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By L. D. Jaffe

From the limited experimental data in the literature, preliminary values were derived for the thermal diffusivity of titanium alloys and for the quenching severity of various mediums used in heat treating them. The thermal diffusivity, under quenching conditions, was found to be approximately 0.006 sq in. per sec. The quenching severity H for brine is approximately 8, for water 4, for oil 0.9, for air 0.08, and for argon 0.02 in. -' The quenching severity of the Jominy-Boegehold end quench water jet against titanium alloys appeared effectively infinite. Using these results, graphs were prepared showing ideal round sizes and Jominy positions having cooled conditions equivalent to those at the center and surface of titanium alloy rounds, plates, and sheets quenched in various media. THE importance of proper quenching of steel parts has long been recognized, and much quantitative work has been done on the subject. Recently, it has become evident that for titanium alloys, too, the rate of cooling from high temperature is important in obtaining high strength and hardness. Maximum hardness and strength may not be attained in the as-quenched condition but rather after a subsequent tempering or aging treatment. Nevertheless, if cooling from temperatures near the ß transus is too slow, for the hardenability of the alloy used, a soft a-ß structure will be produced which will not harden on subsequent aging.'-" The quenching of parts of practical interest can usually be approximated by simple shapes, such as cylinders (rounds) and plates (or sheets) of various thickness and combinations of these. A standard that has been used extensively for comparison purposes is the center of an ideal round: a cylinder quenched in a medium that instantly cools its surface to room temperature." For steel, considerable practical use has been made of the Jominy-Boegehold end quench hardenability specimen,".' and its value for titanium alloys is becoming evident. It therefore appeared worthwhile to attempt comparison of cooling conditions in titanium alloy rounds and plates of various sizes quenched in various media with cooling conditions in ideal round and Jominy quenches. These comparisons are based upon measurements reported in the literature. Quenching Severity of Jominy Water Jet and of Brine As one starting point, there were available the data of Phillips and Tobin8 for positions on a Jominy specimen having the same hardness as the centers of round bars of various size quenched in 5 pct NaOH brine, shown in Table I. The Jominy speci- men is a round bar, normally 1 in. diam and 4 in. long, quenched by a water jet at one end and air cooled on the other surfaces.' After quenching, hardness is measured vs distance from the quenched end on longitudinal flats ground 0.015 to 0.10 in. deep. The data of Table I were based on a subsized specimen of 3/4 in. diam. Since the positions tested are close to the jet quenched end, cooling there may be taken as due solely to the jet, and air cooling can be neglected. These positions are then equivalent to various locations near one surface of an 8 in. plate jet quenched on both sides. Assuming that the thermal diffusivity is constant and that Newton's law of cooling holds, temperature vs time curves at corresponding positions in Jominy specimen and round bar then may be calculated for various assumed quenching severities of the water jet and of the brine. Cooling curves are generally taken to be metallurgically equivalent when they show the same time to reach a temperature halfway between the initial (heat treating) temperature and the final (quenching medium) temperature.5 On this basis, using Russell's tables,9 upplemented by heat flow tables derived in similar fashion by the author for positions near the surface of severely quenched plates, it was found that the experimentally observed equivalence, Table I, was best matched if the quenching severity H of the Jominy water jet was taken as infinite (H = co). This means that the jet quenched surface should be considered as instantly cooled to the temperature of the water

