Search Documents

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By M. Kaufman, A. E. Palty

The phase structure and aging characteristics of two nickel-base alloys, Inconel 718 and 702, were investigated. Wrought and cast Inconel 718 showed ArisCb as the major hardening phase, as well as ture was positively identified. Inconel 702 had Ni3Al as the major hardening phase, as well as Cr7C3-of the phase amounts with temperature was determined. 1 HE value of phase structure and aging rate information in the utilization of alloys has been well established. As part of a continuing program, the results obtained on two nickel-base alloys, hconel 718 and Inconel 702, are presented here. Inconel 718 is a relatively new alloy considered for application in both sheet and cast form. Its novelty lies in the use of high columbium tantalum levels in a Ni-Cr-Fe base. No previous work on this type of alloy has been reported in the literature. Inconel 702 is being used now as an oxidation-resistant sheet alloy. Occasional fabrication problems spurred work on its basic structural behavior. The composition of 702 is essentially nichrome plus aluminum and titanium for strengthening and added oxidation resistance. This puts it in the basic class of other nickel-base alloys which have already been studied. The two alloys will be treated separately. INCONEL 718 Phase Study Methods. The phases present after the various conditions investigated were determined by X-ray diffraction analysis of two different elec-trolytically extracted residues and microscopic examination. The extraction methods, using 10 pct HC1 in alcohol and 10 pct H3PO, in water and the X-ray technique have been described previously.' The effect of temperature on the phase behavior was studied on sheet material using the following heat treatments: 2250°F, 2 hr, ice brine quench 1300 100 hr, water quench 2250°F, 2 hr, ice brine quench 1400°, 100 hr, water quench 2250°F, 2 hr, ice brine quench 1500°F, 100 hr, water quench 2250o 2 hr, ice brine quench 1700°F, 48 hr, water quench 2250°F, 2 hr, ice brine quench 1850°, 24 hr, water quench 2250°, 2 hr, ice brine quench 2000°F, 6 hr, water quench The high solution temperature was an attempt to dissolve as many phases as possible without causing melting. Aging exposures were made longer than normal heat treating times in order to approach equilibrium conditions more closely. Cast material was examined only in the as-cast condition and with the normal heat treatment (1700°F, 1 hr, air cool 1325oF, 16 hr,air cool). Materials. The full phase study was performed on sheet specimens approximately 1/2 in. by 2 in. by 1/16 in. The cast pieces were cut from the gating system of a vacuum-cast test piece. An all weld-metal specimen was made by running many weld beads on the sheet using filler made from the sheared edges of the sheet. All external contamination was removed by belt-sanding followed by an electro-polishing treatment. The typical composition of wrought Inco 718 is as follows: The alloy is air-melted. Cast hco 718 may have higher molybdenum. Due to the expectation of finding a Ni-Cb phase (Ni, Cb) for which no X-ray diffraction pattern was available in the ASTM Index, a special 5 Ib heat to the stoichiometric composition of this intermetallic

