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By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By H. E. Stauss, G. Sandoz

THE purpose of this note is to draw attention to the possibility that a melt may be contaminated by a material not in direct contact with it by means of gaseous intermediate agents. In recent years silicon has assumed a position of importance because of its use in rectifiers and transistors and close attention has been required to control of both purification and contamination during all stages of preparation.' This note reports the observation that a graphite heater may have contaminated silicon ingots without direct physical contact through reactions that developed gaseous products. Several ingots made with the equipment of Hino and Stauss,2 using a graphite heater in a dried helium atmosphere, were found to have a small amount of a very hard substance on the free surface. X-ray analysis by F. W. von Batchelder showed the sub- stance to be Sic. Similar contamination was not found when the heater was tantalum, indicating that the carbon had not come from an original impurity in the silicon powder. One source of the carbon could have been volatile matter released from the graphite heater. This heater had been used about ten times at the time of the observations. A second source of carbon could have been a direct reaction between the quartz crucible and the graphite heater to form CO, or an indirect reaction involving a crucible-melt interaction and volatile SiO as an intermediate product. Such reactions should have developed Sic on the heater; and in fact a yellow powder did form on the inside of the graphite heater although its composition could not be determined. References 'H. C. Torrey and C. A. Whitmer: Crystal Rectifiers (1948) Chapter 10. New York. McGraw-Hill Book Co. 2 J. Hino and H. E. Stauss: Trans. AIME (1952) 194, p. 656; Journal of Metals (June 1952).

Jan 1, 1954

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By G. Wranglen

On account of the possibility of isolating carbides in steel it is generally assumed that the electrode potential of iron carbide is more noble than that of ferrite.1,2,3,4,5 Differences from 0.032 V1 to 0.4 V4 have been recorded. However, it is important to realize that the more noble behavior of cementite in relation to ferrite is not an issue of thermodynamics but of reaction kinetics. Theoretically, cementite is less noble than ferrite, which is a direct consequence of its thermo-dynamic instability. With the value ?F°298 = +4700 cal per mol for the free energy of formation of cementite6 it is easily calculated that the electrode

