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By D. E. Etter, J. E. Selle

HIGH-PURITY cerium metals, supplied as 99.9 pct pure, by various suppliers, vary widely in melting points and in the shapes of the differential thermal-analysis curves obtained as the samples are heated. A definite correlation is noted between the melting point, amount of premelting, and the number of inclusions present in the material. Briefly, the DTA apparatus, previously de-

Jan 1, 1964

By G. K. Manning, M. C. Udy, L. W. Eastwood

Those who have examined beryllium and beryllium-rich alloys under the microscope have noted the results of the difficulties encountered when preparing these materials for examination. Hard constituents are readily chipped and pulled out of the matrix, and the soft ones are easily gouged out or embedded with abrasive or other material. The matrix is easily deformed, which makes it very difficult to remove the effects of scratches. Furthermore, the matrix and some of the constituents are also readily pitted during etching, which makes the structure difficult to develop. The metallographic techniques designed to avoid these difficulties are neither radically new nor necessarily the best possible procedures. They were developed at Battelle to fill immediate requirements as part of a study of the preparation and pouring of beryllium melts as described in a separate paper. A part of the research program on the causes of gas unsoundness in beryllium castings entailed a study of the effects of such gases or gas formers as oxygen or oxides, nitrogen or nitrides, and carbon or carbides. These gases or gas formers, if dissolved in the melt, might be an important factor in the study of unsoundness caused by gas evolution in beryllium. Because it was necessary to be able to distinguish these gases or gas formers, if present as alloy constituents, from metallic phases also present as alloy constituents, a series of alloys was prepared with additions of the various possible metallic and non-metallic constituent formers. It should be emphasized that the constituents referred to as gases or gas formers are important in the study of gases in beryllium only if they form a part of the alloy, that is, if they dissolve in the liquid or solid metal. During the first part of the development of metallographic techniques, the Massachusetts Institute of Technology, unpublished report (TC 3315, Nov., 1945) by Paul Gordon, describing various microconstituents in beryllium, was quite useful. Of particular interest in this report is the confirmation of one of the conclusions drawn from the present investigation, that is, that a distinct oxide phase apparently does not occur in beryllium. The Preparation of Metallographic Specimens GRINDING PROCEDURE The original specimen is either sawed or cut on an abrasive wheel to a convenient size. For best results, the surface to be polished should not be more than about 1/4 in. square, and it is convenient to mount the specimens in bakelite to facilitate handling. Two alternative grinding procedures have been developed. As one alternative, specimens are ground successively on 120-, 240-, and 400-grit, wet-or-dry metallographic discs. The abrasive discs are revolved at 1750 rpm on a conventional pedestal grinder. The coarsest disc (120 grit) is used either wet or dry, and in most instances, it can be eliminated from the procedure. Grinding on the two finer discs (240 and 400 grit) is accompanied by the application of kerosene. The technique consists of holding an oil can, containing kerosene, in one hand and the mounted specimen in the other hand. While the grinding is being done, several drops of kerosene are applied every few seconds close to the center of the disc. Carbon tetrachloride serves at least as well as kerosene as a lubricant; perhaps it is slightly better, but it volatilizes so readily that an additional health hazard is involved. Light oils and water are not satisfactory for the finer grinding operations. The second procedure is perhaps slightly slower than the first and requires a more careful technique, but it eliminates the use of kerosene. The specimen is first ground wet on a 240-grit disc, followed by dry grinding on a 400-grit disc. Finer grinding does not appear to be necessary with either of the two alternative procedures. The pressures used throughout either grinding operation must be extremely light, that is, barely sufficient to hold the specimen in contact with the disc; otherwise, flow and chipping are almost certain to occur. In both procedures, it is essential that the discs be sharp and that they be discarded as they show evidence of becoming dull or loaded. In general, not more than four or five specimens can be ground on a disc before the disc becomes dull enough to warrant discarding it.