Jan 1, 1962

By J. H. Swisher, E. O. Fuchs

Rate equations were derived to describe the kinetics of internal oxidation of cylinders and spheres. The derived equations for cylinders were checked experimentally by means of sub scale thickness and electrical conductivity measurements on Cu-Cr alloy wires. The properties of the internally oxidized samples were examined with conductivity applications in mind. It was possible to produce uniform dispersions of Cr2O3 in copper with an initial chromium content as high as 3 wt pct. While electrical conductivities only a few pct less than that of OFHC copper were obtained, the Cr2Os particle size and spacing were too large for effective dispersion hardening. T.HE process of internal oxidation has been used widely in basic studies of the permeability of gases in metals. In a review article, Rapp1 has discussed the principles of internal oxidation in considerable detail. From a technological standpoint, internal oxidation is often considered undesirable, since it is a means by which inclusions can be introduced into an otherwise clean material. Another important aspect of internal oxidation is its use as a means of dispersion hardening a material. Broutman and Krock2 discuss this and other methods for making dispersion hardened alloys. The only internally oxidized material known to the authors which is commercially available is a Cu-BeO alloy.3'4 This alloy is made from Cu-Be alloy powder, using a so-called Rhines pack. It has a tensile strength of 80,000 psi and retains its strength at relatively high temperatures. The objectives of the present study were to derive rate equations for the internal oxidation of cylinders and spheres, to check the derived equations for cylinders experimentally, and to examine the structure and properties of internally oxidized Cu-Cr alloys. The Cu-Cr system was chosen for this study because uniform dispersions are obtainable at high alloy contents, which is a desirable characteristic in dispersion hardened materials. RATE EQUATIONS FOR VARIOUS GEOMETRIES A number of authors5--9 have derived equations to describe internal oxidation kinetics. These derivations differ somewhat in mathematical assumptions and approximations, and all except one of the derivations deal exclusively with the internal oxidation of plates. The exception is a brief treatment of cylindrical and spherical geometries given by Meijering and Druy-vesteyn9 as a part of a comprehensive paper on the general subject of internal oxidation. These authors did not obtain rate data to check their derivations, although they did show that the hardness profile across an internally oxidized sample is directly related to the rate of interface movement. For cylindrical and spherical geometries, a quasi-steady-state approximation is needed to circumvent mathematical complications in obtaining a solution to the basic differential equations. In using this approximation, we consider the concentration gradient of dissolved oxygen in the internally oxidized zone or sub-scale to be the same as the gradient which would be present if there were no movement of the subscale interface. The steady-state approximation introduces an error of about 1 pct in computing the rate of internal oxidation of an Fe-1.0 pct Mn alloy plate, if the present method is compared to the more exact method of Wagner.7'10 The details of the derivations of the rate equations for cylinders and spheres are given in the Appendix, and only the results of these derivations are given below. The final equations obtained by Meijering and Druyvesteyn9 can be shown to be equivalent to our Eqs. [1] and [2], although the two approaches are somewhat different. Cylindrical Geometry. [2] where r1 is the outer radius of the cylinder or sphere, cm, r2 is the radius of the unreacted core, cm, see Fig. l(a), D is the diffusion coefficient of oxygen in copper, cm2 per sec, %O is the concentration of dissolved oxygen at the surface of the specimen, wt pct, %Cr is the initial chromium concentration in the alloy, wt pct, and t is the reaction time, sec. Plate Geometry. The analogous rate equation for a plate has been derived previously for internal oxidation of Fe-Al alloys.8'11 For Cu-Cr alloys, we may write the same equation as follows: [3] where r1 is the half-thickness of the plate, cm, and r2 is the distance from the mid-plane to the subscale intherate is An analysis of Eqs. [1], [2], and [3] shows that for a plate the rate is completely parabolic. The initial

