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By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.', ' No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers' it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.' The majority of values reported in the literature7-', ' were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.' cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

Jan 1, 1954

By Clifford Frondel

THE aluminum oxide known as corundum has several varieties that have been used as gem materials since ancient times. These include the red variety called ruby, the blue variety sapphire, and the asteriated types of ruby and sapphire. Asteriated sapphire was known to the ancients under the name of astrios, and descriptions of this gem were given by Pliny and other early writers. The relation of these gem materials to each other as varieties of a single species, corundum, was first clearly established by Haüy in 1805 and J. M. Güthe1 in 1809. Natural gem corundum is obtained principally in Ceylon, Siam, Burma, India, and Australia. Star sapphires and rubies always have been highly prized and in recent years have become particularly popular in the United States. Natural star rubies of large size and fine quality are extremely rare and rank with large and fine emeralds and diamonds as the most valuable of gem stones. Interest thus attaches to the recent success in commercially synthesizing star sapphires and rubies of a size and perfection unmatched by nature.

Jan 1, 1954

By H. Buttner, F. H. Udin, J. Wulff

GRAIN boundaries, the interface between adjacent crystals differing only in respective orientation, have been the object of much experimental and moderate theoretical attention for many years. The earlier experimental work was primarily concerned with the effect that grain boundaries have on the physical behavior of metals, while the basic nature of the boundaries themselves drew only secondary attention. A complete turnabout has been witnessed in more recent years, however, as researchers are now undertaking investigations bearing as directly as possible on the character and physical properties of the grain boundary. Quite comprehensive reviews of the past literature on the subject of grain boundaries have been reported on numerous occasions by various authors, and together these references represent a thorough coverage.'-? It becomes evident in these reviews and other papers"" that the properties of grain boundaries can be explained by regarding a grain boundary as a crystalline region of transition between two unmatched grains. Studies show that grain boundaries have a definite interfacial energy. By measuring the geometry about a point where three interfaces meet in equilibrium, the energy of any two boundaries can be measured with respect to the third. If the absolute interfacial energy of one boundary is known, the absolute energy of the other two boundaries can be calculated. This apparently holds true for any system of phases and interfaces.""25 Most studies have been carried out on solid-solid or liquid-solid systems, or systems of both. However, if about the point of intersection one phase is vapor and the other two are disoriented grains, then two interfaces are surfaces, and one is a grain boundary. Investigations leading to relative grain boundary energy for this particular system have been made by Fullman,23 Greenough and King," and Bailey and Watkins." Herring" treats the system mathematically and arrives at an equation, which appears as Eq. 1, in a form consistent with the reference angles indicated in Fig. 1, ( d?1 ?n = x sina + cosa ( ------- 2 ?2 Sinß da + C0Sß (d?2/d As the system of interfaces comes to equilibrium, a groove of angle appears at the intersection of the grain boundary with the surface, an effect first observed by Rosenhain and Humfrey." Eq. 1 is essentially a summation of the vertical components in Fig. 1 set equal to zero, where ?1 and ?2 are surface tension vectors lying along the side of the groove at point 0 in the groove root. The differential vectors represent the forces tending to rotate the surface into a position that will expose a crystal cleavage surface of lowest energy. Chalmers, King, and Shuttleworth- simplify Eq. 1 by assuming the differential vectors equal to zero, ?1 = ?2= ?Surface and arrive at the following equation: ?B = 2?s cos [2] Greenough and King24 use Eq. 2 for determining the grain boundary energy of silver using prepared bi-crystals of known orientation. Bailey and Watkins25 have done the same for copper, as did Chalmers and others on lead. These authors report the grain boundary values as ratios relative to the surface energy. In the above work, the orientation of grains forming the grain boundary in all cases was controlled so