Jan 1, 1950

By R. F. Dickerson, D. A. Vaughan, A. F. Gerds

ALTHOUGH the metallurgy of uranium has been under intensive study since the early 1940's, no systematic effort has been made to identify the non-metallic inclusions in uranium. Uranium carbide (UC), which is probably the most common inclusion found in graphite-melted metal, has been tentatively identified by previous investigators, but the other nonmetallic inclusions have received little attention. Since metallography is a valuable tool in metallurgical studies, the metallographic identification of the nonmetallic inclusions in uranium is important. Such an investigation has been completed and the identification of slag-type inclusions and of uranium monocarbide, uranium hydride, uranium dioxide, uranium monoxide, and uranium mononitride is described. Metallographic Preporation It is often possible to prepare specimens for metal-lographic examination equally well by several methods. The specimens which were examined in this work were prepared by one of two acceptable methods. For the convenience of the reader, both methods will be discussed in detail and will be referred to simply as Method I or Method II in the subsequent sections. For both Methods I and 11, specimens for microscopic examination usually were mounted either in bakelite or in Paraplex room temperature mounting plastic. Method I—Specimens were ground in a spray of water on a revolving disk covered successively with 120-, 240-, and 600-grit silicon carbide papers. It was necessary to perform the final grinding operation carefully on worn 600-grit paper to keep the scratches as fine as possible. After washing and drying, the specimens were polished for 3 to 4 min on a slow speed wheel (250 rpm) covered with a medium nap cloth. Diamet Hyprez Blue diamond polishing paste, Grade 00, 0 to 2 µ, was used as abrasive with kerosene as lubricant on the wheel. Specimens were washed thoroughly in alcohol and final polished electrolytically in an electrolyte composed of 1 part stock solution (118 g CrO, dissolved in 100 cm3 H2O) with 4 parts of glacial acetic acid. A stainless steel cathode was used. At an open circuit potential of 40 v dc, a polishing time of 2 sec retained inclusions well with the bath at room temperature. If additional etching was required to sharpen the interface between the metal and the inclusions, an electrolyte composed of 1 part stock solution (100 g CrO3 and 100 cm8 H20) and 18 parts glacial acetic acid was used at room temperature. Best results were obtained by etching for from 10 to 15 sec at 20 v dc in the open circuit. Surfaces obtained by this method are suitable for microscopic examination. However, if desired, they may be etched further with other chemicals. Method 11—Rough grinding was done on a wet 180- or 240-grit continuous grinding belt. The specimen was then ground by hand successively on 240-, 400-, and 600-grit silicon carbide papers in a stream of water. Final polishing was accomplished on a 4 in. high speed wheel (3400 rpm) covered with Forstmann's cloth. Linde B levigated alumina, suspended in a 1 volume pet chromic acid solution, was the abrasive. Specimens usually were polished in 5 min or less by this technique. Often the inclusions present in the metal were identified in the mechanically polished condition. When etching was required to outline inclusions more sharply, one of the two following methods was used. In the first method, the specimen is etched lightly while electropolishing in the chromic-acetic acid solution described above (1 part of stock solution to 4 parts of acetic acid). The electrolyte was refrigerated in a dry ice-ethyl alcohol bath and specimens were etched at 60 v dc on the open circuit for 2 or 3 cycles of 3 to 4 sec each. The second technique utilizes electrolytical etching at about 10 v dc (open circuit) in a 10 pet citric acid solution at room temperature. X-Ray Diffraction Technique The major problem in the identification of inclusions in metals by X-ray diffraction techniques is the extraction of a sufficient amount of each type of inclusion to obtain an X-ray diffraction pattern. In the present study, X-ray diffraction patterns were obtained from individual inclusions of the order of 10 µ diam. The polished and etched samples shown in the micrographs were examined at a magnification of X54 or XI00 with a binocular microscope. This allowed sufficient working distance to extract the inclusions with a needle probe for powder X-ray diffraction analysis. Friable inclusions such as MgF2, CaF2, UO2, and UH3 could be freed from the metal by probing the as-polished and etched surface. The fine particles then were picked up on the end of a Vistanex-coated glass rod (0.002 in. diam) which was held in a brass adapter made to fit the powder X-ray diffraction camera. The end of the glass rod was centered in the path of the X-ray beam. In the case of the UC, UO, and UN inclusions which are smaller in size, more metallic in appearance, and less friable than the other inclusions, it was necessary to etch the inclusion in relief before extraction. UN inclusions etched sufficiently in relief in the electrolytic polishing solution described in Methods I and II by increasing the polishing time. UN inclusions were relief etched by extending the