Jan 1, 1956

By Nick Holonyak

Halogen vapor-transport synthesis of Ga(As,-,Px) and its preparation into laser junctions are described. Electrical and optical properties of Ga(As,-,PX) laser junctions are discussed. The present limitations in these properties are related to material proble?vzs and the very early state of development of Ga(As,-,PX), and are discussed in this context. Inhonzogeneity problems, fluctuation of As :P ratio, and problems with deep-level contaminants are described and related to Ga(As,-,PX) junction performance. Laser junctions are demonstrated which operate to wavelengths as short as 6470 A (77°K). The prospect that Ga(As,-,P,) will operate to wavelengths perhaps 100A shorter is mentioned. IN this paper we wish to describe some of the more important features of almost 1 year of experience in the preparation and properties of Ga(As,-,P,) p-n junction lasers. Because much data so far available are far from complete, some of the results still must be considered tentative and subject to correction and revision as work on Ga(As,-,P,) crystal problems progresses. Although the electrical, optical, and device properties of Ga(As,-,P,) junction lasers are understandably of considerable interest, the work to date points out that by far the most serious problems extant and those deserving first attention are problems involving the growth, doping, and perfection of Ga(As,-,P,) crystals. One of the most formidable of these is to grow Ga(As,-,P,) sufficiently free of deep levels, either due to contaminants or to structural imperfections, to allow fabrication of laser p-n junctions which can be cooled and not suffer from "freeze-out" of carriers on deep levels (and consequent double-injection behavior). In addition to the problems of growing crystals adequately free of deep levels and generally of the highest perfection, so that the best possible laser junctions can be realized, the further goal remains of increasing the phosphorus content well beyond 40 pct in an attempt to determine the practical lower wavelength limits of laser action in the Ga(As,-,P,) system. Even though the laser junctions prepared in Ga(As,-,P,) are of importance in their own right, we have considered them at this point mainly a means to study the growth and crystal problems of the material. It can be concluded that the laser junctions now available are almost completely limited by the purity and structural deficiencies of Ga(As,-,P,) crystals, and cannot be fairly compared with, for example, GaAs p-n junction lasers until Ga(As,-,P,) crystal growth has been more extensively developed. The basis for the statements above will become evident in the following sections which describe Ga(As,-,P,) crystal and junction preparation, and laser-junction properties. G(As,-,P,) CRYSTAL GROWTH As previously reported,2 we have found it convenient to employ the halogen vapor-transport process3 for synthesizing Ga(As,-,P,) crystals for use in laser junctions. Commercially available GaAs and Gap, separately prepared by halogen vapor tranport, are sealed in the desired ratio in a quartz vessel with a quantity of column-VI donor and a small quantity of metal halide which supplies the halogen for transport. The sealed ampoule, as shown in Fig. 1, is heated at a temperature in the range from 1025" to 1100°C at the position of the source GaAs and Gap. The GaAs and Gap are simultaneously vapor-transported and deposited as Ga(As,-,P,) at one end of the ampoule

Jan 1, 1964

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.' The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,' but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,' but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By Jean Howard

ThE formation of the (100) [001) texture in 3-1/4 pct Si-Fe strip was first reported by Assmus ef a1.l in 1957. Since then much experimental work has been carried out with a view to establishing the mechanism involved. The papers cited above state that the (100) [001] texture was developed in strip rolled from material melted and cast in vacuum. (The impurity content of the ingot is reported as 0.005 pct.) The present note records that similar results can be obtained in material processed by powder metallurgy. A processing schedule is described.which enables the texture to be formed in strip up to 0.010 in. thick, but there seems no reason why this should not be achieved in thicker strip, provided that large grains are developed after sintering. The materials were prepared from Carbonyl Iron Powder Grade MCP (particle size 5 to 30 p) of the International Nickel Co. (Mond) Ltd. The powder contains about 0.15 pct 0, 0.01 pct C, 0.004 pct N, <0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni— that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The silicon powder was 99.9 pct purity, or material of transistor quality (ground in pestle and mortar). The mixed powders (3-1/4 pct Si to 96-3/4 pct Fe) are heated in hydrogen at 350" and 650°C to deoxidize the iron before sintering loose at temperatures between 1350" and 1460°C (depending upon the ultimate thickness of strip required) for up to 24 hr. The object of the high-temperature sinter is to develop a large grain size at this stage. Alternatively, the loose sintering can be done at a lower temperature followed by rolling or pressing and then annealing at temperatures between 1350" and 1460°C. Both methods produce large grains, which remain large throughout the process. The compact is then hot-rolled to approximately 1/8 in. with high-temperature interstage anneals if necessary. This step is taken to avoid intercrystalline cracking which would occur if the material of such large grain size were cold-worked. The bar is then annealed at 1050°C and reduced to its final thickness by approximately 50-pct reductions and 1050°C interstage anneals. Throughout the process the dew point of the hydrogen furnace atmosphere is maintained at about -40°C. Samples were annealed in hydrogen at various temperatures and times. Secondary recrystalliza-tion to (100) [001] was developed on the thinner material (i.e., up to 0.002 in.) by annealing in hydrogen at 1050" to 1200°C with a dew point of - 40°C or in vacuum (10-5 Torr) at 1050°C. With the thicker materials (i.e., up to 0.010 in.) the best results were obtained by annealing in hydrogen at 1200°C with a dew point of - 55°C. Complete secondary recrystal-lization to (100) [001] textures was obtained. Above these temperatures secondary recrystallization to (110) [001] tended to develop. The final annealing of samples was normally carried out with the samples placed between recrystal-lized alumina plates, but some experiments were performed with the samples suspended so that their surfaces were not in contact with anything except hydrogen, and these were equally successful in developing secondary crystals. An approximate determination of the proportion of material (before secondary recrystallization took place) having crystals with the (100) or (110) planes in or near the rolling plane showed that 11 pct of the sample had (100) and 16 pct (110). The method used for the determination is described below. A sample was annealed at a temperature just below the secondary recrystallization temperature and etched to reveal the (100) planes. The approximate area covered by crystals having (100) or (110) in or very near the surface was measured on the screen of a Vickers projection microscope. This was repeated for twenty positions chosen at random and a mean of the results calculated. The main hindrance to developing the secondary crystals in the thicker materials was the difficulty of obtaining a large enough initial primary grain size before secondary recrystallization. This was overcome by increasing the particle size of the silicon powder used. During the course of the work, it had been observed that the larger the grain size after sintering the more likely it was that the material would be successful in developing secondary crystals at a later stage. An experiment was therefore carried out to determine whether the material with the larger grain was more successful in developing secondary crystals due to the large grain produced at the sintering state per se or whether it was due to the greater reduction of silica brought about when the sintering temperature was raised in order to increase the grain size. A comparison was made between two compacts, one of which was made with silicon powder of 60 to 100 mesh, the other with silicon powder which was finer than 200 mesh. F?r this experiment, use was made of a phenomenon previously observed that the larger the particle size of the silicon powder employed in making a compact, the larger is the grain size of the compact. The silicon powder was ground

