thickness of less than 100Å and observed a dependence of the current density j on the field of the form j = jo exp(ßF1/2) on a thin sample thought to be 40Å thick. Assuming that this was a Schottky emission process and that the appropriate dielectric constant for such a mechanism would be closer to a low-frequency value of 7.6, Foote and Kazan calculated from ß an independent thickness of the mica of 36Å. No further investigation was made of the phenomenon. However, the work reported in this paper indicates that the film measured by Foote and Kazan was probably 60Å thick, the error arising from the measurement of the very small metal-insulator-metal diode areas that were used, along with the diode capacitance and dielectric constant, to calculate the thickness. In the research reported in this paper, Foote and Kazan's technique was modified to cleave muscovite in a vacuum of 10-6 Torr, immediately after which metal electrodes were evaporated creating Au-mica-A1 diodes. Aluminum was chosen because of its strong adhesion to mica, as necessitated by the

Jan 1, 1965

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.'-' It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer' has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

By A. A. Collins

H. R. BIANCO*—I should like to ask Mr. Collins if that statement he made about the addition of drosses to the blast furnace slowing down the blast furnace is a result of his own experience or a result of the experience of some older metallurgists; and perhaps I should ask him to define the type of drosses that he means. A. A. COLLINS (author's reply)— That has been my own personal experience with dross. On various occasions at Chihuahua we attempted to incorporate the dross in our regular blast furnace charge and to shut down the dross re-verberatory to try to save some money. As expected, we had very poor results. I think that Ed Fleming will well remember on one occasion, that was back about 1933, when we attempted the first experiment along this line, and as a result of the sulphur addition to the blast furnace to matte out the copper we ended up with hanging furnaces and mushy slags and abandoned the dross experiment, once again turning to the use of the reverbera-tory for handling dross. H. R. BIANCO—Is that dross you refer to from the drossing kettle ? A. A. COLLINS—Yes, the dross that I am referring to came from drossing kettles. Furthermore, to back up my previous assertion, I had occasion in 1943, while up at Leadville, to once again experience the routing of dross through the blast furnace with its sulphur addition, since they had no dross re-verberatory, and to observe that once thf dross was removed, the furnace was speeded up almost 100 tons a day. All of these are personal experiences and I think that Mr. Feddersen also has had a little experience along this line —in fact, I believe all of us have had some experience. H. R. BIANCO—I know at Trail they recirculate considerable dross through the blast furnaces and we also recirculate dross at Herculaneuin and I am not aware that it has done much towards slowing down the blast furnace. A. A. COLLINS—We have always had very poor results. In the first place you have got to add a sulphur addition to pick up that copper and once you do that, that sulphur is apt to combine with some of the zinc and you are going to form a little mush; before you know it you have furnace hangs and a poor working furnace. Now of course that depends on the amount of zinc you have on charge. But in 1943, Leadville had roughly about 7 pet zinc in their slag and it worked very poorly. Previously when they had 4 or 5 pet zinc in their slag it did not matter. B. L. SACKETT* At Tooele we had a great deal of experience with copper. We have always been able to keep a lead well, however, in spite of the fact we have run as much as 5 pet copper and only 15 pet lead on the charge. But regarding the handling of dross, our dross reverberatory furnace is only 7 or 8 years old. Before that we recirculated the dross through the furnace and thought we were doing a pretty nice job. Of course these things are all more or less relative—in other words you establish a certain condition much better than one of a few years ago and possibly as good as any other of which you know and you think you have pretty good results. When we first took the dross off of the blast furnace and put it through the dross reverberatory furnace we immediately found out that we had gained something very real in furnace speed. Since that time there have been occasions when, because of the dross reverberatory being down, we have had to use dross again through the blast furnace and that has checked our original experience in slowing down the furnace very definitely. So we feel that a dross reverberatory is a very valuable asset at the Tooele Plant. A. A. CENTER*—Mr. Sackett's being here reminds me of trying to run with a minimum of lead concentrates the maximum of dross producing electrolytic zinc plant residue. He came up from International Smelting Co. to help us get started on that. We took an old copper blast furnace at Great Falls, Montana, and made a lead furnace out of it by putting a lead well on the other long side which of course is a very unorthodox lead blast furnace. Our aim was to treat the residue from the electrolytic zinc plant, as I said, with a minimum of lead concentrates. That meant a maximum amount of dross. At that time selective flotation was not general practice, so our zinc concentrates ran relatively high in copper and other dross-producing elements; and of course these were largely in the zinc plant residue. I think we might call it muscle metallurgy, but we had an interesting, successful experience there and we ran for over a year thanks to Mr. Sackett's helping us get started. I have the details, but time does not permit. We did well enough so that the A. S. and R. Co. at East Helena kept boosting up the offer to us for the electrolytic zinc plant residue and there was not enough lead concentrate to supply two lead smelters there in Montana, so the matter finally finished up by the A. S. and R. Co. taking all of the residue under long term contracts.