Jan 1, 1950

By Paul A. Beck

THE occurrence of the (100) [lOO] or "cube" texture upon annealing of cold-rolled copper has been much investigated.' The conditions favorable for its formation were found to be a high final annealing temperaturez or long annealing time," a high reduction of area in cold rolling prior to the final anneal,' and a small penultimate grain size." The effects of penultimate grain size and of rolling reduction were found by Cook and Richards4 to be interrelated in such a way that any combination of them giving lower than a certain value of the final average thickness of the grains in the rolled material leads to a fairly complete cube texture with a given final annealing time and temperature. Also, according to the same authors, at a higher final annealing temperature a larger average rolled grain thickness, i.e., a lower final rolling reduction, is sufficient than at a lower temperature. These somewhat involved conditions can be understood readily on the basis of recent results obtained at this laboratory. Hsun Hu was able to show recently by means of quantitative pole figure determinations that the rolling texture of tough pitch copper, which is almost identical with that of 2s aluminum: may be described roughly as a scatter around four symmetrical "ideal" orientations not very far from (123) [112]. In the case of aluminum, annealing leads to retain-ment of the rolling texture with some decrease of the scatter around the four "ideal" orientations, and to the appearance of a new texture component, namely the cube texture." A microscopic technique, revealing grain orientations by means of oxide film and polarized light, showed that the retainment of the rolling texture is achieved through two different mechanisms operating simultaneously, namely "re-crystallization in situ," and the formation of strain-free grains in orientations different from their local surroundings, but identical with that of another component of the rolling texture. Thus, a local area in the rolled material, having approximately the orientation of one of the four "ideal" components of the texture, partly retains its orientation during annealing, while recovering from its cold-worked condition, and it is partially absorbed at the same time by invading strain-free grains of an orientation approximately corresponding to that of another "ideal" texture component. The reorientation here, as well as in the formation of the strain-free grains of "cube" orientation, may be described as a [Ill] rotation of about 40°, see Fig. 1 of ref. 6. The preferential growth of grains in such orientations is a result of the high mobility of grain boundaries corresponding to this relative orientation.' " It appears very likely that in copper the mechanism of the structural changes during annealing is similar to that observed in aluminum (except for the much greater frequency of formation of annealing twins in copper). In both metals the new grains of cube orientation have a great advantage over the new grains with orientations close to one of the four components of the rolling texture. This advantage stems from their symmetrical orientation with respect to all four retained rolling texture components of the matrix; they are oriented favorably for growth at the expense of all of these four orientations. As a result, the growth of the "cube grains" is favored over the growth of the others, as soon as the new grains have grown large enough to be in contact with portions of the matrix containing elements of more than one, and preferably of all four component textures. It is clear that this critical size is smaller and, therefore, attained earlier in the annealing process if the structural units, such as grains and kink bands, representing the four matrix orientations are smaller, i. e., if the average thickness of the rolled grains is smaller. Hence, for a given annealing time and temperature, a smaller penultimate grain size and a higher rolling reduction both tend to increase that fraction of the annealing period during which the above condition is satisfied. Consequently, the percentage volume of material assuming the cube orientation increases. The same is true also for increasing time and temperature of annealing when the penultimate grain size and the final rolling reduction are constant, since the average size attained by the new grains during annealing increases with the annealing time and temperature. For the same reason, at higher annealing temperatures a given volume percentage of cube texture can be obtained with larger rolled grain thickness (larger penultimate grain size, or smaller rolling reduction) than at lower annealing temperatures. The well-known conspicuous sharpness of the cube texture may be interpreted as a result of the fact that selective growth of only those grains is favored that have an orientation closely symmetrical with respect to all four components of the deformation texture and exhibit, therefore, a high boundary mobility in contact with each. The effect of alloying elements in suppressing the cube texture, as described by Dahl and Pawlek,' appears to be associated with a change in the rolling texture. For face-centered cubic metals, such as copper, which do exhibit the cube texture upon annealing, the rolling texture is always of the type described above, i. e., scattered around four "ideal orientations" of approximately (123) [112]. The addition of certain alloying elements, such as about 5 pct Zn or 0.05 pct P in copper, has the as yet unexplained effect of changing the rolling texture into the (110) 11121 type. This texture consists of two fairly sharply developed, twin related components. In such cases, as in 70-30 brass and in silver, the annealing texture again is related to the rolling texture by a [lll] rotation of about 30°, however, because of the different rolling texture to start from, it has no cube texture component. At higher temperatures, both in brassm and in silver," grain growth leads to a further change in texture: A [lll] rotation of the same amount, but in reversed direction, back to the original rolling texture.

Jan 1, 1952

By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.'-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard' has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn' who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99' pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.' Recent work' indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken's 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. 'V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By L. S. Richardson, N. J. Grant

REACTIONS of oxygen and nitrogen at low pressures with titanium have recently been studied by a number of investigators.1-3 Gulbransen and Andrew' noted that the reaction with nitrogen followed the parabolic rate law whereas the reaction with oxygen deviated slightly from this law in the temperature range 300° to 800°C. In the work reported here, commercial titanium (75 A) was used as the test material. Cylinders 2.5 in. long and 0.25 in. in diameter were machined from heavier bar stock. The test pieces were given a metallographic finish, immersed for 30 min in cold concentrated HC1, washed in water, then acetone, and dried with lint-free cloth. Reaction rates were determined in a modified Sieverts type apparatus by measuring the decrease in gas pressure of the reacting gas contained in a constant volume. The amount of gas added could be measured in a calibrated gas burette to an accuracy of 0.01 mm. During the course of a run the temperature never varied by more than 10°C and then only for brief moments. After placing the specimen in the furnace, the system was first evacuated for 12 hr at room temperature, and then flushed with purified argon five times, adsorbed gases being discharged during this period from the glass system with a high frequency spark coil. The flushing and discharging were repeated at 400°C. This rather involved procedure was found necessary after a number of trial runs indicated extraneous effects traceable to the system. Reaction periods up to 2 hr were used, at initial gas pressures of 0.2 to 0.5 atm. Experimental Results Fig. 1 shows the decrease in oxygen pressure for tests at 0.5 atm at various temperatures as a function of the square root of the time. Deviations from linearity are minor and the parabolic rate law is obeyed. Fig. 2 shows the same plot for the nitrogen reaction. A definite deviation from linearity is noted; however, it is probable that the higher initial rates are caused by the presence of small amounts of oxygen contamination, the initial faster rate changing to the slower rate after about 5 to 10 min. Calculations of the rate constants were made on the basis of the latter portion of the curves. The parabolic rate law constants calculated from these curves are shown for oxygen and nitrogen in Fig. 3. In spite of some scatter the average curves are quite definite. Changes in gas pressure of the order of 20 pct did not result in a measurable change in the rate law constants. The activation energy for the oxygen reaction was calculated to be 47,400 cal per mol (above 700°C), which is not in agreement with the value quoted by Gulbransen and Andrew' for lower temperatures, their value being 26,000 cal below 600°C. The activation energy for the nitrogen reaction was calculated to be 45,400 cal per mol above about