Jan 1, 1964

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder&apos;s joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger&apos;s vectors in order to produce a lattice match. The .&apos;dangling bonds&apos;&apos; resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By W. Shockley

THIS lecture can best begin with a statement of the chief conclusion: The metallurgical industry will find profit in supporting fundamental research on dislocations. This support should be done both in their own laboratories and in universities. My lecture consists of an exposition of the basis for this conclusion. The experience on which I base it is drawn largely from two fields in solid state physics—one field is transistor electronics and the other is dislocation theory. At present the relationship of solid state physics to technology is different in these two fields. In electronics without question, the physics has led the technology. In metallurgy, on the other hand, the technology in the form of metallurgical art is far ahead of the fundamental science. In transistor electronics, physics has suggested and can still suggest previously unachieved combinations of matter that will have new and useful properties; that is, the physicist can make specific predictions. The physicist can also have some confidence that the predicted devices will actually come into existence in a matter of months or years and that they will live up to the predictions. In metallurgy, the physicist cannot to a comparable degree make predictions and have the same hope that they will lead to something new and valuable. There are a number of reasons for this difference. The first is simply historical. Transistor physics is young. It may be regarded as dating from the announcement of the transistor, in which case it is about four years old, or from the first real control of semiconductors as materials (this was accomplished largely by metallurgists, by the way) in which case it is about ten years old. Metallurgical art, on the other hand, is thousands of years old. There is no doubt that the advance of this art has been and will be hastened by a good fundamental understanding of the quantum theory of atomic phenomena. It, is too much to expect, however, that theory will soon catch up with the lead that practice has gained in a thousand years, and that theory will then point out specific pathways to better materials. It seems more probable that modern atomic theory will serve to interpret and organize information much as thermodynamics has done through phase diagrams. In this lecture, I shall emphasize an important feature common to both solid state electronics and to metallurgy. This common feature is the harmonizing principle that justifies discussing electronics and metallurgy as related topics in solid state physics. In both cases the important properties of the materials arise from imperfections. By imper- fections I mean deviations of the materials from perfect single crystals. The imperfections may be of many forms. From the point of view of utility they may be either good or bad, and a given type may be good or bad depending on circumstances. The technical material of my lecture will be divided into two parts. The first will be chiefly concerned with four types of imperfections in germanium crystals. The control of these imperfections makes possible the fabrication of useful electronic devices. A good example of such control is the junction transistor, which I shall discuss from this viewpoint later. The junction transistor, as some of you may have heard, can be used as an amplifier of electrical signals and in a number of respects surpasses what has hitherto been achieved with vacuum tubes. The second part of my technical material will be concerned with dislocations. For about fifteen years the theoretical physicist has had dislocations in mind as the most important kind of imperfection in metals. He has, however, until recently had experimental material of a highly speculative nature to back up his assertions. I am fortunate in the timing of this lecture to be able to describe some recent results that put dislocations on a far more definite basis than has been the case in the past. In fact there are now some experiments which reveal the characteristic properties of dislocations almost as clearly as experiments in transistor physics reveal the properties of holes and electrons, properties that I shall soon describe. It is this advance in the status of dislocations that emboldened me to make my initial assertion that the metallurgical industry will profit from supporting fundamental research on dislocations. Transistor Electronics In order to discuss imperfections in semiconductors, it is necessary to visualize a reference condition that may be regarded as perfect. In the cases of silicon and germanium, which find application in transistor electronics,&apos; the perfect structure is the diamond structure shown in Fig. I. In this structure, each atom is surrounded by four neighbors with which it forms four covalent or electron-pair bonds. These bonds use all of the four valence electrons possessed by each of the silicon or germanium atoms. The electronic structure of the crystal is thus complete and perfect. A crystal of silicon or germanium with a perfect electron-pair bond structure would be an insulator, In order for electrical conduction to occur, it is necessary for imperfections to arise in the electronic structure. In this lecture, I shall discuss four possible imperfections whose symbols and relationships are indicated in Table I. We shall consider first, as an example, a crystal of silicon containing an arsenic atom as an impurity.