Jan 1, 1957

By J. T. Norton, N. J. Grant, A. R. Chaudhuri

MOST of the recent work to establish the mech-anism of creep in metals at high temperatures has utilized aluminum as the experimental material. It was thought desirable to initiate an investigation of a hexagonal close-packed metal, because of the relatively simple slip system, and compare the observed deformation characteristics with those that have been observed for the face-centerd cubic metals. High-purity magnesium was chosen for this purpose, first, because its strength and other mechanical properties are similar to those of aluminum in the same temperature range, and second, because the existing equipment was ideally suited to observe magnesium during creep. It is proposed in this paper to present a pictorial and qualitative account of the changes that high-purity magnesium undergoes during creep at 500°F. The characteristics of deformation of aluminum described below have been observed by various workers and accounts of these may be obtained from the papers of Chang and Grant.'- These characteristics are: slip, subgrain formation, grain boundary sliding and migration, fold formation, deformation bands, and kink bands. It is well known that in a flat magnesium specimen, slip on the basal plane (0001) in the [1120] direction results in the formation of straight bands on the surface of the specimen. Schmid and co-workers' have shown that this system is operative in the temperature range of -185" to 300°C (-300° to 572°F). They have also shown that a second system, slip on the pyramidal planes {1071} or {1012} in the [1120] direction, is operative at temperatures higher than 225°C (437°F). Between 225° and 300°C (437" to 572°F), therefore, deformation by both these systems is expected. Bakarian and Mathewson5 confirmed the occurrence of pyramidal slip on the {1011} plane and found that it resulted in irregular markings on the surfaces of their specimens. Burke and Hibbard6 obtained evidence of pyramidal slip in single crystals of magnesium deformed at room temperature. Bakarian and Mathewson5 suggested that the irregular appearance of these bands was due to slip on both of the pyramidal planes occurring simultaneously but in the same direction, the close angular relationship between the planes making this process possible. Furthermore, since neither of these planes is close enough to the basal plane, slip on the latter does not exhibit the irregular appearance of slip bands resulting from pyramidal slip. Experimental Procedure High-purity magnesium, supplied by the Dow Chemical Co., was used in these experiments. The analysis was as follows: Al, 0.0002 pct; Mn, 0.0018; Fe, 0.0024; Cu, 0.0002; Sn, 0.001; Ca, 0.01; Ni, 0.0003; Zn, 0.01; Pb, 0.0005; Si, 0.001; and Mg, 99.972. The magnesium was supplied in the form of 1/2 in. diam rods. The specimens had an overall length of 21/4 in., the round ends being threaded to fit the specimen holders. The previously round 3/16 in. diam gage section of the specimen had two parallel flats machined on opposite sides for microscopic observation, yielding a test zone having the dimensions of lx3/16x7/64 in. The specimens were electrolytically polished (without prior mechanical polishing of the machined flats), in a solution composed of 375 ml of ortho-phosphoric acid and 625 ml of ethyl alcohol.' The cathode was a stainless steel sheet bent so that the specimen was completely surrounded. The voltage for successful polishing was 1.5 v at 100 to 300 milli-amp current. Electropolishing for about 45 min sufficed to obtain a good metallographic surface on the specimens after they had been machined. The creep tests were performed under constant load, and two types of equipment were used. In the first, designed by Servi and Grant,V he specimens were beam-loaded, and a furnace could be lowered to surround the specimen. As the microstructural changes could not be observed during the course of the test, the tests had to be interrupted periodically by removing the specimen for microscopic examination. The second unit was a high temperature microscopy furnace designed by Chang and Grant.' The furnace was fitted with an optically flat quartz window having area dimensions 1.25x0.5 in., so that the whole test portion could be viewed through it at magnifications up to x240. The metallurgical microscope had three mutually perpendicular axes of motion, and, in addition, it was possible to measure angular displacements by rotation of the eyepiece. It was thus possible to make precise observations of the specimen during creep, and micrographs could be taken by attaching a camera to the eyepiece of the microscope. The average grain size of the specimens that were tested was about 1 to 3 mm. This grain size could