Jan 1, 1954

By C. Goldberg, R. H. Wynne

WHEN using an optical goniometer to determine crystal orientation' it is advantageous to use a preferential etchant so that the etch pits have plane faces which are parallel to crystallographic planes, all of which are of the same "form." "Westinghouse Silver Etch" (WAg), a preferential etch for germanium, is made up as follows: 40 ml of 49.7 pct hydrofluoric acid, 20 ml of 70.7 pct nitric acid, and 40 ml of distilled water containing 2.0 g of silver nitrate. Examination of metallographs of WAg etched surfaces (Fig. 1, for example) indicates that, regardless of crystal orientation, the faces of the etch pits are (111) surfaces. Optical goniometer examination of these WAg etched surfaces also indicates that the faces of the etch pits are (111) surfaces, i.e., all bright reflections are from (111) planes. When using an optical goniometer of the type described by Barrett,' not only (111) reflections from a WAg etched germanium surface but also other reflections of lower intensity will be observed. These latter reflections can cause confusion. We have used an optical goniometer made from a war surplus astrocompass and a galvanometer lamp. The reflections are observed by using the goniometer in a darkened room and letting the reflected light be in- cident upon a piece of white paper. The resulting decrease of goniometer sensitivity enables (111) reflections only to be observed. This in turn permits the crystal orientation to be determined in a matter of minutes, since only two measurements are necessary. The authors wish to acknowledge the help received from R. E. Davis who assisted in making the metallographs and aided the authors in the interpretation of the metallographs.

Jan 1, 1954

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 L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:' This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By W. A. Backofen, B. B. Hundy

THE pole figure interpretation in a recent paper' on the torsion texture of copper was questioned in discussion,2 nd a simpler alternative interpretation was proposed. In the hope of reaching a positive decision in favor of one or the other, further studies were undertaken with 70-30 brass and Armco iron. This additional work has not answered all the questions about torsion textures, but the new pole figures do offer support for the original interpretation and show that the texture is more complicated than the alternative suggests. From the previous paper,' the appropriate method of describing the texture in a twisted bar is known to be a pole figure plotted on a plane tangent to the surface of the bar. The axes of the pole figure are chosen to coincide with directions in the tangent plane which are parallel and at right angles to the bar axis (the longitudinal direction, L.D., and the transverse direction, T.D.), for these directions define symmetry axes of the texture. Therefore any ideal orientation that might be selected to represent the texture gives the crystallographic plane parallel to the tangent plane and the crystallographic direction parallel to the axis of the torsion specimen. A unique texture was assumed in the original interpretation, and the four ideal orientations, (112) [111], (111) [112], (110) [001], and (112) [131], were used in its description. Of the four orientations, the first three provide possible slip directions along the direction labeled T.D. in the pole figure, which is one of maximum shear stress in a specimen being twisted. The alternative, however, simply considered the texture to be made up of two components, one a [Ill] alignment along the specimen axis with a random orientation about the axis as in the wire texture, and the other a superimposed orientation (110) [0011. Experimental evidence for this simpler interpretation was derived from two observations: 1—twisting did not alter the orientation of a single-crystal torsion specimen of a brass in which an octahedral plane was perpendicular (and a [Ill] direction parallel) to the axis, and 2—deformation bands with approximately the (110) [001] orientation were seen to develop in the crystal during the test. The new pole figures were obtained with a brass and an iron torsion specimen of 3/4 and 1 in. gage length diameter, respectively. After annealing, polishing, and twisting, seven rods, about 0.030 in. in diameter and with different orientations, were prepared from material near the surface of each specimen; these were required for the method of constructing pole figures by using a Geiger counter as developed by Norton.5 Since the shear strain gradient in plastic torsion is linear, it was readily computed that the material supplying the brass rods had been subjected to a shear strain of about 3.2, and that supplying the iron rods had received a shear strain of about 2. All details concerning specimen design, testing procedure, rod preparation, and use of the Norton technique can be found in ref. 1. Only this procedure was followed in working out the (111) and (100) pole figures for brass, Figs. 1 and 2. However, X-ray photograms were also involved in the construction of the (110) pole figure for Armco iron, Fig. 3. The photograms were made according to the conventional transmission diffraction technique using a small sheet taken parallel to the specimen surface and etched to a thickness of about 0.0025 in. They were especially important in locating the boundaries

