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By C. G. Rhodes, D. Kramer

High-field critical transport current density (J) measurements at 4.2 °K as a Junction of applied magnetic field (H) were made on samples of cold-rolled and annealed columbium with H parallel to J. Microscopic examination of the samples revealed a well-defined planar fiber structure produced by the cold rolling. J was found to he lower when fibers are parallel to the direction of magnetic field penetration than when they are perpendicular. This effect may he a consequence of the interaction of flux movement with fiber boundaries. THE severe changes in microstructure brought about by cold working superconductors leads to profound changes in their superconducting behavior. In particular, the ability of a superconductor to carry a transport current with zero resistance (the maximum value of this current density will be called "J" in the presence of large external magnetic fields (to be referred to as "H") is greatly influenced by the microstructure. In the case of columbium, LeBlanc and Little1 and Autler et a1.2 have observed an increase in J due to cold work. LeBlanc and Little also observed an anisotropy in J in cold-rolled columbium strips, which Hake et al.3-6 have shown to depend upon the angle between H (H ? J) and the rolling plane. An increase in J due to cold work has been found in a variety of high-field superconducting alloys3'4'7-9 as has the anisotropy effect.10 First explanations of why cold work raised J invoked the idea that dislocations carried the high-field supercurrents,8,11 since cold working drastically increases the dislocation density and presumably the number of supercurrent paths. However, recent ideas on the nature of high-field superconductivity together with new experimental evidence reveal that the bulk of certain superconductors can remain superconducting in high fields while carrying high transport currents. These later developments have been discussed by Berlin-court and Hake12 and a comprehensive review has been prepared by Berlincourt.13 According to the ideas of Gorter14 and Anderson,15 one would expect that the influence of microstructure on high-field supercurrent density will depend on tine interaction between microstructure and penetrating flux and on the direction of the Lorentz

Jan 1, 1965

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1'3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By M. E. Glicksman, G. S. Ansel

It has been shown by Walton and Chalmers,&apos; that the mechanism of the development of solidification textures in castings involves the preferential growth of dendrites along certain crystallographic directions as determined by the influence of prevailing heat-transfer conditions. Specifically, this growth is parallel to the direction of heat flow. The purpose of the present investigation was to determine the applicability of this mechanism to: 1) commercially pure aluminum (99.75 pct) solidified to coarse columnar crystals, 2) an aluminum-silicon casting alloy (5.25 Si, 0.38 Fe, 0.02 Cu, 0.10 Ti, 0.002 S) cast to a fine-grained structure under complex and reproducible heat transfer conditions. PROCEDURE AND RESULTS 1) Specimen Preparation—Using a technique similar to that employed by Northcott and Thomas,2 samples were melted in the directional solidification mold, Fig. 1, by heating the entire assembly to 670° C. The mold was then end cooled using a water jet. From considerations of harmonic analysis, the likely distribution of isotherm normals encountered by the growing crystals is shown in Fig. 1. 2) Orientation Analysis—The pure aluminum sample froze to large columnar crystals, nucleated close to the metal diaphragm, with the growth direction parallel to the mold axis. Using the back-reflection Laue technique, the growth direction of these crystals was determined to be a <100>, which coincided within 53 deg to the mold axis. Metallographic examination of the relatively fine-grained aluminum-silicon sample revealed a dendritic mode of growth having its primary dendrite arms along isotherm normals. Back-reflection Debye-Scherrer patterns, taken with the specimen rotating about its cylinder axis, yielded rings displaying symmetrical arcing, thus proving that the sample did, indeed, possess the solidification texture inferred from the preliminary metallographic examination. To determine the extent and orientation of the texture in the aluminum-silicon alloy, a density distribution of the (111) poles of the sample was plotted using the transmission Debge-Scherrer