Jan 1, 1954

By R. A. Spurling, C. G. Rhodes

SATISFACTORY metallographic sample preparation of very soft metals, such as lead and its alloys is generally difficult. The prime requisite of any technique must be that the result gives an undis-torted microstructure for the microscopist to examine. A small amount of mechanical polishing followed by a chemical or electrolytic polish is usually the most desirable way to obtain an undis-torted surface. Several chemical-4 and electrolytic3-' polishing solutions have been developed for dilute lead alloys. Perchloric acid mixtures (with acetic anhydride, ethyl alcohol, or water) are among the most prominent electropolishing solutions used for lead; however, the presence of bismuth in the alloy precludes the use of any perchloric-containing solution. The other solutions1-7 were found to be unsatisfactory on alloys ranging from 10 to 65 wt pct Bi in lead. With increasing bismuth content, the microstructure shows a lead (terminal solid solution), 0-6 mixture, E (peri-tectically formed hexagonal phase), and E bismuth mixture (eutectic at 56.7 wt pct Bi).9 The metallographic samples were mounted in "Araldite" epoxy (the heat generated during polymerization does not alter the microstructure), ground by hand on well-waxed silicon carbide papers (400 and 600 grit), and polished with 3- and 0.25-CL diamond paste on billiard and microcloths, respectively. The use of the various polishing and etching solutions reported in the literature resulted in the formation of irremovable reaction products on the sample surface when applied to "as-ground" or "as-polished" surfaces. The E phase was the most difficult to clean chemically and in the development of an etchant for this system several solutions which satisfactorily etched the bismuth or a phase were unacceptable because of their reaction with the E. It was found that a mixture of 50 ml lactic acid 30 ml nitric acid 20 ml (30 pct) hydrogen peroxide (Solution #1) was a satisfactory etchant for the a-matrix alloys. The samples were prepared as before and etched after 1 min of polishing with 3-p diamond paste. The etchant was applied by swabbing (light pressure) for 30 sec to 1 min and the sample was then rinsed in running water. The E has a slight stain and the a is fairly bright, Fig. 1.

Jan 1, 1965

By P. R. Sperry

Aluminum alloy 3S was examined to determine the relationship between the applicable phase diagram and the microstructures produced under conditions tending toward non-equilibrium as well as equilibrium. The only phases present in the alloy were aluminum, (Mn,Fe)A16, aAI(Mn,Fe)Si, and silicon. It was found that the alloy behaved essentially as though it belonged to the Al-Mn-Si system. The effects of various solidification rates and of various homogenization treatments were studied. Particular attention was given to a nonuniform precipitate distribution which reflected the solute distribution in the cast aluminum solid solution. Some possible explanations for the solute distribution based on characteristics of the Al-Mn-Si or AI-Mn systems were discussed. ALUMINUM alloy 3s (aluminum plus 1.25 pct Mn) is one of the oldest and the most widely used of the wrought aluminum alloys. In spite of this fact, there are some aspects of the metallography of 3s which have not been revealed or which have not been brought to the attention of the metallurgist working with the alloy. The purpose of this investigation was to demonstrate in general how some of the fundamentals of equilibrium phase diagrams may be applied to the study of an alloy and to show specifically the origin of certain metal-lographic features of aluminum alloy 3s. It is hoped that this information can serve as a basis for solving specific problems relating microstructure to such things as mechanical properties, recrystallization, grain growth, and surface finish. Literature Survey Considering that alloy 3s contains only one alloying addition, manganese, it seems reasonable that it would have characteristics pertaining to the A1-Mn system. However, those characteristics might well be altered by the impurities in the commercial alloy, especially iron and silicon. Therefore, not only the simple binary but also more complex systems had to be reviewed. One characteristic of the A1-Mn system worthy of mention is its sluggishness, which leads to conflicting solubility data1,'2 and makes it relatively easy to supersaturate the solid solution and shift the eutectic composition during rapid solidification.3'4 Another characteristic is the strong influence which small amounts of impurities, especially iron, exert in lowering the solid solubility of manganese. Undissolved manganese is ordinarily present in an intermetallic phase, MnAl,, having an orthorhombic crystal structure. A metastable precipitating phase designated as "G" has been reported but small amounts of iron and silicon suppress this phase entirely." Raynor has established that MnA1, can dissolve a considerable amount of iron by a substitution of iron for manganese atoms up to 50 atomic pct.'" Consequently, in the Al-Mn-Fe liquidus diagram, the eutectic valley separating the primary aluminum and (Mn,Fe)Al, fields is fairly close to a constant Mn + Fe content." This is an important consideration in regulating the composition of 3s and also other aluminum alloys with high manganese additions."