Jan 1, 1954

Jan 1, 1954

By P. A. Fisher, J. B. Wilson, D. J. Whitehead, C. J. P. Ball, A. C. Jessup

The properties of a new magnesium alloy ZT1 containing 3.0 pct Th, 2.5 pct Zn, 0.7 pct Zr are described. The alloy possesses good creep and fatigue resistance up to 650°F, is free from microporosity, and is readily sand-cast. ZT1 is shown to be superior to zinc-free Mg-Th-Zr alloys. THE advent of the jet engine created a demand for a light sand-casting alloy capable of being cast into large complex shapes and capable of resisting creep at temperatures up to 500°F. This demand has been largely met by alloys of the magnesium-cerium mischmetal-zirconium types, containing about 3 pct Ce mischmetal and 0.7 pct Zr, typified by Elektron magnesium alloys MCZ and ZREI, the latter alloy also having a zinc addition of 2.5 pct. These alloys utilize the valuable properties at elevated temperatures conferred by the addition of rare earth metals to magnesium, a fact which has been known for many years and discussed by several investigators.1-1 Murphy and Payne8 showed that the addition of the powerful grain-refining element zirconium to Mg-Ce mischmetal alloys produced alloys with attractive room temperature properties combined with good creep properties and castability. With the increasing power of modern jet engines the temperatures to which some of the magnesium parts are subject are likely to exceed the safe working range of the cerium-mischmetal-containing alloys, and at the beginning of the research considerable interest had been shown by aeroplane engine designers in a magnesium sand-casting alloy suitable for service at higher temperatures, e.g., 600°F and above. At an early stage in the development of this type of alloy a check on the fatigue properties at elevated temperatures indicated that, since the fatigue limit even at 108 eversals was appreciably higher than any permissible creep stress, the main emphasis of the research could be concentrated on creep behavior. The primary aim in developing the new alloy has therefore been to attain maximum creep resistance; but due consideration has also been given to other important properties such as castability, tensile strength, and cost. It is by now well established that it is not possible to correlate creep strength with other short time mechanical properties such as are obtained in tensile