Jan 1, 1960

By J. O. Brittain, E. P. Lautenschlager, D. A. Kiewit

Compression tests were run in the temperature range of 700° to 900°C ox 0&apos; phase NiAl intermetal-lic alloys of several grain sizes. At these temperatures the minimum strengths were observed at the stoichiometric composition. While significant increases in strength occurved in both the low-nickel (vacancy) and high-nickel (substitutional) regions, the highest strengths were found in the high-nickel region. During deformation serrated flow was sometimes observed in the low-nickel alloys. After deformation transgranular cvacking and deformation striations were observed in all compositions tested. AS part of a general investigation of the properties of NiAl inter metallic compounds, a preliminary study of the role of point defects upon plasticity was made by high-temperature compression tests on ß&apos; NiAl specimens of several grain sizes and compositions. ß&apos; NiAl is an intermetallic compound having a CsCl structure and a rather wide range of composition from A1-45 at. pct to 60 at. pct Ni.1 According to Bradley and Taylor2 and to cooper,&apos; it possesses a defect lattice in which departures from stoichiometry in the direction of decreased nickel content lead to the presence of vacant nickel sites (although Cooper&apos;s work indicates that a small amount of substitution also occurs) whereas departures on the high-nickel side lead to substitution of nickel on aluminum sites. NiAl forms congru-ently from the melt at approximately 1650°C,1 and thus has a higher melting point than either of its component elements. Up to this time, although this and other high-melting intermetallic compounds have been suggested for elevated-temperature usage,4 only the hardness4 and a few tensile-strength measurements5 have been reported for NiAl at high temperatures. In the present investigation the effects of composition upon the compressive-strength properties in a range of 700° to 900°C have been measured for NiAl of several grain sizes. EXPERIMENTAL PROCEDURES The alloys were made as described elsewhere6 from an A1-46.8 at. pct Ni master alloy furnished by the International Nickel Co. with additions of high-purity nickel and aluminum. The charges were vacuum-induction-melted in A12O3 crucibles with small amounts of helium added to the atmosphere to suppress vaporization. They were cooled slowly from the melting temperature to achieve uniform grain size. In order to refine the as-grown grain size a special rolling technique was developed. Alloys were packed into 0.10-in. wall-type 302 stainless-steel tubes which were partially filled with magnesium oxide to prevent bonding between the alloy and the steel jacket. The ends of the tubes were closed by hot forging, and the packets were then hot-rolled. The alloys with greater than 50 at. pct Ni were rolled at 1100°C, but it was found necessary to increase the temperature to 1350° C before alloys with less than 50 at. pct Ni would roll without cracking. With these temperatures, reductions as high as 48 pct were achieved in a single pass. The rolled alloys will hereafter be referred to as "fine grained" whereas the as-grown material will be designated "coarse-grained&apos;&apos;. The compression specimens were made by cutting square cross-sectional pieces, approximately 3/16 by 3/16 by 1/2 in., with a water-cooled diamond cut-off wheel from the as-grown or the rolled alloys. Specimens were ground to their final dimensions by polishing through 3/0 grit silicon carbide papers. The final shape was a rectangular parallelepiped of square cross section having a height-to-width ratio of 3:1. Compression testing was carried out in a compression rig of our own design mounted on an In-stron Floor Model. The specimen chamber could be heated to 1000°C and was controlled within ±2°C. The compression rig was enclosed within a bell jar and was maintained at a 50 µ of mercury vacuum throughout the duration of the test. The test cham -ber was heated from room to test temperature within 15 min. Specimens were then held at the test temperature 30 min prior to testing. Previous experiments indicated that no grain growth would occur within this time. An Instron Variable Crosshead speed unit was used to adjust for small variations in specimen lengths in order to have a constant initial strain rate, €, for all specimens of a group. For the fine-grained specimens the strain rate was changed rapidly at constant temperature by a factor of 10 with the speed lever on the Instron. For a given € the compression data was analyzed in terms of true plastic strain (E) and true compressive stress (0).

Jan 1, 1965

By H. C. van Elst

Ultrahigh-speedphotographic and electronic meth-ods were applied to an investigation of details of brittle-fracture propagation in steel. The brittle fractures studied were obtained in steel plate with the aid of a Robertson apparatus. It was found that a brittle fracture proceeds by discrete steps ranging from 30 mm near the stop temperature to less than 2 mm at lower temperatures. The halting FROM prior metallographic observations of brittle fracture in steel&apos; it could be concluded that the distribution of mechanical twins along a brittle fracture was similar to the distribution of mechanical twins induced by explosive deformation. It was therefore assumed that a running brittle fracture created stress waves, cf. Refs. 2-7. An emission of stress waves by a brittle fracture, however, seems only conceivable if the fracture propagates by discrete steps. For this reason a study of the details of times between successive steps drop in this tem-perature region from 20 usec to about 1 psec. The stepwise propagation mechanism is accompanied by an intermittent emission of stress waves of the order of 100 to 200 kg per sq mm. These stress waves seen1 to play an important role in the mechanism of brittle fracture as will be discussed. brittle-fracture propagation was undertaken to investigate the possible determination of the fracture steps and the emitted stress waves associated with the assumed mechanism. The more practical object of this work is the development of a test method for the determination of the ductile-brittle transition in small specimens. This has special advantages for the study of irradiation damage in steel. In this test method, which will be published in a following paper, the stress waves emitted by an actual brittle fracture are reproduced with explosive or electrical means and are then transmitted through small specimens at various temperatures. In the present paper only the results of the brittle-fracture study will be reported.