Jan 1, 1970

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By G. O. Hiers

IN 1948 in the United States, 184,300 tons of lead was fabricated as coverings for electric power and communication cables. Such covering generally is called "sheathing" for the principal lengths of the cables, while the short lead encasements of the joints are called "sleeves." For the purpose of this paper, both lead sheathing and lead sleeving can fittingly be called lead tubing. In the United States in the same year, 34,262 tons of lead was consumed in making extruded lead pipes. Such pipe is employed frequently for water or chemical solution conveyance with gage pressures up to 100 psi. Consequently, the walls are thicker in ratio to diameter than is the case with the cable sheaths. For this discussion, lead pipes can be thought of as tubes or tubing. About 19 centuries ago, the Romans produced metallic lead of about 99.9 pct purity. Evidently this was cast in flat sheets of Y8-in. thickness, for instance. Such sheet of 10-ft lengths was bent around a removable core producing a tube somewhat oval in cross-section and with a typical internal diameter of, say, 3 in. This method of production necessitated a seam or longitudinal joint evidently made by casting the seam metal adherently. The seam metal, as analyzed recently, contains about 1 ½ pct Sn. Blow pipes were said to have been employed when the joint was made. Specimens of such pipe were found both in Italy and in the British Isles. It is believed the pipes conveyed water for drinking purposes and for baths. Numerous specimens are still in existence in a good state of preservation, due to lead's usual inertness in air or water. According to Claude E. Pearson,1 there were various stages in the evolution of lead extrusion presses for making tubes: I. First press by Joseph Bramah, 1797. 2-First successful press by Thomas Burr, 1820. 3-First bridge die press, J. and C. Hanson, 1837. In 1845, Wheatston and Crooke made the first lead sheathed electric cable. Flat lead strip was wound spirally around the insulated conductor. Overlapping edges of lead were soldered. Early cables were also made by pulling insulated conductors into 50-ft lengths of lead tube. Borel in France, and Wesselau are credited with devising the first presses for extruding lead sheaths directly on cables in 1879. In the United States, Eaton, in 188o, and Roberston, in 1885, introduced new presses of improved design. Following Cunningham's original idea of making lead traps and. bends in 1873, the presses apparently were improved and made successfully soon thereafter. Between the years 1930 and 1940, two continuous extrusion presses for lead were developed abroad. One apparently was originated by Dunsheath and made by the Henley Telegraph Works Co. The other was developed by the Pirelli-General Cable Co. CURRENT PRODUCTION In addition to the several descriptive chapters on lead extrusion in Pearson's book, the Metals Handbook2 recently described pipe, sheath, and collapsible tube production. The latter is by impact extrusion.

Jan 1, 1951

By R. G. Wheeler, J. W. Goffard

The Larson-Miller parameter was used to correlate time, temperature, and indentation creep of magnesium, aluminum, and some of their alloys. In the temperature range 300" to 450°C, the short-time Meyer hardness of pure magnesium was less than that of the magnesium alloys tested, but for long times the pure magnesium has greater indentation creep resistance. Aluminum (1100 alloy) had 1.5 to 2.5 times more indentation creep resistance than magnesium at 300" and 450oC, respectively. Hardening of aluminum with a dispersion of Al2O3 was effective in the time and temperature ranges studied. New technologies have required the development of new materials and the utilization of the more familiar materials for new and unusual applications. The use of magnesium and aluminum and some of their alloys, because of their desirable nuclear characteristics, light weight, low cost, and ready availability, has been extended to the 300" to 450°C temperature range. In this temperature range the basic consideration of these materials must be their rate of plastic flow rather than offset yield strengths. The indentation testing reported here arose from a need for design data for the load-holding ability of supports made of these materials. Test Procedure—Hardness indents were made with a 0.275-in.-diam quartz indentor and a 10.65-lb load. The indentor was made by fire-polishing a spherical surface on the end of a fused quartz rod. The samples were held at temperature in a graphite crucible controlled to ±2°C. A thermocouple was attached to the sample and test temperatures were recorded. The diameter of the spherical indentation was measured at the end of a test period and the compression stress (Meyer Hardness) was determined by: H___________load__________ m = projected area of indent Samples were 1 in. in diam and at least 1/4 in. thick. It was observed that at the higher temperatures and longer times, the quartz indentor would stick to the magnesium sample. The quartz indentor was, therefore, frequently inspected and fire-polishing repeated when necessary. The area of sticking was always a small fraction of the area of indent and was therefore considered to have an insignificant effect on results. Correlation of Hot-Indentation Test Data with Time-Temperature Parameter—Sherby and Dorn' have correlated creep or tensile data of a' solid solutions of aluminum with a temperature and strain-rate parameter suggested by Zener and Holloman. underwood2 used this parameter to correlate creep properties of some steels with hot hardness, and upon the basis of this correlation a means of obtaining creep properties from short-time (and inexpensive) hot hardness tests has been demonstrated. Since the validity of the correlation of creep properties with a time-temperature parameter and the correlation of creep properties with hot hardness have been shown, it follows that hot hardness may correlate with the time-temperature parameter. The hot-indentation data obtained was expressed as Meyer hardness, and was shown to be time and temperature dependent. Correlation of Meyer hardness, time, and temperature with the parameter was made using the relationship: Hm = Meyer hardness t = time, hours T = absolute temperature, OK K = constant A value for the constant K was calculated by equating In l/t + K/T at different temperatures and times but at the same hardness. The correlation was tested by plotting Hm vs the parameter, In 1/t +K/T. Since materials are being sought which have high hardness at low indentation creep, i.e., a high Meyer hardness for long time at high temperatures, low values of the parameter are ofthe most interest. TEST RESULTS Magnesium—Pure magnesium (99.98 pct) cut from extruded rod was indentation tested perpendicular to the rod axis at temperatures of 300°, 350°, 400°, and 450°C for times ranging from 6 sec to 112 hr. Fig. 1 shows the time dependency of Meyer hardness at the four constant temperatures. Fig. 2 shows the correlation of the Meyer hardness of pure magnesium with the time-temperature parameter using a K of 22,720 in Eq. [I]. At the bottom of Fig. 2, the effect of doubling the time of indentation t2 = 2(t1), on the abscissa for any time is shown graphically. This effect is of constant magnitude. Also shown graphically are the magnitudes of the effects on the

