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By R. Steinitz, L. Seigle, R. Resnick

THE rates of growth of the carbide phases MC and M2C in the Ta-C and Cb-C systems have been measured at various temperatures and the results used to estimate the rate of carbon diffusion within the inter metallic phases. Sheets of high-purity tantalum (50 ppm Cb, <25 ppm Ti, 10 ppm Fe, 5 ppm Cr, <50 ppm Mo, W, and all other metals, 15-75 ppm O2, 10-30 ppm N2, and 10-30 ppm C) approximately 1/4 by 1/2 by 0.020 in. were heated to temperatures between 1800" and 2700°C in a carbon resistor furnace under an atmosphere of argon plus sufficient methane to maintain an excess of carbon at the sample surface. The thicknesses of the carbide layers, illustrated in Fig. 1, were measured with a filar micrometer and plotted logarithmically as a function of time. Fig. 2 is a typical plot for the TaC phase. The points may be represented within experimental error by lines with slope equal to 1/2; therefore the growth of the layers may be described by the usual expression X = kt1/2, where X is the layer thickness, t is the time, and k is a temperature-dependent constant. From these data and compositions at the phase boundaries, it is possible to estimate values for the diffusion coefficients of carbon in each phase, assuming that layer growth occurs by carbon diffusion alone, and that the dif-fusivity is not a function of composition within each

Jan 1, 1965

By A. J. Griest, P. D. Frost, H. A. Robinson

The flow characteristics and uniform elongation of alpha-beta titanium alloys in the solution-treated condition were shown to be markedly affected by the solution temperature. Two classes of alpha-beta alloys were distinguished, based on the effect of solution temperature on the uniform elongation. Martensitic alpha-beta alloys, which are relatively weakly beta-stabilized, showed decreasing values of uniform elongation as the solution temperature was initially increased. However, after solution-treatment at still higher temperatures in the alpha-beta field, the uniform elongation of these alloys was again high, and often attained its maximum value. Nonmartensitic alpha-beta alloys, which are more heavily beta-stabilized, showed a continuous decrease of uniform elongation with increasing solution temperature. The behavior was rationalized in terms of the alpha-beta ratio and the alloy content of the beta existing at the solution temperature. The data indicate that in commercial practice close temperature control may be required to get maximum uniform elongotion, and hence, maximum potential formability, in solution-treated sheet. Bend-test data also were obtained for the solution-treated conditions. A MOST important objective of current titanium research is the development of age-hardenable alloys with superior formability in the solution -treated condition. Alpha-beta titanium alloys have been shown to be amenable to high-strength aging treatments after solution-treatment in the alpha-beta field.&apos; However, heat-treatment data on the properties of solution-treated sheet, such as uniform elongation, minimum bend radius, and flow properties, which have a bearing on the potential formability, have not been widely available. This paper presents only the most significant results of a research program conducted at Battelle for the Air Force in an effort to develop sheet alloys that can be formed readily as solution-treated and subsequently aged to very high strengths. Data for 10 compositions representative of the more than 25 alloys studied in this program are presented. A primary objective of the paper is to demonstrate the pronounced dependence of the flow characteristics and uniform elongation on solution-treatment temperature. This effect is believed to be vitally important in the commercial heat-treatment of age-hardenable titanium sheet alloys. Experimental Procedures Melting and Fabrication—The nominal and actual compositions, beta transi temperatures, and rolling temperatures of 10 of the 30 alloys studied are presented in Table I. Stock :€or two of the alloys, E (Ti- 8Mn) and J (Ti-6A1-4V) was obtained from commercial heats. The remaining heats, except D and I, were double melted as 10-lb heats in a consumable-electrode furnace. Melting stock was 120 Brine11 hardness sponge. The oxygen and hydrogen analyses spotted throughout the heats indicate the range of interstitial levels resulting from the melting practice used. Heats D and I were melted as 20-lb ingots with the same grade of sponge. These ingots were cut in half and one portion used in the present evaluation. The ingots, which were about 4 in. diam and 4 in. in height, were upset forged and drawn at 1750°F to sheet bar 5/8 in. thick by 2 1/2 in. wide in such a manner that the top of the ingot corresponded to the top of the sheet bar. Slabs of the sheet bar, 5 1/2 in. in length were scalped to 1/2 in. thickness and rolled at the temperatures indicated in Table I to approximately 0.055 in. sheet. Elongation during rolling took place at 90" to the original forged length. The fabrication procedure used is described in some detail since the experimental heats showed considerable directionality in mechanical properties. The rolling procedures for the commercial heats were unknown, but were such as to produce essentially isotropic properties. All heats, as rolled, showed microstructures typical of alpha-beta alloys worked in the alpha-beta field; that is, the structures consisted of equiaxed alpha particles in a beta matrix. Heat Treatment— The effects of solution and aging heat-treatments on the properties of the alloys were evaluated uSing longitudinal and transverse tensile and bend coupons sheared from the sheet. Two or three solution-treated conditions were evaluated for each alloy. In addition, the alloys were also tested after annealing at 1200°F for 4 hr and furnace cooling. The solution-treated and annealed conditions were those in which the alloys might be expected to