Jan 1, 1964

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein&apos; and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y&apos; phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y&apos; and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951

By A. H. Willis

In this paper the results of an exploratory study conducted by personnel of the Knolls Atomic Power Laboratory on 18.6, 22, and 40 wt pct uranium-zirconium alloy will be presented. LARGE power output and long life or endurance from small, compact nuclear reactors require the use of enriched uranium for a fuel material. However, the ability to remove heat from the element, the tolerable fission product concentration, or some physical limitation of the system can limit the allowable fuel enrichment, or the volume of the fuel. In such an event, the fuel-element designer must find a suitable diluent for the uranium. Zirconium is an attractive material for such a purpose as it has good nuclear properties and a low absorption cross section. Because it has a good corrosion resistance in water, zirconium is a suitable cladding and the uranium-zirconium alloy makes a good core material. The alloy has a high thermal conductivity, a low elastic modulus, and a low thermal-expansion coefficient, all of which tend to minimize the thermal stresses in the core. Furthermore, the unirradiated material is reasonably ductile and has adequate strength. DESCRIPTION OF SAMPLES Two types of cylindrical samples were used in this study 1) short, 1/2-to 1-in.-long samples to test the irradiation stability of the alloy and 2) 2-ft-long samples to investigate the resistance of an element to longitudinal deformation. Composite samples having 0.060-to 0.140-in. core diameters and clad with a 0.010-in. thick zirconium jacket were fabricated by coextrusion and by hydrostatic pressure bonding of the cladding to the preformed core material. Both fabrication processes produced the uniform metallurgical core-to-cladding bond which was felt necessary to minimize the uncertainty of the central core temperature. Both consumable-arc and induction-melting techniques were used to melt the uranium-sponge zirconium core alloy. Since a graphite crucible was used in induction-melting this alloy contained more carbon impurity, which resulted in a finer grain size than the arc-melted alloy. The core to cladding interface was uniform in elements coextruded from the fine-grain, induction-melted core material, while those elements fabricated using arc-melted core material had very irregular interfaces because of the coarser grain size. Both cold-worked and heat-treated fuel materials were irradiation tested. Cold-worked alloys were swaged to about a 5 pct final reduction in area without subsequent annealing. The heat-treated alloys were heated to 800°C, held at temperature for 15 min and furnace-cooled to about room temperature. This

Jan 1, 1960

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By F. V. Lenel, G. S. Ansell, M. J. Salkind

An experiment is described in which the growth of interparticle necks in an array of loose spherical silver powder at temperatures near 300°C was determined by measuring changes in the electrical resistance of the array. The activation energy for neck growth of contacts was derived by abruptly changing temperature and noting the change in the rate of neck growth. Since the experiments were run under an external load, the changes in activation energy with stress could he determined. The activation energy was found to decrease rapidly with increasing stress. It is concluded that the material transport in the experiments is one of plastic flow by dislocation motion. The variation of activation energy with stress is typical for cross slip of dislocations, an important material transport mechanism in the temperature range investigated. THE process in which powder compacts or aggregates of loose powder are held at an elevated temperature under an external load is called hot pressing or sintering under pressure by powder metallurgists. In this investigation the early stages of this process as applied to loose spherical silver- powder aggregates were studied. The powder particles were approximately 100µ in diameter and the temperature was near 300°C, i.e., below one half of the melting point of silver in degrees Kelvin, where volume diffusion is not expected to contribute to sintering. In the process, the contact or neck areas between powder particles grow. Since this involves plastic deformation of the particles under a constant external load (even though not under constant stress) it would be termed creep by mechanical metallurgists. On the other hand, the growth in neck area observed in compacts or loose-powder aggregates held at elevated temperature without the application of an external load is termed sintering by powder metallurgists. During sintering the major driving force is the stress due to surface tension. However, even when no load is placed on the compact or powder aggregate, an external stress, i.e., gravity, plays an important role in sintering in addition to those stresses arising from surface tension, as was shown in two previous investigations.&apos;" It is therefore postulated that no sharp dividing line can be drawn between the phenomena of "creep" and "sintering". Different material transport mechanisms may be involved in either of these phenomena, but they will depend upon the temperature and the level of stress, but not necessarily upon the nature of the driving force: surface tension or external load. At the low temperatures of this investigation, an external stress much higher than the stress due to surface tension is necessary to obtain measurable rates of neck growth. In order to avoid misunderstanding this phenomenon will be called "creep". The rate of growth in contact area in the loose silver-powder aggregates was determined by meas-