Jan 1, 1956

By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,' has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers' measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett's measurements on lithium indicated an angle of 3". According to the Burgers' mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers' mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

By J. S. Bowles

DISCUSSION, M. Cohen presiding J. W. Christian (The Inorganic Chemistry Laboratory, oxford, Englandl)—I was very interested in Dr. Bowles' results on the suppression of the transformation by solid films of alcohol or propane. The transformation in cobalt, which is also martensitic, can be explained by a mechanism involving the reflection of "half dislocations" down a series of atomic planes.* This reflection process is similar to that considered by Frank13 for plastic deformation on a single slip plane and, as he pointed out, reflection would be impossible if the metal were immersed in a liquid of higher density. It seems possible that solid films of alcohol have a similar effect on the lithium transformation. Reflection should also be possible at a grain boundary, though a higher kinetic energy of the dislocation, and hence a lower temperature would be required. As Dr. Bowles used coarse grained polycrystalline speci- mens, transformation on cooling should still have occurred in grains which did not form part of the outside (free surface) of the metal. This may account for the X-ray lines of the low temperature phase which were found. There is thus the interesting possibility that in a polycrystalline specimen a liquid, or in some cases a solid, film of material of or or higher density will lower M,, while in a single crystal it should suppress the transformation completely. In the case of cobalt it is necessary to find a dense liquid which will not react with the metal at the transformation temperature. The most promising liquid appears to be pure lead, but it is very difficult to devise a method of investigating whether or not this does suppress the transformation.

Jan 1, 1952

By F. V. Lenel, G. S. Ansell, E. C. Nelson

IRMANN'S' discovery that extrusions of fine alumi-num-flake powders possess remarkable high-temperature strengths has led to the production of a new class of engineering materials whose properties are derived from a fine dispersion of oxide particles in a metallic matrix. A fundamental study of such materials and elucidation of the mechanism whereby the oxide parti-

Jan 1, 1958

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,' little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.' Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By William Klement

THIS note reports the results of some attempts to metastably extend the primary solid solubilities of tin, antimony, and silicon in silver by rapidly quenching these binary alloys from the melt. The procedures employed for alloy preparation, quenching, and Debye-Scherrer X-ray diffraction measurements have been described elsewhere. The lattice parameters obtained for the fcc structures in Ag-Sn and Ag-Sb alloys are presented in Fig. 1, together with the results of Owen and Roberts.4 Alloy compositions are believed to be within ± 0.2 at. pct on the basis of negligible weight losses during preparation and reproducibility of the lattice spacings. Diffraction lines from hcp phases were also detected: the relative visual intensities of the fcc (200) and hcp (10.2) lines were estimated as shown in Table I. The intensities were m for the (200) and w for the (10.2) in a quenched 13.6 at. pct Sn alloy: a lattice spacing for the fcc structure could not be reliably obtained, however. As seen from Fig. 1, the lattice parameters vary linearly with composition up to 8., at. pct Sb and 13." at. pct Sn, respectively, which may be compared with the maximum equilibrium solid solubilities5 of 7.2 at. pct Sb and 11.5 at. pct Sn, respectively. The presence of the hcp phases, which were found together with the fcc phases, is a consequence of the competition1,3 in the nucleation and growth processes during solidification. Both the fcc and hcp phases must be of the same composition for those alloys in the range where lattice parameters increase linearly with solute concentration. Despite much effort with quenched alloys of several silicon concentrations, it has not been possible to obtain lattice spacings of sufficient precision to establish the variation of lattice parameter with composition or the maximum metastable solid solubility: the equilibrium data5 suggest little primary solid solubility of silicon in silver. For alloys containing less than 16 at. pct Si, the Si (111) diffraction line was not observed. For alloys containing 10 to 25 at. pct Si, faint low-angle lines were detected and these could be indexed as the (10.0), (00.2). and (10.1) reflections of an hcp structure with a = 2.87 + 3A. c = 4.52 ± 3A, and c/a = 1.57 ± 2. The 16 at. pct Si alloy was quenched to, and examined at. liquid nitrogen temperatures without any change observed in the proportion of the hcp phase. These experiments were jointly supported by the Atomic Energy Commission and Office of Naval Research under a program directed by Professor P. Duwez. The assistance of H.-L. Luo and A. Abu-Shumays is acknowledged. as is the support afforded