Jan 1, 1959

By Robert Archer

IT is now well known that the structure of aluminum-silicon alloys can be refined in a rather remarkable manner, with consequent improvement of physical properties, by certain treatments applied to the molten metal shortly before casting. The differences between the treated and the untreated alloys are so marked that special terms are used to distinguish them, the untreated alloys being referred to as "normal" and the treated alloys as "modified." The first practical method of accomplishing this result was that of A. Pacz,1 which consists in treating the molten metal with a, salt flux of which the, active ingredient is sodium fluoride. The result can also be brought about, and in a more economical manner, by the addition of small quantities of metallic sodium (or potassium) to the molten alloy shortly before casting.2 The action of the Pacz flux evidently consists essentially in the production of free sodium by the reaction of sodium fluoride with aluminum. The changing of a normal alloy to a modified alloy is referred to as "modification&apos; and any process for accomplishing this result is a "modifying" process. Modified aluminum-silicon alloys were introduced several years ago, and it has been demonstrated both in the laboratory and in commercial practice that it is no simple matter to produce castings having the maximum or nearly the maximum properties which under favorable circumstances can be obtained. The alloys are rather sensitive to small changes in chemical composition, and the modifying process must be carried out in a very particular manner to obtain the best results. Extensive experimental work has been carried out in the laboratories of the Aluminum Company of America with the object of determining the conditions that must be observed to make these alloys of the greatest possible

Jan 2, 1926

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.&apos; on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-&apos; (g S per sq cm)&apos; corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.&apos; The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By I. Tamura, J. O. Brittain, T. Mura

Plain carbon steel in the cold worked or marten-sitic conditions has an internal friction peak at about 250 oC at a frequency of I cps. The influence of substitutional alloying elements on this peak was examined experimentally. The alloys were vacuum melted Co-, Cr-, Mo-, Ni-, and Si-iron (about 3 pct alloying elements), and carburized Si-iron. The internal friction of the alloys in the temperature range 30o to 500 OC was determined by means of a torsion pendulum. The 250 oC peak of the cold-worked alloys was lower in height than that observed in plain C-iron and steel. Carburized Si-iron in the quenched condition had a peak which occurred at a slightly lower temperature than in quenched plain C-steel, but the height of the peak was substantially greater than that found for the same alloy in the cold-worked condition. The activation energy of this peak for martensitic Si-steel was about 35 kcal per mol. ANNEALED a iron has two internal friction peaks due to nitrogen and carbon at 20o and 40o C respectively, at a frequency of 1 cps. If a iron is cold worked, these diffusion peaks become smaller and a new peak appears at about 250o C. The activation energy for the 250o C peak is in the range of 32 to 44 kcal per mol and has an average value of 38 kcal per mo1. It has been experimentally verified that both interstitial solute atoms and dislocations are necessary for the 250o C peak. 3 Wert has also shown that an incubation period precedes the appearance of the 250 C peak.4 With regard to quenched martensitic steel, Ke et al.596 observed two peaks at around 130o and 250o C. They conjectured that the 250o C peak in martensite was due to the same mechanism as the 250°C peak in cold worked a iron, and the 130°C peak was due to the nature of tempered martensite. They did not report the activation energy for these peaks. Chernikova7 found only one peak at about 200° C in tempered martensite. In a previous paperS we reported an activation energy of approximately 40 kcal per mol for the 250° C peak in plain carbon martensitic steels. Ichiyama8 found the activation energy to be about 36 kcal per mol for the 250° C internal friction peak in steels in the martensitic condition. The present authors proposed a theory for the 250°C peak for cold worked and quenched iron and steel.= The theory for the peak is based upon the addition of a strain-energy term to the free energy for the formation of a carbide precipitate due to the presence of a disclocation. The model employed for the relaxation process consists of the growth and solution of a carbide precipitate of critical size as a consequence of an oscillating dislocation. In this report, the influence of substitutional alloy ing elements on the 250° C peak is examined and the experimental results are discussed in terms of our theory for the peak. Most of the experimental work on the alloy steels was confined to the Fe-Si-C alloys.