Jan 1, 1965

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.&apos; The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750&apos; and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By H. B. Hunter, F. G. Stone, F. J. Dunkerley

Introduction and Literature Survey This is the second in a series of papers coming from this laboratory on the correlation of the low temperature tensile properties of tin-binary alloys with microstructure. These engineering data and those of the previous paper1 were obtained as the initial part of a long-range program to determine the changes in the fundamental mechanical properties accompanying the beta to alpha phase change in tin and its binary alloys below 13.2°C. Since it appears now that the more fundamental studies will be delayed,* and since no summary of the low temperature properties of these tin-base white bearing alloys was found in the literature, it was decided to publish all the engineering data thus far obtained. Accordingly, the tensile properties of thirteen binary alloys containing from 0.1 to 60 pet cadmium and 0.1 to 10.43 pet antimony measured at six temperatures from —196 to +23°C are presented here and their variations rationalized in terms of microstructure. A literature search showed that these systems had not been investigated at low temperatures, although both the tin-cadmium and tin-antimony2,3,4,5 and the tin-rich corner of the ternary system67 have been studied at room temperature. Hanson and Pell-Wal-pole5 and Homer and Plummer4 determined the tensile properties of alloys containing from 0 to 10 pet cadmium. The same authors3 determined the tensile strength and elongation in the tin-antimony system from 2 to 18 pet antimony at room temperature while Pell-Walpole et al.6,7 studied the properties of high tin and tin-antimony-cadmium alloys. Since there were many variables besides composition in these tests, it was difficult to make a valid comparison with the room temperature data of the present study, but in general the tensile strength and ductility values are in reasonable agreement. Pell-Walpole2 also determined the effect of grain size on the tensile strength of pure tin and 1 pet alloys of both antimony and cadmium. The true maximum stress was found to decrease exponentially as the number of grains in the cross-section increased. This effect of grain size was strikingly revealed in the present work, as indicated in a later section. Hanson and Pell-Walpole8 placed the solid solubility limit of antimony in tin at 3.5 pet at 20°C, increasing to 4 pet at 190°C, and then sharply increasing to 10.3 pet at 246°C (the latter being a peritectic point). Their results are in disagreement with those of previous investigators,9 and the discrepancy seems to lie in the micro-graphic observation of the second phase

Jan 1, 1950

By K. Winterton

The effect of a near-saturation unidirectional magnetic field was to decrease slightly the endurance life in Armco iron in the annealed condition. This is expected since the energy-absorbing mechanism associated with domain wall movemenfs is inhibited bv the strong field. THE factors determining failure under dynamic loading are not yet clearly recognized. One of the properties of a metal which might be thought to influence fatigue life is its damping capacity. Foppl1 conducted an alternating torsion test at a frequency of 700 cpm continuously for a period of 3 years, without the test piece breaking or showing any sign of deterioration after 1100 Million cycles of stress; the rate of dissipation of energy was sufficient to maintain the test piece at about 100°C above the ambient temperature. cazaud2 concludes from this, and others follow him, that (&apos;the capacity for dissipation in the form of heat by internal damping is unlimited" and that therefore "damping is not directly related with fracture by fatigue." Future work may necessitate qualification of this rather uncompromising view. It is shown later that in all

Jan 1, 1960

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By Larry Kaufman, Morris Cohen

THE solid phase equilibria&apos; and the martensitic transformation in the iron-nickel system have been the subject of considerable study. In addition, there have been numerous investigations on the calorimetric and thermodynamic properties of iron-nickel alloys. The purpose of the present work is to extend the existing information concerning the martensitic reaction in the iron-nickel system, and to develop a general thermodynamic treatment which will encompass the equilibrium and non-equilibrium phase