Jan 1, 1953

By M. B. Bever, A. B. Michael

The solidification of aluminum-rich aluminum-copper alloys was investigated for different solidification rates. The measured amounts of nonequilibrium eutectic were compared with the amounts calculated on the assumption of no diffusion in the solid. The morphology of the eutectic was studied and dendritic spacings were measured. Compositions of the cored primary solid solutions were determined by quantitative autoradiography after activation of the solute copper by neutron irradiation. CONSIDERABLE progress has been made in recent years toward an understanding of the solidification of metals. This is especially true for the factors involved in nucleation, the controlled growth of metal crystals from melts, and various aspects of the freezing of ingots and castings. Many features of the solidification process, however, are not understood adequately and much further work is required. In the research reported here the solidification of a series of aluminum-rich aluminum-copper alloys was investigated. Different degrees of deviation from the idealized case of equilibrium solidification were attained by varying the rate of solidification. Thermal analysis and microscopic examination were supplemented by lineal analysis and autoradiography. The latter required the use of radioactive tracers and was adapted to the quantitative determination on a microscale of concentrations of copper dissolved in aluminum. The tracers were produced in situ by activating the copper with neutrons. These techniques permitted a correlated interpretation of the temperature-time history, the amounts of nonequilibrium eutectic and the general morphology of the alloys, and yielded quantitative data on microsegregation. Nonequilibrium Solidification In the general case of the solidification of a solid solution in accordance with the phase diagram, the composition of the coexisting liquid and solid must change continuously. This change requires diffusion, which at best remains incomplete in the solid during solidification. The resulting inhomogeneity of the solid solution crystals is well-known as coring, dendritic segregation, or microsegregation. The generally accepted analysis of coring assumes that, 1—no diffusion occurs in the solid, 2—diffusion is complete in the liquid, and 3—the composition of the solid formed on cooling through any infinitesimal temperature interval is given by the solidus of the phase diagram. On this basis, In this equation m designates mass, x designates the concentration of solute and the subscripts L and S refer to the liquid and solid phases, respectively; the subscript o indicates the initial state, in which the liquid is identical with the entire system. Eq. 1 or its equivalent has been derived repeatedly&apos;-7 and an analogous equation, known as Rayleigh&apos;s equation, has been used for distillation. The assumptions on which Eq. 1 is based do not include an infinitely fast cooling rate as sometimes stated. In fact, Olsen and Hultgren %ave shown by experiment that very high solidification rates suppress coring, presumably by preventing diffusion in the liquid and by the effect undercooling has on the composition of the nucleus. Coring thus occurs at rates of cooling which are too fast for a close approach to equilibrium in the solid and too slow to suppress diffusion in the liquid and to cause marked undercooling. If the liquidus and solidus approximate straight lines, Eq. 1 simplifies to The fraction of liquid present at any temperature during nonequilibrium solidification can be calculated from Eqs. 1 or 2. By the lever relation it is

Jan 1, 1955

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information&apos; on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-&apos;. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.&apos; The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By James H. Bechtold