Jan 1, 1962

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.&apos;-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys&apos; and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By J. D. Defilippi, E. M. Gilbert, K. G. Brickner

FCC chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Transformation to martensite is considered to be responsible for this behavior in some metastable Cr-Mn-N steels. However, very stable Cr-Mn-N steels also exhibit a ductile-to-brittle transition. The results of this study indicate that deformation faulting is the probable cause of the brittle behavior of stable Cr-Mn-N steels. Deformation faulting accounts for the ductile behavior of these steels in a tension test at -320°F and brittle behavior in an impact test at -320°F. Deformation faulting also accounts for the toPological features observed on the fracture surfaces of impact specimens of these steels. FACE- centered- cubic chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Many Cr-Mn-N steels transform to martensite during deformation,l-5 and several investigatorsl-3 have suggested that the brittle behavior of these steels is caused by martensite formation. However, very stable Cr-Mn-N steels also exhibit brittle behavior. Schaller and Zackeyl reported that a very stable Cr-Mn-N steel (less than 3 pct martensite formed at -320°F) exhibited a transition temperature higher than that for steels in which large volume fractions of martensite formed during testing. The explanation given by Schaller and Zackey for this observation was that in the very stable steel the martensite, because of its higher interstitial content, was more brittle than that formed in their other steels. This explanation was questioned by Tisinai and samans4 and Baldwin.6 Moreover, because the toughness of stainless martensite at cryogenic temperatures is generally very low, this explanation does not account for Thompson&apos;s7 observation that small additions of nickel (1 to 3 pct) greatly improve the toughness of high nitrogen (0.35 pct) Cr-Mn-N steels. The present paper summarizes the results of an investigation of the low-temperature brittleness in very stable Cr-Mn-N steels. The importance of the mode of deformation on the toughness of these steels is discussed. Table I. Compositions of the Steels Invertigated, Pet Steel C Mn P S Si Ni Cr N - A 0.09 14.70 0.018 0.011 0.47 0.22 18.40 0.54 B 0.12 14.90 0.001 0.008 0.48 0.14 17.80 0.38 C 0.12 14.95 0.004 0.005 0.62 3.95 18.43 0.38 MATERIALS AND EXPERIMENTAL WORK The compositions of the steels investigated are shown in Table I. Steels A and B had compositions within the limits of a proprietary Cr-Mn-N stainless steel,* whereas Steel C was similar in composition to the proprietary steel except for its 3.95 pct Ni content. All steels were hot-rolled to 1/2-in. thick plate. The plates were subsequently annealed for 1 hr at 2000°F and water-quenched. Standard longitudinal and transverse Charpy V-notch impact specimens were machined from the annealed plates. Duplicate longitudinal and transverse impact specimens were tested at 212", 80°, 32", 0°, -100°,-160°,-200°,-256", and -320°F. Longitudinal tension-test specimens were also machined from the plates and tested at a crosshead speed of 0.05 in. per min at the aforementioned temperatures. The fractured impact and tension-test specimens of all three steels were examined to determine whether martensite had formed during testing. Magnetic, X-ray, electron-diffraction, and electron-microscopy techniques were used to detect the presence of martensite in the highly deformed areas of these specimens. Metallographic examination of highly deformed areas of impact and tension-test specimens revealed the presence of dark-etching bands, such as those shown in Fig. 1. These bands were observed only in deformed samples and were thought to be associated with the low-temperature brittleness of the Cr-Mn-N steels. Accordingly, a sample 1 in. wide by 3 in. long was cut from the 1/2-in.-thick plate of Steel C. This sample was surface-ground to a in. and then cold-rolled 60 pct at -320°F. Thin foils were prepared from the cold-rolled sample and examined in a JEM electron microscope. Brightfield, dark-field, and selected-area diffraction techniques were used to determine the cause of the dark-etching bands. Fractographic experiments were also performed. Impact specimens Of Steels A, B, and C were broken at -320oF, and the fracture surfaces of these specimens were immediately shadowed with carbon. The carbon replicas were examined in a Siemens electron microscope, and attempts were made to correlate the topological features of the fracture surfaces with the deformation mechanisms that could be occurring during an impact test of these steels.