Jan 1, 1960

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By F. D. Patchen

Changes in the properties of partland cement upon the addition of fine-ground silica are discussed. Data were collected from formulations cured for periods up to 60 days at temperatures varying from 180" to 350°F. Compressive strengths, permeabilities and thickening times are compared. It is demonstrated that addition of find-ground silica in proper proportion results in a hydrated cement with superior properties above 230°F; i.e., early compressive strengths are higher and increase with additional curing, permeabilities are significantly lnrver and thickening times are increased. X-ray analysis of hydrated cement samples have been used to determine more fully the complex chemistry of these systems. Dicalcium silicate alpha-hydrate was found in all neat cements cured above 260°F. A 10 weight per cent silica addition produced a maximum amount of this phase. Xonotlite and tobermorite have been identified as hydration products at 320°F in systems containing 35 or more weight per cent silica. Formation of these components appears to be primarily responsible for the gain in strength and reduction of permeability observed after the addition of silica. INTRODUCTION For several years it has been recognized that loss of compressive strength occurs when portland cement is cured at a temperature above 250°F. This phenomenon has been called "strength retrogression". More recently it has been recognized that increased permeability usually is associated with decreased compressive strength at these temperatures. At curing temperatures above 300°F, these factors reach serious proportions. A compressive strength loss of 50 per cent between curing times of 24 hours and 14 days has been reported,' and permeabilities as high as 10 md have been measured in neat cements cured at 320°F for seven days.' Earlier investigators,' although unsuccessful in eliminating strength retrogression, stated ". . . .it appears possible that by the proper selection of additives for cement, strength loss with age at high temperatures can be either eliminated or considerably lessened". One solution suggested was the use of a pozzolanic material, hydrated lime, and a retarder. Menze15 in 1934 discovered that portland cement containing finely divided silica possessed high compressive strengths when the curing temperature was 350°F. The use of such a composition is now an established practice in the manufacture of steam-cured cement blocks. It is reasonable to assume that the same beneficial effect can be used advantageously in high-temperature oilwell cementing operations. Ludwig first mentioned the use of sand for this purpose. Later, a portland cement containing moderate additions of silica flour and retarded with CMHEC, a cellulose derivative. was recommended for high-temperature application." These formulations have been successfully employed in the field."'" This paper presents the results of a research program to test the efficacy of finely ground silica in increasing the compressive strength and reducing the permeability of oilwell cement compositions containing portland cement. Included also are X-ray diffraction patterns of powdered samples which have been used to determine some of the important chemical reactions occurring in these systems. LABORATORY PROCEDURES AND MATERIALS All compressive-strength test specimens were prepared and cured from a slurry in accordance with API RP 10B, with two modifications. A final curing pressure of 5,000 psi was maintained for a one- or three-day period; but, for further curing, pressures were reduced to the vapor pressure of water at the curing temperature. Also, the water content was varied in samples containing silica to maintain the slurry viscosity within a range of 5 to 15 poise as measured on a consistometer. Test specimens at 180°T were cured in a water bath at atmospheric pressure. At higher temperatures the specimens were cured in a steam-jacketed high-pressure curing vessel at 5,000 psi for a one- or three-day period. cubes cured for longer periods were removed from the pressure-curing vessel after 24 hours, sealed in small bombs containing water and placed in an aging oven.

