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By W. B. Triplett, H. I. Aaronson, G. M. Andes

THE morphology and mechanism of the proeutectoid a and the eutectoid reactions have been recently investigated in some detail in an iodide-base Ti—7.22 pct Cr alloy.' These studies have now been extended to an iodide-base Ti—10.8 pct Cr alloy in order to evaluate the effects of composition on the proeutectoid and eutectoid transformations in titanium-chromium alloys. The alloy used in this investigation had the following composition: 10.8 Cr, 0.0327 0, 0.011 N, 0.0063 H, and 0.011 pct C. Specimens of this alloy were heat treated in evacuated and internally get-tered Vycor capsules. The specimens were solu-

Jan 1, 1959

By H. I. Aaronson

The nucleation of pearlite at proeutectoid ferrite is inhibited, to an increasing extent, at the following locations: At twin boundary-nucleated ferrite, between closely spaced ferrite sideplates, and at intragranular plates. These effects are discussed in terms of the influence of transformation strain energies and of the interfacial free energy of austen-ite:ferrite boundaries on the rate of pearlite nucleation. The growth of pearlite into the interiors of austenite grains from the region of the grain boundaries is markedly restricted when low reaction temperatures and large austenite grain sizes permit the development of interlocking networks of intragranular ferrite plates. PREVIOUS investigators have made extensive studies of the interactions which occur between the proeutectoid ferrite and the pearlite reactions from the viewpoint of the mechanisms through which pearlite interferes with the nucleation and growth of proeutectoid ferrite.1-3 In the present investigation, the processes through which proeutectoid ferrite (hereafter termed simply "ferrite") can reduce the rate of formation of pearlite have been explored in some detail. A steel with a relatively low carbon content, in which the ferrite reaction can compete successfully with the pearlite reaction over a wide range of reaction temperature, and exceptionally coarse-grained specimens, which further emphasize the role of the ferrite reaction, have been employed for most of this work. A brief examination also has been made, however, of the effects of smaller austenite grain sizes upon these processes. Experimental Procedure The steel employed had the following composition: 0.29 pet C, 0.76 pet Mn, 0.25 pet si, 0,007 pet S, and 0.005 pct P. This alloy was homogenized for 48 hr at 1250°C. The investigation was performed

Jan 1, 1959

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By D. D. Pollock, D. I. Finch

PREVIOUS work' on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,' except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By A. P. Young, F. C. Holden

IN many of the early investigations of the aging of titanium alloys, it was observed that the retained beta phase could be aged to a high hardness without an apparent change in microstructure; moreover, in some alloys it was found that even a very rapid quench produced beta having an anomalously high hardness. What appeared to be hard beta phase was designated as "beta prime," to distinguish it from the softer normal retained beta phase. Frost and co-workers'.' demonstrated that the increased hardness is caused by the formation of a metastable phase, omega, which can be identified from its X-ray diffraction pattern. This reaction also has been studied by Brotzen, et a1.,3 and the structure of the omega phase has been published by Silcock, et al.," and by Austin and Doig.3 The X-ray diffraction analysis by Austin and Doig indicated that omega is low in alloy content, approaching the composition of the stable alpha. The aging process proceeds by the path Thus, overaging results in the formation of alpha and the ultimate disappearance of omega. This is accompanied by a decrease in hardness and a recovery of ductility. The present work represents a study of the aging process in a high-purity Ti-6.4 Mn alloy, in which optical and electron microscopy, X-ray diffraction, and hardness data were correlated. The specimens, 1/8-in. sections cut from 1/4-in.-diam rod, were heated in argon to a temperature just into the beta field (810°C), held for 1 hr, and water-quenched. The aging samples were heated in air for 1 hr at 300 to 500°C. The specimens were ground and mechanically polished, finishing with alternate etching and polishing on a slow-speed wheel to remove disturbed metal from the surface. The surface finally was swab-etched, rinsed with tap water, and air-dried. The etchant used was an aqueous solution containing 1 1/2 pct HF and 3 1/2 pct HNO3. This procedure is identical with that used for preparing metallographic specimens, except that the optimum degree of final etching required for electron microscopy may vary from that used for light microscopy. Metal replicas, backed with silica, were prepared from plastic strip-pings for examination with the electron microscope. Complete details of the procedures used for preparing these replicas are available elsewhere." Fig. 1 shows a comparison between the structures revealed by the electron microscope and those obtained by conventional light microscopy. Hardness and X-ray diffraction data are listed in Table I. No evidence of a second phase is apparent in the optical micrographs for the as-quenched sample, or for the specimens aged at 300 or 400°C; fine alpha particles can be seen in the specimen aged at 500°C. In the electron micrographs, visible equiaxed pocks appear in the as-quenched specimen, and, with increasing density, in the samples aged at 300 and 400°C. After aging at 500°C, the structure becomes markedly coarser and develops an oriented appearance of a second phase, coincident with the appearance of visible alpha particles in the light micrographs. These observations are confirmed by X-ray diffraction and hardness data. In these specimens, aged for 1 hr, the intensity of the omega pattern increases to a maximum at the 400°C aging temperature, corresponding to maximum hardness and the maximum density of pocks in the electron micrographs. At this point the beta phase shows a definite enrichment in Mn. At 500°C, little or no omega re-