Jan 1, 1970

By W. A. Koehler, M. E. Hinkle

INTRODUCTION THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: I. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of fer¬rous (iron) sulphate and some sulphuric acid. 2. The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages nor¬mally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio¬bacillus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not yet been established. Apparently it does not promote the oxida¬tion of ferrous iron compounds in mine, drainage to the ferric state. The second organism has not been identi¬fied by name but is described as "Gram negative, non-spore-forming rods approxi¬mately 0.4 micron wide by o.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur com¬pounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced percentage of oxygen and increased percentage of carbon dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. ACID COAL MINE DRAINAGE Acid coal mine drainage has been the concern of coal mine operators, industrial¬ists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1948

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j&apos;ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.&apos;-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura&apos;&apos; was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura&apos;s equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By Richard Pearce

H. M. Howe, Boston, Mass. (Communication to the Secretary): One by one our venerated idols are shattered, our cherished beliefs are filched away. Mr. Pearce&apos;s interesting experiments on the effect of an intermixture of coal in expelling arsenic from roasting copper-ores seems at the first blush to spike one of the great cannons of our faith. Plattner, however, is so positive that coal does lead to the expulsion of arsenic that we may well pause before accepting Mr. Pearce&apos;s results as final, and ask whether there is not some explanation of the discrepancy between them and Plattner&apos;s statements. Plattner states that while ferric arseniate decomposes easily under the action of carbonaceous matter with expulsion of arsenic as arsenious oxide (As2O3) and sub-oxide of arsenic (it is now generally thought, I believe, that this supposed sub-oxide is really but a mixture of metallic arsenic and arsenious oxide); cupric arseniate, on the other hand, undergoes this decomposition with difficulty, usually forming a certain proportion of arsenide of copper. Now, may not the whole matter lie just here? Mr. Pearce experimented on an ore containing its arsenic as enargite, sulph-arsenide of copper. This, in roasting, would probably give rise to arseniate

Jan 1, 1890

Jan 1, 1933

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375&apos;C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin&apos; 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos&apos;20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By M. Gangal, B. Paul

It may be seen from Maurer&apos;s survey (Maurer,l 1966) that most of the common methods used in rock drilling today depend upon mechanical loading of the rock. In order to predict the behavior of rock under an imposed system of stresses, it is necessary to have a valid criterion which delineates those combinations of stress which cause macroscopic rock failure from those which do not. Admittedly, the conditions under which brittle materials fracture depend very much upon statistically variable local effects such as inclusions, grain boundaries, minute imperfections, etc. However, it is extremely desirable to be able to predict fracture under complex states of stress by means of a stress-criterion of failure, where, for a given material, the effects of the other variables mentioned are incorporated into a small number of experimentally observable parameters. One of the most successful of these "macroscopic stress criteria" has been the Coulomb-Mohr theory 2,3 (also see Jaeger 4 and Terzaghi 5), modified by the addition of tension cutoffs (Paul 6). At first thought it might seem rather odd that a macroscopic theory is capable of predicting fractures which originate at highly localized random imperfections at an atomic level (or more likely at the level of individual mineral grains in rocks). However, Griffith7 showed that fractures originating near the tips of randomly oriented elliptical cracks lead to the macroscopic stress criterion of failure indicated in Fig. 1 (a). Fig. I (a) is to be interpreted in the following way: P and Q represent the maxi mum and minimum principal stresses (compression is considered positive) in a macroscopically isotropic body; fracture will not occur for any combination of principal stresses lying within the &apos;fracture curve&apos; shown, but