Jan 1, 1955

By H. C. Vacher, C. J. Newton

EXTENSIVE investigations in the field of residual strain measurement by X-ray diffraction have been made by Bollenrath, Hauk, and Osswald,1 by Smith and Wood,2'3 by Greenough; by Rosenthal and Norton." and many others. Since X-ray strain measuremeits apply only to those crystals of the test body which are of the proper condition and orientation to diffract and since the residual strains revealed may be accompanied by either body or tex-tural stresses, there has been considerable disagreement among investigators with respect to the validity of conclusions in this field. Although the experi-mentors have employed a variety of loading schemes, surface preparations, and X-ray wave lengths, the observations almost invariably have been made only on the outer surfaces of the specimens. The present note is not to be construed as an exposition of a new method of stress analysis by X-ray strain measurements on sections but as a presentation of some results which point to interesting possibilities for further experiments with sections. The two test rods used in this study were of ingot iron annealed at 910°C. The initial length of the gage section was 2 in. and the diameter was 0.415 in. Cross-sections were cut from the ends of the annealed rods to provide strain-free material. The tensile rod was axially loaded the desired amount in a commercial testing machine. A 1 in. portion of the gage length was cut from the other rod and was subjected to compression in the same machine. Details of this plastic straining of each rod are given in the upper half of Table I. A half-cylinder piece about 1/4 in. long was obtained by making a short longitudinal plane cut containing the axis of the rod near the center of the gage length. From adjacent material a disk about 1/8 in. thick was cut to provide the cross-section specimen. Later another section was cut from this same region with an angle of 30" between the normal to its surface and the axis of the test rod. A cross-section and a longitudinal section were cut from the compression rod in a similar manner. All of these as well as the strain-free cross-sections were mounted in Bakelite and used as specimens for the following X-ray strain measurements. During the course of the study, it became apparent that the condition of the surface of a specimen was a highly critical factor. One of the annealed strain-free specimens as a control was subjected to about 24 hr of polishing with fine alumina, interrupted about every 2 hr for etching with 1 pct nital. Its lattice parameter was determined at intervals from measurements on back-reflection X-ray diffraction patterns, which were calibrated with diffraction from tungsten powder. The parameter gradually approached the value found in the literature for strain-free iron and remained there, within the limits of the experimental error. This determined a long polishing and etching procedure which was adopted for all the specimens and which gave X-ray results from the surfaces believed to be representative of each specimen as a whole. A large number of back-reflection patterns were made with cobalt and chromium radiation, all at normal incidence. Except for some preliminary stationary exposures made to monitor the removal of cold work from the surfaces, each exposure was made with the specimen slowly translating and the film slowly rotating. In appropriate cases a thin layer of a standard metal powder, tungsten with cobalt radiation and silver with chromium, was dusted over a film of vaseline on the surface of the specimen to serve to calibrate the X-ray patterns. After the preliminary work, four films were made,