By E. Maltby Shipp

YouR committee's secretary submits the following report, or summary, to the members of the committee, in an endeavor to lay before them a general review of the information so far received and also his own knowledge of the work as carried on at a number of plants, this being done in part to secure further information and suggestions from members and lead to a more effective means of furthering the work of the committee. It is suggested that more detailed data be compiled regarding engineering features involved, and that papers be contributed which will deal with the safeguarding of underground electrical installations. There are few operating companies which have not started a more or less systematic campaign to safeguard their employees from accidental injuries and unhealthful surroundings, but a great deal is to be gained by experience. All may welcome the advice and cooperation of those who have been actively engaged in the work and have demonstrated the results obtainable by organized effort, and it is, therefore, exceedingly gratifying to note the ready assistance and hearty cooperation rendered by the companies that may be truly termed pioneers in the movement. No solution of the safety problem is to be found in a skrict standardization of methods, rules or devices, as the various mining, milling and metallurgical practices present too many conditions differing broadly in general principles, but some standard system embodying principles already proven to be efficient should be created, which may be modified or elaborated to meet specific requirements of each individual company, or to fit working conditions as they exist in the various mining camps throughout the country. An industrial plant is primarily a business undertaking, therefore the economic side of a safety or welfare campaign is of importance. Many small operators have been deterred from undertaking the work by their belief that it involved an expense beyond their means, and one that could not be counterbalanced by greater efficiency or saving along other lines. This idea is generally due to a lack of knowledge of the actual costs of such work, and of the results secured by judicious selection of a method commensurate with the size and nature of the opera-

Jan 1, 1918

By James R. Cost

The increasing emphasis upon the use of refractory metals has resulted in a closer look at some of the properties of these materials. In the course of a study of the Nb-N system it became necessary to re-examine one such property, the spectral emissivity, e. Experiments were performed in order to determine e for solid niobium as a function of both temperature and nitrogen content. The results of these experiments, which indicate a small but significant correction to the spectral emissivity of pure niobium, are reported herein. In addition, data on the total emissivity, et, of niobium and the spectral emissivity of the nitride Nb2N are given. To this author's knowledge, neither of these emissivities are as yet reported in the literature. Previous studies of the spectral emissivity of niobium have been few. In 1915, Burgess and Waltenburgl obtained a value of 0.49. Whitney? in 1935, used a Mendenhall V to obtain the commonly accepted value of 0.374. A recent investigation of sintering of niobium graphically reported a value of about 0.36= using a solid block of the metal with a blackbody hole drilled into it. In the present experiment a method similar to that of Worthing4 was used. An 8-in. long and 3/16 in. diam hollow tube was formed from smooth surfaced 0.0013-