Jan 1, 1967

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K&apos; = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By J. Chipman, H. R. Larson

The data previously reported for the quantity as a function of oxygen pressure at 1550°C have been used to compute the activities of Fe, FeO, Fe2O3, and COO in slags of the ternary system. Activities of the first three have been obtained also for two quasi-ternaries involving fixed CaO:SiO2 ratios. IN a previous paper1&apos; the authors reported the results of an investigation into the effects of oxygen pressure on the composition of various simple slags analogous to some of those which are found in steel-making practice. The ratio of ferric iron to total iron was studied at 1550°C in iron oxide melts to which lime, magnesia, lime-plus-silica, and other oxides were added. The oxygen pressures involved those of air, carbon dioxide, and carbon dioxide plus carbon monoxide in several proportions. Although very low oxygen pressures could not be used, the slag-metal equilibrium studies of Fetters and Chip-man&apos; permitted extending the results to slags in equilibrium with iron. For the ternary system CaO-FeO-Fe,O, the oxygen pressure-composition relationship has been determined from zero percent lime to lime saturation over an oxygen pressure range from air to that represented by equilibrium with liquid iron. Lime and silica were added to iron oxide in the ratios 0.54, 1.306, and 2.235 to form three quasi-ternary systems which were also studied over the entire region of liquid melts at 1550°C. Ternary Gibbs-Duhem Equation Wagner" has developed a method by which the activities of two components of a ternary system can be calculated if&apos; the activity of the third component is known throughout the composition range being considered. The fundamental form of the Gibbs-Duhem equation for ternary systems is N, d In a, + N2 d In a, + N3 d In a3 — 0. Wagner has developed a usable form of this equation by introducing the term y = N3/(N3 + N1) and rearranging the equation to give (? In a1/?N2)x = -y/(1-N2)2 (? In a2/?y) x2 N2/1-N2 (? In a2/?N2) y To apply this equation to the slag system CaO-FeO-Fe,O,, the activity of one of these components must be known. However, the only activity which is known from the experimental data is the activity or pressure of oxygen in the gas phase with which the slag is in equilibrium. The activity of oxygen in the slag can be defined as the square root of the oxygen pressure. In order to use oxygen as one component, the composition of the slags must be converted to the basis Fe-O-CaO. Oxygen, exclu-sive of that contained in CaO, then becomes com-ponent 2 in Eq. 1, Fe is selected as 1 and CaO as 3. Then y = Ncao/(Ncao + NFe). Eq. 1 then becomes (? In a fe/? Nx) y = -y/(1-No)2 (? In ao/?y) xp - No/ 1- No (? In ao/ O No) y. In order to evaluate Eq. 2, the boundary conditions must be known. The obvious choice of a standard state for iron is to assign slags in equilibrium with iron an activity of one. Then In a,., or log aFe, which is substituted for convenience, is determined by integrating along a line of constant y from the slag in equilibrium with iron to the composition at which log a,, is to be determined. Mathematically this can be expressed as log aFe (Nlog y) = log a&apos;Fe + (? log a Fe/? No) dNo where the primes indicate equilibrium with liquid iron and a&apos;Fe = 1. When Eq. 3 is integrated along a line of constant y, the following is obtained: log a Fe (No, y) = - y No ?/ No ? y ( log ao/(1- No)2) No d No - No/1-No d log ao. Lime-Iron Oxide Slags Iron Activity: The oxygen pressure of lime-iron oxide slags is shown in Fig. 1 as a function of j, de-fined as j = Fe+++/(Fe++ + Fe +++) for various constant mol percentages of lime. The j values at 0 to 60 pct lime were then determined for oxygen pressures of 1, 10-1, etc. to 10-" atm. For purposes of calculation, the line for zero percent lime was extrapolated to

Jan 1, 1955