Jan 1, 1950

By W. C. Winegard, J. E. Gruzleski

The stages in the development of cells in the Sn-Cd eutectic have been studied by unidirectionally solidifying specimens under known conditions of growth rate, temperature gradient, and impurity concentration. By means of a quenching technique, the shape of the solid-liquid interface during solidification could be observed. Cells are shown to develop from defects or depressions which exist on the solid-liquid interface of even a pure eutectic. Th,e container wall, grain boundaries , and fault lines in the micro structure play an important role in cell development. A two-phase eutectic dendrite found at high impurity concentrations is described. L HE cellular or colony structure formed during eutectic solidification caused much confusion among early workers in their attempts to classify eutectic structure, and a major advance in our understanding of eutectic solidification was made when the colony structure was identified with a cellular interface caused by the presence of impurity elements.1'2 To date, however, no detailed investigation of the stages in cell development in eutectics has appeared, and little work has been done on the cell morphology. The present paper presents the results of such an investigation. EXPERIMENTAL The Sn-Cd eutectic was used in this investigation with lead as the impurity element to promote cell formation. Materials of 99.999 pct purity were zone-refined to an approximate purity of 99.9999 pct. Alloys as close as possible to the eutectic composition, 67.75 wt pct Sn, were prepared using zone-refined tin and cadmium. The alloys were then zone-melted to the exact eutectic composition, as described by Yue and Clark,3 using a total of twenty to twenty-five passes on each eutectic bar. Only those portions of the bars which contained no primary phases were used in subsequent experiments. Master ternary alloys were prepared by melting together the required amounts of lead and the Sn-Cd eutectic in a sealed Pyrex tube under argon, and these alloys were then diluted with pure Sn-Cd eutectic as required. Unidirectional solidification was conducted vertically upward using the two-element resistance furnace shown schematically in Fig. 1. With this apparatus, it was possible to obtain a range of growth rates and temperature gradients so that the cell structure could be studied under different growth conditions. Growth rates in the range of 0.4 to 9.1 cm per hr and temperature gradients from 2.25° to 1475°C per cm were used. To ensure steady-state solidification, power to the furnace was stabilized, and the entire apparatus was enclosed in a large box in which the temperature was controlled to within ± 0.2°C. The apparatus was arranged so that the specimen could be quenched in situ during solidification by pouring a large quantity of water down the central vycor tube. Excellent delineation of the solid-liquid interface at the time of the quench was obtained because of the structural changes accompanying the rapid solidification of the remaining liquid. The quenching rate was always extremely rapid as no evidence of a transition in the lamellar spacing at the interface was ever observed. The alloys to be solidified were contained in degassed, high-purity graphite tubes, 1 cm OD and 0.6 cm ID. The specimens were about 18 cm in length. After the alloy had been cast into the tubes, three 0.8-mm holes were drilled in the tube to the center of the specimen. One hole was placed 1 cm from the bottom of the ingot, and the other holes were placed at 8 and 9 cm, respectively, from the base of the ingot. Thirty-four-gage chromel-alumel thermocouples were sealed in the holes. The lower thermocouple was used to position the solid-liquid interface at the start of each experiment,

Jan 1, 1969

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,' to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,' was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.' Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?'s. The grain boundary angles can be calculated from the w'S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951

By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

By C. C. Templeton, S. S. Rushing

Methods previously developed for the study of air-liquid displacements in microscopic capillaries (inner diameters of 3 to 40 microns) have been used to investigate oil-water displacements in capillaries initially filled with water. Displacement calculations assuming perfect displacement and no capillary pressure hysteresis yielded oil effective viscosities smaller than the macroscopic viscosities. For a given liquid pair, the oil effective viscosity decreased both with decreasing capillary size and with increasing oil-water viscosity ratio. This behavior can be explained by the existence of an annular water film (20 A to 260 A thick) on the capillary wall. When the capillary was first filled with oil, the ratio of the oil effective viscosity to the normal oil vircosity was highest for the first water displacement and decreased with subsequent displacements. Sometimes the oil effective viscosity ratio during the initial water displacement was greater than unity. INTRODUCTION In a previous paper1 a technique was described for studying air-liquid and liquid-liquid displacements in very small capillaries of uniform diameter, in the hope that such microscopic data would further the understanding of the nature of multiphase fluid flow through porous media. That paper contained comprehensive data for air-liquid displacements in Pyrex capillaries, with a few data for oil-water displacements in capillaries initially filled with water. The purpose of this paper is to present more complete results for oil-water displacements in capillaries initially filled with water, and to describe for the first time such observations in capillaries initially filled with oil. In this way the effect of the wetting history of the system upon the displacement process may be studied. METHODS The basic techniques employed were described in the previous paper.1 The measuring procedure and the working equations will be briefly summarized here and a few modilications will be pointed out. For the present study, temperature control within 0.l °C was obtained by placing the microscope and its immediate accessories in a thermostated air bath made of a steel frame covered with plexiglas. The water and oils used in this work were the same as in the previous paper,1 with the addition of "Medium Mineral Oil, U.S.P. supplied by the Harshaw Scientific Co. When the first liquid was introduced into the horizontal capillary, the air-liquid static capillary pressure Poc was measured along the observable length of the capillary. From the relation Poc = 4y cos 0/d, the capillary diameter d could be calculated from Poc if the "microscopic" air-liquid boundary tension, To = y cos On, was taken as equal to its known "macroscopic" value. This calculation involves assuming that cos 6 = 1 and that capillary size or the resulting high interfa-cial curvature has no effect on surface tension, or y cos 6, as was verified by our work, and also by that of Cohan and Meyers on air-liquid-solid systems. For several capillaries these calculated diameter values were compared with values measured visually with a filar micrometer eyepiece. For a given capillary the average values for the two methods agreed within 1 or 2 per cent, but the visual values were less reproducible than the calculated values. Further the calculated values were much less subject to personal bias and took into account any slight ellipticity that might be present. Hence diameters calculated from air-liquid Poc data were used throughout this paper. The second liquid was introduced in such a way that a single spherical interface separated the two liquids. Displacements were always made with a constant pressure, Pt, between the ends of the capillary. The times (t) at which the interface passed certain