Jan 1, 1965

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By H. L. Luo, W. Klement

By rapidly quenching Ag-Pt alloys from the melt, a continuous series of solid solutions has been obtained. At equilibrium''2 these fcc elements form a peritectic system, Fig. 1. Weighed amounts of silver and platinum powder (325 mesh, purity greater than 99.9 pct) were mixed for 24 to 120 hr, pressed into compacts, sintered at 1000°C in a hydrogen atmosphere for at least 16 hr, and then furnace-cooled. Because of the difficulty in achieving homogeneity in alloys containing more than about 40 at. pct Pt, the sintered compacts were induction-melted under hydrogen in alumina crucibles and then cold-rolled into wires. Small amounts ("30 mg) of alloys cut from various sections of the sintered compacts or rolled wires were heated to at least 50' ~ above the liquidus in an alumina insert held within an induction-heated graphite crucible; then the molten alloy was ejected by a blast of helium onto a lightly polished copper strip held on the inner periphery of a rotating wheel. The flakes thus obtained were typically 1 sq mm in area or often slightly larger for the silver-rich alloys. X-ray diffraction patterns were obtained with nickel-filtered copper K radiation in a 114.6-mm-diam Debye-Scherrer camera with rotated specimens. Lattice parameters and associated uncertainties were estimated from extrapolations against the Nelson-Riley function. High-angle lines were always resolved and spacings were computed relative to r(CuKa!,) = 1.540508 The details of these techniques have been discussed previously.s'6 Lattice parameters of the solid solutions are plotted in Fig. 2, together with the data of Schneider and Esch,' Johansson and Linde,' and Novikova and pudnitskii. Each of the present lattice spacings represents two or more independent determinations. The alloys were homogeneous within 2 at. pct of nominal composition as estimated from the uncertainties in the lattice spacings. Many of the mechanisms involved in the achievement of metastable solid solutions by rapidly quenching from the melt have been previously discussed. There is some evidence" that such solid solubility cannot be obtained when the liquid alloys are cooled

Jan 1, 1963

By N. A. Richard, A. E. Austin, R. E. Maringer

AS part of a detailed study of the structure of metallic meteorites, the concentration and distribution of iron and nickel in the various phases of meteor -itic iron have been measured using an electron-probe microanalyzer. The specimen used was cut from a position about 3 in. below the surface of the Grant meteorite, a one-half-ton iron specimen (containing 9.35 pct Ni) found in New Mexico some years ago. A photomicrograph showing the general Widmanstztten structure, somewhat typical of iron meteorites, is shown in Fig. 1. The line across which the analyses were made is indicated by arrows. This area was chosen so as to evaluate the iron-nickel concentration in the three principal phases visible in Fig. 1. These phases, in the language of meteoritics, are kamacite, taenite, and plessite. Kamacite is the a-

Jan 1, 1960

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,' Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies' in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,' supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.&apos; DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.&apos;-4 Samsonov et al.&apos; reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami&apos;s Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965