Jan 1, 1957

By J. G. Early, F. V. Lenel, G. S. Ansell

The isothermal shrinkage rates of copper-powder compacts were determined in the temperature range from 760o to 1060oC. The rates for compacts fabricated from a pure spherical copper powder were compared, on the one hand, with those fabricated from a spherical powder containing a dispersion of aluminum oxide in the copper matrix and, on the other hand, with those fabricated from a pure copper powder having irregularly shaped particles. The irregular copper-powder compacts shrank much faster than the spherical copper-powder compacts and these, in turn, shrank faster than dispersion -strengthened copper -powder compacts. The experiments were run under a small external load. By varying this load, the stress dependence of the isothermal shrinkage rate could be measured for compacts from spherical-copper powders. This stress dependence was found to be approximately proportional to the 4th (dispersion-strengthened alloys) or 4.5th (pure metals) power of the stress. It is concluded that the material-trans port mechanism is due to dislocation climb rather than to Herring-Naharro creep. In this investigation the isothermal shrinkage rates of compacts made of copper powder with an average particle size of 70 g in the temperature range from 780o to 1060°C were studied. The aim of the investigation was to determine the mechanism of material transport responsible for the shrinkage of these compacts. Since the phenomenon observed in this investigation was shrinkage of compacts at high temperatures, it will be necessary to consider all the material-transport mechanisms possible in sintering. It is unlikely that evaporation and condensation, surface diffusion, or even volume diffusion of vacancies, in which surfaces of small radius of curvature are vacancy sources and those of larger radius of curvature vacancy sinks, will materially contribute to a sintering process involving shrinkage, i.e., one in which the centers of adjacent particles move towards each other. The two principal mechanisms which were considered were the so-called Nabarro-Herring mechanism and a plastic deformation mechanism by dislocation movement. Both of these mechanisms were originally conceived to explain creep, i.e., the plastic deformation of metals at elevated temperatures under a constant applied stress. The shrinking of metal-powder compacts which was studied in this investigation can be readily treated as a creep process. This means that the shrinkage rates observed are considered as creep rates under the influence of an applied stress. It is true that the stresses in sintering experiments are generally not constant but decrease continually with time, but, by considering creep rates or shrinkage rates over a relatively short time interval, the small changes in stress during this time interval can generally be neglected. Nabarro-Herring microcreep is a high-temperature deformation mechanism which is caused by a diffusional flow of vacancies from boundaries under a tensile stress towards those under a compres-sive stress. Herring1 has shown that in this type of microcreep the strain rate e is proportional to the applied stress and follows an equation of the form ma, aexp(-Q/RT) [l| where <j is applied stress, Q is the activation energy for self-diffusion, R is the gas constant, and T is the absolute temperature This type of creep can explain the shrinkage of a porous compact. The surface of the pores are subjected to the tensile stress of surface tension, while the grain boundaries are under a compressive stress also due to surface tension. Vacancies diffuse from the pore surface through the lattice to the grain boundaries, where they are eliminated. In order to maintain vacancy equilibrium at the pore surface the vacancies leaving the region of the pore surface are replenished from the volume of the pore, which means that the pores shrink.

Jan 1, 1964

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,&apos; in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young&apos;s modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y &apos; and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? &apos; phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?&apos; and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

By R. A. Vandermeer, Paul Gordon

On the basis of a unified concept, theoretical erPressions for grain boundary migration in recrys-tallization are derzved for impurity-controlled and impurity-independent migration. The expression in the former case is analogous to that Previously derived by Lucke and Detert, and in the latter is shown to be equivalent to that usually obtained on the basis of absolute reaction rate theory. The equations are tested with quantitative experimental data for boundary migration obtained for the recrystallization of poly crystalline zone-refined alumimnz and for binary "alloys" of this aluminum with 0.00021, 0.00043, 0.0017, 0.0034, 0.0068, 0.0124, and 0.0256 at. pct Cu, respectively. All the essential characteristics of the e@erimentally determined boundary migration rates check both qualitatively ard quantitatively with the predictions of the theoretical equations. THE rates of transformations are customarily analyzed phenomenologically in terms of the two component rates—N, the rate of nucleation and, G, the rate of growth of the nuclei. The scientific aim of both theory and experiment is to describe the fundamental atomic phemmena involved in these two component processes with the hope that parameters calculated from theoretical equations will check those found experimentally. In solid state transformations, the theoretical and experimental problems are both generally of almost prohibitive complexity, for in addition to changes in composition and in such properties as density which may accompany transformations in amorphous, nonrigid materials, transformations in crystalline substances also involve structural changes, crystal reorientations, and the development of stresses. In studying such transformations it thus becomes; highly desirable, if not essential, to focus on a transformation and a set of conditions which minimize the number of active variables. This principle has been applied with considerable success by Cohen and his associates&apos; in their evaluation of nucleation theories using the martensite transformation as the basis of study. A similar possibility exists for the evaluation of growth theories by the use of recrystallization after cold-deforming. If an unalloyed metal is employed as the subject of investigation, the recrystallization transformation involves basically only a change in strain-conditions and orientations. In spite of this possible simplilfication, however, until recently little quantitative success has attended attempts to correlate recrystal1ization parameters measured experimentally with those calculated theoretically. It seems highly probable that this lack of success may be attributed, both in the experimental and theoretical treatments, to one or more of the following factors: a) conditions have usually been studied under which apparently* both nucleation and growth are active;

Jan 1, 1962