Jan 1, 1954

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

Jan 1, 1954

By J. P. Nielsen, H. Margolin, E. Ence

The Ti-Ni phase diagram has been investigated up to 68 pct Ni with iodide titanium base alloys by metallographic, X-ray, and melting point methods, and from 68 to 90 pct Ni by examination of as-cast structures of sponge titanium base alloys. NVESTIGATION of the nickel-rich portion of the I Ti-Ni phase diagram was first reported by Vogel and Wallbaum in 1938.' This work was subsequently extended to lower nickel contents by Wallbaum' who indicated the possibility of a eutectic reaction for nickel contents below 38 pct. Long et al.3 studied the titanium-rich portion of the phase diagram and found eutectic and eutectoid reactions below 38 pct Ni. However, the temperature of the eutectic indicated by Long et al. was considerably lower than that suggested by Wallbaum. Long and his coworkers synthesized their alloys by powder metallurgical techniques and encountered oxygen and/or nitrogen contamination. Thus the diagram which was obtained did not represent binary alloying conditions. However from these results the features of the binary diagram were predicted. At Battelle Memorial Institute4 the Ti-Ni diagram was investigated up to approximately 11.5 pct Ni with sponge titanium alloys. The range of temperatures used was not sufficient to define the eutectoid temperature or composition. The data of Wallbaum2 and Long et al.8 were of particular interest for the present study, and although the work was originally concerned with the region below 40 pct Ni, the investigation was extended to higher nickel contents in an attempt to resolve the differences between these workers. Experimental Procedure Preliminary work on the Ti-Ni system was carried out with duPont Process A sponge titanium alloys to reduce the amount of subsequent work to be done with iodide titanium base alloys. The sponge titanium used contained 99.71 to 99.77 pct Ti, 0.1 pct Fe and 0.005 to 0.009 pct Ni. The iodide titanium obtained from the New Jersey Zinc Co. contained 99.9 to 99.95 pct Ti. Nickel used with sponge titanium was 98.9 pct pure. The high-purity nickel alloyed with iodide titanium was cobalt-free with approximately 0.05 pct C and was obtained through the courtesy of the International Nickel Co. The 15 g sponge titanium charges for melting were prepared by compacting in a die or by placing the weighed portions of nickel and titanium directly into the furnace. Iodide titanium charges were made by drilling holes in the as-received rod and inserting the nickel or by wrapping the nickel in sheet. Sponge titanium alloys containing from 0.2 to 90 pct Ni and iodide titanium alloys containing 0.2 to 68 pct Ni were prepared by these methods. In addition to these alloys several 1/2 1b sponge titanium alloys were supplied by the Allegheny Ludlum Co. The charges were melted in an arc furnace under an argon atmosphere. The procedures used were similar to those reported in the literature5,' and the furnace has been described.' Except for iodide titanium alloys with 40 to 68 pct Ni (see section on copper contamination), each alloy was melted for 1 min, then either turned over or broken before re-melting for an additional minute. Currents of 200 to 400 amp were used depending on the melting point of the alloy. Prior to heat treatment, alloys containing less than 14.5 pct Ni were hot-forged at 750°C. With the exception of alloys in the homogeneity range of the compound TiNi, alloys of higher nickel contents could not be hot-forged. Heat treatment of iodide titanium base alloys was carried out in argon-filled quartz capsules which were broken under water at the conclusion of heat treatment to quench the specimens. Temperatures were controlled to ±5oC and annealing times up to 48 hr were used. For melting point determination, specimens were placed in carbon crucibles which were in turn en-capsuled in argon-filled quartz capsules. The start of melting was determined by rounding of corners and by metallographic examination. Complete melting was considered to have occurred at that temperature at which the specimen assumed the shape of the crucible. Specimens were prepared for metallographic examination by mechanical polishing or by an electrolytic procedure." For alloys containing up to 80 pct Ni Remington A etch7 50 pct glycerine, 25 pct HNO,, 25 8 HF) was used. For higher nickel alloys aqua regia and Carapella's etch (5 g FeCl,, 2 ml HNO,, and 99 ml methyl alcohol) were employed. Specimens to be exposed for powder patterns were prepared by filing, by breaking specimens in a

Jan 1, 1954

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By J. H. Frye, D. L. McElroy, E. E. Stansbury

The rates of growth of pearlite in high-purity Fe-C alloys have been measured as a function of the transformation temperature. These and other data have been correlated in terms of a derived rate equation. Activation energies for the growth were found to be 24,200 cal per mol of austenite for the 0.78 pct C alloy and 27,600 cal per mol for the 0.93 pct C alloy. Theoretical implications are discussed. AN excellent review of the the theoretical and experimental studies on the mechanism and kinetics of the eutectoid reaction has been presented recently by Mehl and Dube.' They have pointed out that these investigations have followed two lines of approach: 1—experimental studies and derivations of expressions for the overall transformation characteristics, and 2—derivation of expressions for the nucleation and growth rates in terms of fundamental processes. Investigations of the latter type have been concerned for the most part with the nature of the growth at the austenite-pearlite interface in plain carbon and alloy eutectoid steels. They discuss two theories of the rate of growth of pearlite from aus-tenite—those of Brandt and of Zener. Both derive rate equations which are based on the assumption that carbon diffusion is the controlling mechanism. Mehl and Dube,' Zener,2 and Brandts. " have attempted to calculate growth rates by use of these equations together with thermodynamic and diffusion data. The results are encouraging, but agreement is not so good as to constitute verification of the theories. Furthermore, it Is not clear how these equations are to be used to study the effect of alloying elements which apparently exert little influence on carbon diffusion, but markedly decrease growth rates. It is not clear whether or not the addition to iron of an alloying element which does not diffuse during transformation can alter the rate of growth of body-centered from face-centered cubic iron. That it can greatly decrease the overall transformation rate has