Jan 1, 1962

By J. A. Burkhardt

Field measurements and theoretical studies have been made of pressure surges—momentary variations in fluid pressure—produced by movement of pipe in mud-filled boreholes. Pressure measurements were recorded by five pressure gauges located at various positions in the borehole. An important positive pressure peak was found to occur as the casing moved with maximum velocity. Important negative peaks were found as the casing was lifted from the slips and as brakes were applied to stop pipe movement. A rigorously formulated theory has successfully predicted the sequence and magnitudes of these positive and negative surges and has established a basis for understanding how they occur. Both the measurements and theory indicate that the most important pressure surge is usually due to viscous drag of the flowing mud. The theory of viscous-drag pressure surges has been approximated by simplified graphs and calculation procedures to facilitate ready use in field operations. Comparison of measured results with those predicted by the simplified theory shows that the magnitude of this surge can be predicted accurately. INTRODUCTION It is widely recognized that raising or lowering pipe in a fluid-filled borehole produces momentary variations in fluid pressure, commonly called pressure surges. Both negative (or "swabbing") surges and positive (or "fracturing") surges may occur. In 1934, Cannon1 measured the negative surges and showed that they could be large enough to cause flow of formation fluids into the well-bore and, in extreme cases, lead to blowout conditions. Later, Coins2 measured the positive surges associated with lowering pipe. His results and subsequent field operations strikingly demonstrated that pressure surges could be an important factor in some cases of lost returns. In addition, although the evidence is less clear than in the case of blowouts and lost returns, other investigators 3, 4 feel that pressure surges probably play a part in many instances of minor gas cutting, salt-water flow and other hole trouble. The importance of pressure surges in drilling operations led naturally to attempts to explain the physical causes, nature and magnitude of the surges. Cardwell5 was the first to publish a theory which allowed the quantitative prediction of momentary pressure variations. He assumed that the drilling fluid was a 300-cp Newtonian fluid in turbulent flow. Most field muds have a considerably lower viscosity and are generally believed to be Bingham plastic in nature.6 However, card-well's results were useful because they were presented in a form convenient for field use and, in some cases, gave a reasonably accurate predicted value for the maximum pressure surge. Subsequently, Ormsby7 published a more comprehensive theory of pressure surges. He discussed both laminar and turbulent flow and considered the theory of mud-bypass devices for reducing pressure surges. As a consequence of his more rigorous approach, his results were more accurate but more complex and difficult to use. Further, both Ormsby and Cardwell considered only the pressure surge arising from viscous drag of the moving mud. Clark later published idealized graphs of surges and presented equations for predicting their magnitudes. In addition to pressure variations arising from viscous drag, he considered those caused by inertial effects. His theory was in this respect more complete than those of Cardwell and Ormsby, although he did not discuss pressures due to breaking of the gel. Furthermore, his equations, while not exceptionally complicated, were too complex for ready use at a drilling location. One difficulty common to all three theories is that none was tested rigorously by direct comparison with measured pressure surges. Their accuracy, therefore, could, not be demonstrated. Further, the two theories based on most realistic assumptions (Ormsby and Clark) required the solution of one or more rather complex algebraic equations. The research described in this paper was undertaken to supplement that described and to overcome some of the difficulties noted. It seemed obvious that a fully satisfactory study of pressure surges should encompass three main phases. 1. A valid theory useful in all field situations must be developed. This theory must be based upon realistic assumptions, must be formulated rigorously and should lead to clear concepts whereby the nature of pressure surges can be easily understood. 2. The theory, however complex and involved, ultimately must be presented in simplified form for convenient field use. This may involve extensive machine computations and the use of figures and empirical equations. 3. The accuracy of the simplified equations must be established by comparing measured pressure surges with those predicted by the theory. These must agree both in their characteristic nature and in magnitude. 'This means that careful measurements of surges occurring in actual field operations must be made.