Jan 1, 1956

By E. S. Machlin

THE function of this paper is to present certain results based on the fact that the strain energy arising from the solution of out-of-size solute atoms into the solid matrix is free energy and not internal energy, and that this strain energy is almost wholly shear strain energy as Zener1 pointed out. One natural consequence of this fact is an expression for the excess entropy of mixing due to the strain energy. Also, a derivation of the integral molar free energy of mixing partitioned to strain energy will be made using the model of Lawson2 and thermodynamics. This derivation has the advantage of showing in a simple way the assumptions involved in Lawson's treatment. The excess entropy of mixing partitioned to strain energy can be derived in two ways. The first way makes use of the fact that the strain energy is almost wholly in the form of shear strain energy. In this case, as Zener1 pointed out, the change in entropy due to the addition of shear strain energy is to a first approximation given by ?S/?? p,T = - ?lnµ/?T p,? Hence, the excess entropy of mixing partitioned to strain energy will be given by Sx ? = ?S/?? p,T Gx ? = - ?lnµ/?T p,? Gx ? where, Gx ? is the relative integral molar free en- ergy partitioned to strain energy; S is the entropy; is the shear strain energy; µ is the shear modulus; T is the absolute temperature; p is the pressure; and ? is the shear strain. Zener,1 as well as others, has pointed out that the shear strain energy stored in a compressible isotropic solid due to the insertion of an off-size incompres-sible sphere into a spherical hole in the solid, is approximately given by 2/3 µ/O (O°I - O)2 where a is the volume of spherical hole and no , is the volume of sphere. If we now consider the introduction of one mol of such spheres into an infinite volume of solid, then the relative partial molar free energy excess due to strain energy alone is GM ? = 2/3 µ/v (v ° 1 - v)2 where v is the molar volume of solvent and v°1, is the molar volume of pure solute type 1. Let us consider that these spheres are the two types of atoms in a binary solution, then there will be a similar relation for solute 2. The total relative integral molar free energy excess due to strain is then, to the approximations stated above GM ? = GM ? x1 + GM2 ? x2 = 2/3 µ/v [(v ° 1 - v)2 x1 + (v ° 1 - v)2 x2]. Lawson's relation for the strain energy can be de-

Jan 1, 1955

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-' have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson's reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

By R. Maddin, W. R. Hibbard

A series of X ray experiments conducted by G. I. Taylor' in 1927 and later substantiated in 1939 by J. A. Collins2 both on axially strained aluminum single crystals, revealed evidence that during single slip crystallite rotation occurs in such a manner that " all parts of the material rotated about the transverse direction in the plane of slip."l The actual method of preparing the specimens for X ray examination is not discussed in detail by Taylor except to say that "this specimen was cut parallel to the plane of slip, as calculated from measurements of marks in the surface of the specimen. It was ground and etched till the effect of the new cuts had disappeared. This was verified by applying the same treatment to an un-distorted specimen. The X ray reflectionsl in this case were perfect ones."' Collins, on the other hand, cut his crystals in a mechanical shaper. These surfaces were polished on No. 1, No. 1/0, No. 2/0 and No. 3/0 papers and on a broadcloth lap using No. 600 alundum as a polishing medium. "Finally, the surface was deeply etched in Tucker's reagent. An unde-formed crystal was prepared in the manner described and X rayed to determine whether or not the machining and polishing operations had produced any strain or distortion in the crystal. The Laue spots all seem to be sharp, free from tails and streaks indicating no detectable strains had been introduced in the crystals." Taylor's X ray technique involved the use of "homogeneous X rays from an iron anti-cathode"; whereas Collins used Ka radiation of copper at 31kv and 20 milliamperes. Glancing angle X ray photograms were taken (1) with the axis of rotation of the spectrometer table in the plane of slip and at right angles to the slip direction, and (2) with the axis of the spectrometer table lying along the slip direction. However, eight minute exposures were used in each case and the angle setting of the spectrometer table was increased by one degree for each exposure. With the discovery of the action of three slip systems3 in the plastic deformation of single crystalline alpha brass where, formerly, only one had

Jan 1, 1950

By J. Gordon Parr, D. H. Polonis

IN a previous study of hypereutectoid Ti-Ni alloys' a substructure was observed in quenched powder specimens when the constitution was 100 pet retained ß body-centered-cubic phase. The alloy powders were quenched from 1000°C by a blast of helium gas and precautions already described were observed throughout the work, to minimize contamination. Ogden et al.2 have previously observed subboundaries in the ß phase of a Ti-Mn-N alloy; but this structure was attributed to nitrogen-rich a precipitation. The nitrogen content of the Ti-Ni alloys does not exceed 0.02 pet and the quenching rate was sufficiently rapid to suppress precipitation reactions. Since X-ray diffraction results have confirmed the absence of any second phase which might account for this phenomenon, it seems unlikely that this substructure is explicable in terms of nitrogen content. Fig. 1 shows the substructure in adjacent grains of 100 pet ß phase in a quenched 6 atomic pet Ni alloy. Fig. 2 shows adjacent ß grains in a similarly treated alloy; one grain contains marked intracrys-talline boundaries and the other is completely free from any substructure. The suberystals appear to have fairly regular shapes, suggesting a regular orientation relationship among them. Tempering the retained ß structure at temperatures below the eutectoid eliminates the substructure at an early stage of ß decomposition. At the present time it is possible only to guess at an explanation for this subboundary phenomenon, since very little work has been reported on substructures resulting from phase changes. It is believed that the present phenomenon is due to poly-gonization resulting from unrelieved stresses set up