Jan 1, 1959

By W. A. Backofen, M. L. Ebner, D. H. Avery

Slip on (11221 planes, which do not contain a close-packed direction, has been identified on crystals strained at —190°C. Evidence is also presented to show that (1071) pyramidal slip is a mode of deformation at 25ºC in a limited orientation range. PYRAMIDAL slip (l011) <1120> in magnesium at elevated temperatures has been established for some time.1-2 More recently, Burke and Hibbard reported this mode of deformation at 25"C, but their results were questioned by Craig.&apos; Also, as far as the present authors know, slip in magnesium on pyramidal planes of the second order, Type II (1122)) has not previously been reported, although Gilman"," identified (1122) slip in another hexagonal metal

Jan 1, 1959

By D. E. Swets, P. C. Frank, D. L. Fry

THE hydrogen-steel system has received considerable attention in the past several years. Recent experiments in this laboratory have shown that another group of operations, namely, sanding and grinding,&apos; must be added to the already well-estab- lished list of phenomena that cause hydrogen to permeate steel. Qualitative tests which have been made with a very sensitive ion-gage type of detector similar to that used by Norton,&apos; showed that sanding a steel surface caused hydrogen permeation. A metal type 6~6 vacuum tube was used as the ion gage with an electrometer to measure the ion c~rrent.~ The protective enamel coating was removed from the tube.

Jan 1, 1959

By F. J. Darnell

SINGLE crystals of a-titanium are difficult to obtain because of the phase transformation at 882 °C in which the structure changes from the high-temperature body-centered structure ß to the low-temperature hexagonal close-packed structure a. Preparation of single crystals of a-titanium has previously been accomplished by a strain-anneal method which takes several days and is not generally reproducible. Single crystals as large as 5 mm

Jan 1, 1959

By D. C. Buffum, L. D. Jaffee

THAT the path of brittle fracture in temper brit-tle steel differs from the path in unembrittled steel has been known for some years1 More recently it has been recognized that alloy steels, at least, display two forms of temper brittleness1 which may be called upper-nose and lower-nose. No experimental evidence has been published, however, to show that the two forms can be distinguished by simple inspection of brittle fractures. Fig. 1 is a photograph of the fractured surface of a V-notch Charpy specimen of SAE 3140 steel in which temper brittleness developed during heat treatment in the lower-nose temperature range.&apos; The steel was austenitized 1 hr at 900°, tempered 1 hr at 675", and embrittled 48 hr at 500°C, with water-quenching after each treatment. The temperature of transition from ductile to brittle fracture in the Charpy test was + 2°C (criterion of transition: 100 pet fibrous). The hardness was Re 25; the austenite grain size ASTM 8. This specimen was broken at 150°C in the standard Charpy test and absorbed 6.6 ft-lb; its fracture was rated 0 pet fibrous. Fig. 1 shows that the fracture appeared rough to the naked eye. At the side of the specimen away from the notch (the side which was in compression during the test), the surface as a whole deviated sharply from a plane. At higher magnification, X60, the surface gave