By M. L. Leonardi

THE Searles Lake orebody is located in the north- west corner of San Bernardlno County. It is a dry lake bed with an exposed salt surface covering an area of 12 square miles. Recoverable mineral values are contained in the mother liquor below the surface of the lake. Stratification in the lake bed has separated the brine into two bodies which dlffer in composition. Although liquor is processed from both bodies, this paper will discuss only the upper structure brine. Fig. 1 illustrates a typical cross-section of the two commercial orebodies. The orebody is composed of a porous salt deposit 70 to 90 ft deep. The upper structure is separated from the lower orebody by a 12 to 16-ft thick impervious mud seam, as shown in Fig. 1. These salt structures are composed of 55 pct solid-phase salts and 45 pct voids which are filled with the original mother liquor. The brine wells are drilled to the separating mud seam and cased to wlthin 10 ft of the bottom. This is done to draw the brine horizontally from the bottom of the structure. It is pumped with multistage centrifugal pumps Into the plant at the rate of 3 milllon gal per day. The first process that was successful was developed by Charles P. Grimwood for the recovery of potash. The first evaporator unit was built in 1916. In the early twenties, Dr. Morse worked out a process for the recovery of borax. This made the cycle more efficient, as the end liquor could be sent back to the evaporators rather than being sewered. In 1926 the American Potash & Chemical Corp. was formed as a new company, and the entire plant was remodeled. The plant at that time produced only potash, borax, and boric acid. Since then the American Potash & Chemical Corp. has added processes for the production of USP boric acid, refined potash, sulphate of potash, soda ash, salt cake, lithium concentrates, Pyrobor (Na2B4O7) bromine, phosphoric acid, and lithium carbonate. The main plant cycle may be depicted as a closed cycle, see Fig. 2. The raw material, brine, enters the cycle to be mixed with the end liquor, known as ML2, from the pentahydrate borax crystallizers. The mixture of these two forms evaporator feed. Evaporator feed is pumped to the evaporators where it is concentrated, with respect to potash and borax. In the same operation water vapor, sodium chloride, salt trap salt, and clarifier salt are removed from the cycle, see Fig. 3 for potash plant product. The evaporators produce a concentrated liquor which contains approximately 19.5 pct KCI. This liquor is diluted as it enters the potash plant to keep all salts, except potash (KCI, 97.0 pct) in solution. Here the moist potash leaves the cycle at 100°F. The end liquor, known as ML1, is pumped to the borax pentahydrate crystallizers, where crude borax pentahydrate is crystallized and removed as solid phase. The ML2 is sent back to pan feed to be reconcen-trated, see page 207. Note that the only water to leave the cycle is in the form of vapor and moisture in the solid phase products crystallized. Thus there is a constantly cycling volume of liquor to which brine is added. Since the volume of liquor cycled does not increase, the brine is, in effect, evaporated to dryness. This would be true if there were no liquor losses. But, as in all processes, there are always unavoidable and accidental losses which reduce the volume of cycling liquors. The losses must be made up with brine. The concentration process is the beginning and the end of the cycling liquors. In this process there are three evaporator units of the triple effect counter-current type, that is, there are three pans in each unit and the heat flows in one direction while the liquor flows the other way through the evaporator pans, see Fig. 4. During the evaporation process a great deal of sodium chloride, burkeite, some sodium carbonate monohydrate, and a little lithium-sodium phosphate are crystallized. The volume of these salts is so great that they must be removed as they are formed or the process would come to a standstill. Brine and recycled mother liquor No. 2 enter the third effect evaporator pan from the evaporator feed storage tanks, see Fig. 5. A steady flow of liquor is removed from the bottom of the No. 3 pan and is pumped through the No. 3 cone of the salt trap, a clear liquor being returned to the NO. 3 pan. A portion of this clear liquor is pumped to the second effect pan. This process is repeated in each pan. The liquor from the No. 2 pan is pumped through the No. 2 salt trap cone and returned to the No. 2 pan.