Jan 1, 1957

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By L. Guttman

LESTER GUTTMAN* The question of whether classical thermodynamics alone imposes any lower limit to solid solubilities was raised during a discussion among various members of the Institute for the Study of Metals. Although our conclusions are not new,1 they may be worth reiterating, since confusion on this subject seems to persist. In a binary system (A,B), the conditions for equilibrium, at constant pressure and temperature, between a solid solution and a liquid solution are µAs = µAl [la] µBs = µbl [lb] Here µ denotes the chemical potential either of component A or B, as shown by the subscripts, and the superscripts s and l refer to the solid and liquid solutions, respectively. These two conditions are just sufficient to determine the compositions of both phases. Suppose, however, that the solid phase is found experimentally not to contain any of component B; then we cannot evaluate µbs, which is defined by Here nAs and nBs are the number of mols of A and B, respectively, in the solid, whose free energy is Fs. Eq lb cannot be used, but it is no longer needed: we stated at the outset that the solid has the composition "pure A," and only the liquid composition need now be determined, from Eq la. All the equilibrium properties of the system can be derived from Eq la rigorously and simply. Hence there is no purely thermodynamic reason to exclude phase diagrams which show precisely zero solid solubility. Marsh2 has objected to such diagrams as implying that even the transformation of pure A begins at the eutectic temperature. In any case, the user of the diagram must have a certain minimum knowledge of how to interpret it, and it would seem simpler to remember the general rule that eutectic temperatures have no significance for pure components, rather than to show, say, by broken lines, on a scale which will often be exaggerated, a hypothetical solid-solubility about which we know only that it is less than a certain amount. The case of an intermetallic compound in equilibrium with a binary liquid solution does not require a separate treatment since nothing in the foregoing was dependent on the nature of the components. Therefore, thermodynamics alone does not exclude the possibility that (intermetallic) compounds may exist with compositions always precisely those given by their chemical formulas. With the aid of extra-thermodynamic methods, one may conclude that the solubility of one solid in another is never exactly zero. On the other hand, one would generally expect that the solubility will be small unless the components resemble one another (as do the metals), or form weakly-bound crystals. Therefore, it is useful to know that when there is no direct evidence for solid-solubility, one may neglect it without violating thermodynamic principles.

Jan 1, 1950

By R. L. Segall

AN unusual thermal etch figure in copper is described and an explanation in terms of twinning is suggested. A flat polycrystalline specimen of OFHC copper cut from a rolled sheet was electro-polished in orthophosphoric acid and annealed at 950°C in a vacuum of approximately 10-3 mm Hg for 2 hr. The specimen was found to be thermally etched, the markings on the surface being consistent with the assumption that they were the traces of the (111) planes which are developed preferentially because they have the lowest free energy. However, on one grain (the grain shown in Fig. 1) the traces formed an almost regular pentagon and at first sight it seemed unlikely that they could all be (111) traces. These traces were studied further because it was thought that they might be a type of growth spiral. A fringe pattern showed that this was not so, the grain being sensibly flat and the only features having steps were the striations and the faint curved line passing out from the center of the pentagons. To obtain some additional information, the specimen was deformed in tension. The effect of the stress was first to cause the appearance of lines running from the centers to the apexes of the pentagons and then to tilt the five segments so formed. At a much greater stress, appreciable slip appeared on the grain; these effects can be seen in Fig. 2. The micrograph was taken at a fairly late stage in the deformation and the tilting is quite marked. The magnification is the same as in Fig. 1, and although some slip can be seen it could be observed better by varying the illumination and using higher magnifications. In each segment of the grain, slip (which takes place on the (111) planes) was parallel to the side of the pentagon in that segment. The marked changes in direction of slip from segment to segment seemed to be incompatible with the presence of a regular array of subgrains. These results suggest that some of the five segments were twins. If this is so, since the twinning plane in copper is the (111) plane, the radial lines must be traces of the (111) planes on the surface. From the symmetry of the striations about the radial lines, these planes must be almost perpendicular to the surface. The angle between <III>directions in face-centered-cubic copper is 70&apos;32&apos;. If, in Fig. 3, OAB (triangle 1) is taken as matrix and OA, OB are (111) planes viewed edge on, then AB is in the correct direction to be the trace of either of the other two (111) planes on the surface. If triangle 2 is the twin (about the (111) plane perpendicular to the surface and containing OB) of triangle 1, then once again it can be shown that all lines are traces of (111) planes. Similarly, triangle 3 is the twin of triangle 2, 4 of 3, and 5 of both 4 and 1. (The sequence is, of course, quite arbitrary.) However, if this were the case there would be a discrepancy of 7&apos;20&apos; to be accounted for. It is suggested that the faint curved line passing outward from the center of the pentagon represents either a low angle boundary or a sixth small twin. The slight step shown by the fringes at this line might be an indication that the former is the case. This explanation does not account for the coincidence of obtaining a grain whose surface must be so close to (110) and obtaining the curious twinning described previously; it would be of interest to find a specific mechanism for this.