The yield strength of annealed tungsten was found to have a strain rate exponent 12 times as great as that of low carbon steel. The effects of temperature and strain rate could be correlated through the Zener-Hollomon parameter with a heat of activation associated with yielding of 32,000 cal per g-atom. This heat of activation is independent of strain although both the temperature and strain rate dependence of the yield strength vary with strain. MOST metals have mechanical properties that are relatively insensitive to strain rate, especially at temperatures below that at which creep is important. In iron and molybdenum," however, relatively large strain rate effects are observed in the temperature range where the rapid increase in yield strength occurs which leads to the ductile to brittle transition. In this temperature range Zener and Hollomon&apos; have suggested that the effects of strain rate and temperature T on the yield strength could be correlated through a single parameter, P, in the following manner where Q is a heat of activation characteristic of the metal and associated with some unspecified relaxation process. They also observed that if the temperature is restricted to a relatively narrow range— below room temperature for steel—that the logarithm of the yield strength could be expressed as a linear function of the logarithm of P. From this relation the logarithm of stress should be a linear function of the logarithm of the strain rate at constant temperature: where r will be referred to herein as the strain rate exponent. At a constant strain rate the logarithm of stress should be a linear function of l/T, ay(e = C) ~ eT [4] where q = Qr [5] and is referred to herein as the temperature exponent. These equations have been found to relate the effects of temperature and strain rate on the yield strength of molybdenum in the temperature range wherein the ductile to brittle transition occurs, —75° to +150°C.2 Bechtold and Shewmon3 have shown recently that the ductile to brittle transition in annealed tungsten occurs in the temperature range +150° to +350°C. In this temperature range the yield strength in-

Jan 1, 1957

By John W. Weeton, Max Quatinetz, Robert J. Schafer

Nickel powders of 1-, 0.4-, and 0.2- average particle size were combined with 0.05- p MgO powder. Oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were vacuum hot pressed and extruded at 2100°F. In spite of a general tendency to growth of oxide particles during processing, dispersions of fineness comparable to those of Sintered Aluminum Powder, SAP, were achieved. A small amount of oxide considerably improved 1800°F stress-rupture strength, but further oxide addition resulted in a decrease of strength. RECENTLY there has been much speculation concerning the requisites for strong and stable dispersion-strengthened alloys. The nature of the dispersed phase, the stability of the alloys, and variables influencing the mechanical properties of alloys have been given consideration. Such topics have been reviewed by Bunshah and Goetzel. Of the many parameters related to the mechanical properties of dispersion alloys, mean free path between dispersed particles (a measure of the fineness of the dispersion), particle size, and vol pct of the dispersed phase have been shown to be very important. Generally, strength increases with decreasing mean free path, and there is an optimum vol pct of dispersed phase. Just how fine a dispersion ought to be is somewhat open to debate, but Irmann, Lenel, Backensto, and Rose, Gregory and Grant,4 and others have shown in the original SAP-type alloys, aluminum plus aluminum oxide alloys, that better strength is generally obtained with finer dispersions and the best strengths were obtained when the mean free path was less than . Further, Cremens, and rant&apos; showed that in nickel plus aluminum oxide alloys, stress-rupture strength at 1500°F was definitely increasing with decreasing mean free path. In their investigation, however, the finest dispersions that were produced were about 2.0 mean free path. To determine the potential of the nickel plus oxide type of product, it would be neces- sary to obtain dispersions analogous to those of SAP alloys; namely, ones where the mean free path between oxides is less than . Unfortunately, however, it is very difficult to produce extremely fine dispersions of oxides in metals other than those which naturally form refractory oxide skins. There are several approaches to this problem including such procedures as mechanical mixing, internal oxidation, reduction of mixed oxides, and metal deposition from solution. Work at the Lewis Research Center has shown that metal powders 0.1p or finer could be produced by ball milling, when selected grinding aids were utilized.&apos; Because these unusually fine powders were available, it was an initial objective of this study to determine if by mixing of these fine Ni powders with various amounts of MgO (0.05) a fine dispersion of MgO in Ni comparable to those in Al-Al203 might be achieved. A second objective was then to attempt to relate the parameters of structure to 1800°F stress-rupture strength of the alloys. Nickel powders of 1-, 0.4-, and 0.2-p average particle size were combined with 0.05- average particle size MgO powder. This oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were hot pressed and extruded at 2100°F.

Jan 1, 1962

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962