Jan 1, 1955

By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963

By M. H. Caron

THE most outstanding property of ammonia liquors, used in the ammonia leaching process is their very limited ability to dissolve all compounds present in reduced ore except nickel and cobalt. Although they do have such a high degree of purity, even the smallest amounts of impurities contaminate the precipitate of basic nickel carbonate that may be obtained from pregnant liquors by straight distillation. Figures have been given in a separate paper regarding the extent of such contamination. The product of straight distillation is likely to contain small amounts of Fe, Mn, MgO and SiO2 as well as some sulphate and sulphide. The sulphur can be readily eliminated by calcination of the product at the proper temperature and MgO and SiO2 by reduction and melting of the metal with a suitable flux. After such treatment the metal is relatively pure, and the iron and manganese content will be very small. The cobalt content, however, may vary considerably, depending upon the ore treated. The metal obtained from pure true garni-erite ores usually has only a small cobalt content of less than 1 pct. Metal obtained from medium grade iron-rich nickel ores may show cobalt values from 2 to 3 pct, and the alloy obtained from laterite is likely to contain as much as 10 pct cobalt. By proper treatment a good deal of cobalt may be recovered from lateritic nickeliferous iron ores, and cobalt will become the major constituent of the pregnant liquor if asbolan ores or similar products are treated. The pregnant liquor of "run of mine" nickel ores may have a pinkish shade, indicating the presence of cobalt. It is evident that from such liquors the metals should be recovered separately. Even if cobalt is present in only very small amounts, it would probably be economically justifiable to recover both metals as pure as possible if a suitable process could be devised. The author has made investigations along this line and has patented some processes adapted to the treatment of this type of solutions. Selective Dissolution of Nickel from Basic Nickel Carbonate Containing Some Cobalt: Basic nickel carbonate obtained from true garnierite ores by straight distillation of the pregnant liquors, always contains some cobalt as well as the normal impurities. In. order to improve the quality of the nickel product and to recover most of the cobalt, the following process has been devised. By using liquors with a low CO2 to NH3 ratio, nickel can be redis-solved preferentially to cobalt. It is not a sharp and clean separation but a selective one, for the bulk of the nickel may be redissolved with a small amount of cobalt, and a small residue may hold the bulk of the cobalt. The greatly increased cobalt content of the residue is indicated by a pronounced olive green color, in contrast with the light green color of pure basic nickel carbonate. The following example is given from Dutch patent No. 52788, Klasse 40a. 43 granted June 17, 1942: The original precipitate contained about 0.55 pct cobalt calculated on total nickel + cobalt. Eight hundred and fifty grams of the basic nickel carbonate were redissolved in leach liquor containing 7.12 pct NH3 and 2.12 pct CO2. The weight of the dry residue was about 3.5 pct of the original weight. By analysis it was found that the residue contained: Fe 1.93 pct, Co 6.01 pct, Ni 34.87 pct and also a certain amount of silica. The clear filtered blue liquor was distilled and the precipitate of basic nickel carbonate from this analyzed: Fe 0.008 pct, Co 0.0146 pct, Ni 42.37 pct. It is obvious that this product is considerably more pure, since calculation shows that about 94 pct of the original cobalt remained in the residue. Cobalt and nickel can be recovered by further

Jan 1, 1951

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By C. G. Goetzel

Until recently porous bronzes have found many applications for self-lubricating bearings in the automotive, electrical, household appliance and general machine industries. The bulk of an annual production of several million pounds of copper powder had gone into the manufacture of these articles, of which by now more than a billion are in service. However, the war has brought severe curtailment of these bearings because of the scarcity of the two main constituents, copper and tin. The development of substitute materials of equal or superior properties has led to a large-scale replacement by products made from iron powder. In spite of the diminished interest in powdered copper-tin alloys caused by this trend, it was believed worth while to investigate some mechanical properties of these materials as a reference base for substitutes. In addition, experiments using the hot-press method were incorporated to investigate possibilities of saving vital equipment or opening new fields of applications. It must be assumed that by this time the powder metallurgy process of making porous bronzes, a development that found its first industrial applications more than 10 years ago, is well known in engineering. The patent literature and bibliography is volu- minous, most publications referring to porous, self-lubricating bronzes, containing about 10 per cent tin and I to 5 per cent graphite, with porosities in the range of 25 to 35 per cent.l-7 The excellent antifriction properties of these bearings, caused by the uniform impregnation with oil, are dependent on the interconnection of the pores and the uniform distribution of the graphite inclusions. The sintering mechanism of porous bronze, with its structural changes during the transformation of the metal powder into the sintered bearing has been shown in colored photomicrographs by Hall.* Diffusion between copper and tin was found to begin within one minute, when tin-rich transitory phases were formed. After 25 min. a homogeneous matrix of alpha was reached for an alloy containing 9.5 per cent tin and 6 per cent graphite. Price, Williams and Garrand,9 studying certain metal powder combinations in which sintering is accompanied by the cementing action of a liquid phase, including a 90-10 bronze sintered at 925°C., have found that if the treatment is carried out within the liquidus and solidus temperature range of the system, a peculiar process of alternate solution and precipitation occurs. The particles of the major solid constituent are dissolved in the minor liquid phase, but thereafter are reprecipi-tated on certain nuclei, which develop into large grains, usually rounded.

Jan 1, 1945

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965