Jan 1, 1958

By P. A. Toynbee, D. G. Wilson

The combustion performance of sub-bituminous slack coal is greatly improved by the removal of the smaller size fractions. Screening processes are not well suited to the size separation, at 1/8 in. or 1/16 in., with coals which are normally wet, and the use of an alternative size-separation device has been investigated. It is felt that this classifier might be applied equally well to other minerals in cases such as this, where precise size limits are not essential. Coal is dropped as a curtain onto a curved metal plate, shaped rather like a ski-jump. The smaller particles, slowed up in their free fall to the plate and also by contact with the metal, leave the plate with a lower horizontal velocity; they can be separated from the larger particles by virtue of their shorter trajectory. The principle of the classifier is obvious from the diagram (see Fig. 1) which shows also the positions, relative to the curved plate, of the point of coal feed and of the dividing plate which separates the streams of coal particles. The horizontal distance between the curved plate and the dividing plate is varied in the tests. It is designated in the general case, by X. Tests were carried out using slack coal with a free moisture content higher than that expected in any commercial operation. The results given in Table I. show the percentage recovery of upgraded product, and the cumulative screen analysis of both the upgraded and reject material, for three different positions of the dividing plate. The results show, for example, that the original coal can be upgraded, with a recovery of 80%, to reduce the minus 1/8 in. frac-

Jan 1, 1965

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,&apos;"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By R. A. Bergman, C. J. B. Fincham

THERMODYNAMIC properties of many high-temperature systems containing sulfur, such as slags, metal sulfides, and solutions of sulfur in liquid metals, have been studied by means of equilibration with known gas mixtures.&apos;" This method presupposes a complete and accurate knowledge of the thermodynamic data for all possible components of the gas phase at high temperatures. However, a survey of the data available up to 1952 on the thermodynamics of gaseous sulfur species and compounds, by Richardson and Jeffes,&apos; showed that there was considerable uncertainty in the values of the free energies of formation of S, SO, HS, and CS. In many cases, this uncertainty made it impossible to decide whether or not these species would form a significant proportion of the sulfur present in the gas phase in any given system. After the review by Richardson and Jeffes had been published, St. Pierre and Chipman6 measured, by an indirect method, the free energy of formation of SO. This also enabled a clear choice to be made among the three possible spectroscopic values for the dissociation energy of S2 into atoms10 thereby determining the free energy of formation of S from S2, and fixing the free energy of formation of HS more accurately" The main purpose of the present investigation was to measure the free energy of formation of CS, which was still in considerable doubt. For example, at 1600°C, it could be estimated to be +6 +25 kcal per mole,* most of the uncertainty being in the * Based on the dissociation energles of CS6 and S2,5 the heat of sublimation of graphite, and, the assumption that the entropy of formation of CS is the same as that of CO. value of the dissociation energy." A secondary purpose of the investigation was to determine more accurately the equilibrium sulfur pressures over dilute solutions of sulfur in carbon-saturated liquid iron. General Method Dilute solutions of sulfur in liquid iron, saturated with carbon, were brought to equilibrium at 1600" and 1800°C, with known gas mixtures consisting, initially, of A and CS2. After equilibrium had been reached, the melts were quenched and analyzed for sulfur. In the high temperature region of the furnace, an equilibrium was set up between the various possible sulfur species and compounds in the gas phase; namely, CS2, CS, S2, and S. (It can be calculated that the amounts of S6 and S, are negligible at these temperatures:) Morris and Bueh17 and Kitchener, Bockris, and Libermana had previously studied the corresponding

Jan 1, 1958