Jan 1, 1957

By G. W. Form, W. A. Spitzig

The effects of hydrogen and vacuum shtering treatments on the physical and mechanical properties of arc plasma-sprayed tungsten were inuestigated. Temperatures examined ranged from 3000" to 4000°F in vacuum and 2000" to 3000°F in hydrogen for both single and duplex sintering cycles. Densities of 92 pct of theoretical density were obtained when a long-time hydrogen treatment at 2000°Fpreceded sintering in vacuum at 4000°F for 4 hr. This cycle also produced the highest ualues for modulus of rupture and bend angle. The results of this investigation point out the desirability of using a low-temperature long-time hydrogen treatment prior to a high-temperature vacuum sinter for arc plasma-sprayed tungsten. ADVANCES in the development of arc plasma-generating equipment have provided a high-temperature heat source that makes the fabrication of tungsten shapes possible by a metallizing process. Tungsten in the as-sprayed condition is very brittle. It has a density between 80 and 85 pct of theoretical density, a lamellar structure with elongated pores, and a high interstitial impurity content. To improve these properties, sintering treatments can be applied to the as-sprayed material, similar to those used for the densification of compacted tungsten powder. However, in view of the differences in the density and microstructure of as-sprayed tungsten as compared with compacted tungsten, responses to sintering were expected to be different. EXPERIMENTAL PROCEDURES The tungsten powder used in this investigation had a particle size varying from 3 to 13 p with an average diameter of 8p. The impurity level was less than 0.1 pct. The arc plasma spraying was done with an F-40 Thermal Dynamics Corp. plasma jet. Spraying was performed in air and thus required cooling of the substrate by an air blast in order to minimize oxidation. The spraying parameters employed in the fabrication of all specimens are listed below: Power input, kw 12 Arc-gas flow, cfh 95N2 + 5H2 Powder feed rate, g per min 33 Powder carrier gas flow, cfh ION, Spray distance, in. 3 Traverse rate, in. per min 30 Mandrel speed, rpm 100 Nozzle orifice, in. 7/32 These values of the spraying parameters correspond to optimum conditions ascertained in a previous study. Sintering was conducted at 3000°, 3500, and 4000°F in vacuum (< 0.1 Hg), and at 2000 and 3000°F in hydrogen. Duplex sintering treatments investigated are listed in Table I together with the designations that will be used for reference throughout this paper. The samples were fabricated by spraying onto a copper mandrel which was removed prior to sintering. The specimens used for the sintering analyses had the shape of small hollow truncated cones 1 in. high with an inside diameter varying from 0.500 to 0.125 in. and a wall thickness of 1/8 in. Specimens for bend testing were taken from hollow hexagonal prisms 1-1/2 in. high with a 1-in. diam across the flats and a wall thickness of 1/8 in. The bend-test specimens were ground to the dimensions 0.085 by 0.350 by 1-1/2 in. Prior to bend testing 0.0025 in. of stock was removed from each surface by electro-polishing. Density measurements were made by the water-displacement method. In addition, a porosimeter was used to determine the amount of interconnected porosity for representative samples. Strength and ductility were determined from recorded values in transverse bending using a cross head speed of 0.020 in. per min. The load was applied at the midpoint of a 1-in. span. The deflection data reported herein refer only to the plastic portion of the total deflection. RESULTS AND DISCUSSION The as-sprayed samples had a density corresponding to 83 pct (l pct) of the theoretical density of tungsten. Fig. 1 shows a representative as-sprayed tungsten structure.

Jan 1, 1964