Jan 1, 1954

By P. D. S. St. Pierre

IN recent years the use of high sulphur fuels and charges in steelmaking has necessitated rapid methods of slag control in order to insure the production of high quality steel. Several systems of control have been discussed in the literature, and of these the method described by Philbrook, Jolly, and Henry' has received the most attention recently. In their process the hydrogen ion concentration of an aqueous slag suspension is determined under controlled, but arbitrary conditions. The basicity of the slag may then be derived from a previously established pH-V ratio curve. Thus, by measuring the pH, some indication of the V ratio is gained, from which significant properties of the slag may be deduced. Philbrook et al. made no claims as to the theoretical justification of their treatment, but simply offered it as a rapid means of slag control. Encouraging results caused others to study the method and publish their findings.2-5 Although there was fair agreement on the efficacy of the method, no common parameter was evolved against which pH readings could be plotted. The results of the various determinations were related to such V ratios as CaO/SiO2 and CaO/ SiO2 + P2O5 by some,'-3 while others" plotted against "excess lime." Rivet,' however, found a simple proportionality between the hydrogen ion concentration and the sulphur content of the molten steel beneath the slag. Since slag control in North American practice is largely directed toward the efficient removal of sulphur from steel, Rivet's approach to the problem had the advantage of connecting directly a property of the slag with the impurity being removed. In view of the diversity of parameters used it seemed probable that some fundamental point was being overlooked in seeking a relationship. Examination of the literature revealed that much emphasis had been laid on experimental detail but scant attention paid to the fundamental aspects of the hydrolysis of the aqueous slag suspension. Consequently the present investigation was undertaken with the object of rectifying this deficiency and deriving, if possible, a parameter of general application. Petrographic studies on several matured Canadian open-hearth steel slags have shown that their major constituents are dicalcium and tricalcium silicates set in a complex matrix of iron oxides and ferrites. These phases are shown in Figs. 1 and 2. Free lime is frequently encountered in slags, but is not an equilibrium phase since on continued heating it dissolves forming silicates or ferrites. Thus, it appeared that a study of the hydrolysis of the major phases in steel slags would be profitable. The experimental technique used in the present work was a modification of that described by the other workers.'- Electrical conductivity measurements were also made on the suspensions, since Smith et al." had claimed advantages for this method in their paper on slag control. Experimental Procedure The compounds studied in this investigation were prepared in the laboratory by heating purified oxides

Jan 1, 1954

By W. T. Read, W. Shockley

THE subject of this chapter is the application of the dislocation theory to two problems of physical metallurgy where the theory has been able to give definite predictions that subsequently have been verified by experimental observations. Much of the history of dislocation theory has consisted of the explanation of already established results on the basis of ad hoc assumptions. Scattered bits of fundamental theory were formulated as needed-in particular explanations. The result had the appearance of a hodgepodge of ingenious ideas and exciting but possibly artificial speculations. The review article by Koehler and Seitz in this volume gives an excellent picture of the breadth, diversity, and flexibility that have made dislocation theory attractive to speculative theorists, although occasionally bewildering to others. Since 1950, there have been two developments, which have helped to establish dislocation theory, on the one hand, as a systematic coherent body of theory and, on the other, as a means of making predictions that can be tested experimentally and thereby guide experiment into more fruitful channels. The first and easier of these developments has been the systematic derivation of the classes and properties of dislocations from fundamental crystallographic concepts. An example of one phase of this development is the rigorous treatment of

Jan 1, 1954

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954

LIMA (PERU) Established May, 1952 James S Young, Honorary Member of Section (Legion of Honor Member) Bernard T Colley, Honorary Member of Section (Legion of Honor Member) Edward H Robie, Honorary Member of Section (Secretary of AIME) Carl W Westphal, Chairman Ernesto A Baertl, 1st Vice-Chairman Pierre L Garrigue, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Avenida Santa Cruz 331 San Isidro, Lima, Peru Daniel M Rodriguez, Assistant Secretary Alberto E Brazzini, Assistant Treasurer Robert P Koenig, Section Delegate Irving L Barker, Special Representative

Jan 1, 1954