Jan 1, 1959

By J. J. Gilman

THEORIES of fracture in metals have been based primarily on the dependence of fracture strength on grain size. This dependence was first observed by Masing and Polanyi.l These workers, as well as 0rowan12 and Davidenkov and Wittman,&apos; thought the grain size could be equated with the crack size in the Griffith condition for crack propagation.4 In this way they could account for the observed proportionality between fracture stress and the reciprocal square root of the grain size. The chief results of recent investigations of the fracture strength of polycrystals are summarized in Fig. 1. Low for iron,5 Petch for iron,&apos; Greenwood and Quarrel for zinc, Petch and Zein for zinc,&apos; and Hauser, Landon, and Dorn for magnesium&apos;&apos; have all found that the fracture stress of a polycrystal is proportional to the reciprocal square root of the grain size. Also, they find that, for large grain sizes, the fracture stress lies near the extrapolation of the yield-stress curve determined at small grain sizes; where measurable plastic strain precedes fracture. Low9 has gone a step further and shown that, in Range 1, the fracture stress in tension is almost identical to the yield stress in compression for a given grain size. Homes and Gouzou, 10 and Low also have shown that, in Range 2 of Fig. 1, microcracks form when the yield stress is reached, but they do not cause failure until the stress reaches a much higher value. The fact that yielding always precedes fracture suggests that fracture is induced by plastic flow. A mechanism by which this might occur was first proposed by Zener.11 He pointed out that blocked dislocations would cause stress concentrations which might cause fracture. The blocking would be caused by grain boundaries. This idea has been developed by Eshelby, Frank, and Nabarro,12 by Koehler,13 and by Stroh.14 By means of etchpits blocked dislocations have been observed in brass by Jacquet,15 in zinc by Gilman,16 and in lithium fluoride by Gilman and johnston. The blocked-dislocation theory and the experiments that bear on it have been summarized by Mott.18 One of the strong points of the blocked-dislocation theory is that it can explain the grain-size dependence of the fracture stress in a natural way. However, Low9 has pointed out that the theory is not satisfying when it is considered quantitatively. Gilman10 also has criticized the theory and presented an alternative interpretation of the relation between fracture stress and grain size. Since the blocked-dislocation theory is not the only theory that can explain in the grain-size effect, it is necessary to find other evidence either to support or deny it. In this investigation the following points were studied: 1) If blocked dislocations normally cause fracture, then the fracture stress ought to be very high in the absence of plastic glide. Is it? 2) If dislocations must be blocked in order for metals to fracture, then certain types of grain

Jan 1, 1959

By N. E. Rogen, N. J. Grant

AGE-hardening in nickel-chromium-titanium-aluminum alloys in the composition range characterized by the Nimonic alloys, is dependent upon the precipitation of the Ni3(AI,Ti) (y&apos;) phase.1 This phase is found to precipitate at about 700°C.1 Ni,Al is a face-centered-cubic ordered structure with a lattice parameter of 3.560 A. The atomic configuration is such that the aluminum atoms occupy the cube corners and nickel occupies the cube faces with titanium substituting for the aluminum preferentially. A maximum of three out of every five aluminum atoms can be replaced by titanium atoms in the -y &apos;phase.&apos; When the solubility of the y&apos;-phase is exceeded for titanium the T(Ni,Ti) phase is formed. The T-phase is an ordered close-packed hexagonal intermetallic structure which shows little solubility for the other elements in these alloys. The lattice parameter for T-phase is a - 2.5454 kr and c = 8.2900 kx units."

Jan 1, 1959

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By M. J. Sinnott, J. C. Tobin

A technique for collecting and analyzing the small quantities of gases desorbed on heating metal powders has been developed. The gases collected from copper powders of various types of manufacture have been analyzed and found to contain H2O, CO2, and SO2. The quantities of gas evolved vary from 0.05 to 1.0 milliliter, under standard con-ditons of temperature and pressure, per gram of powder. The source of the gas has been traced to surface films on the powder. IN the powder-metal industry it is recognized that the presence of gases in the powders affects the processing and resulting properties of the sintered product. Several sources for these gases are possible; namely, chemical reactions with the sintering atmospheres, inclusion. of gases during compacting, dissolved gases in the metal powder, and sorbed gases on the metal-,powder surfaces.1, 2, 3 Since the quantities of the gases are relatively small, no direct attempt has been made to collect and analyze them nor to isolate their source. The work that has been done has been concerned with the dimensional stability of the product., its porosity, density, or mechanical and physical properties. Conclusions are drawn on the basis of studies of this type as to the probable effect of gases on these properties. 4, 5, 0 In the present investigation an attempt has been made to obtain quantitative data on the analysis and quantities of gases associated with copper powders manufactured in different ways. Apparatus was constructed to collect gases evolved from loosely packed powder samples on heating to various temperatures under a reduced pressure of helium. The powders were outgassed thoroughly in a vacuum prior to starting the collection operation in order to eliminate mechanically entrapped gases and to prevent the possible reaction of the powder with these gases. Experimental Procedures Materials—The major portion of the investigation was carried out on a single heat of water-atomized, oxygen-free, high-conductivity copper. A relatively coarse fraction of this powder, 20 to 100 mesh, was tested as a mixed powder and as various graded size fractions. The microstructure of this powder showed equiaxed grains and was clean and free from oxides and oxide eutectic. The particle size, as determined

Jan 1, 1959

By F. Weinberg

It has been suggested, for some time, that the behavior of metals under high-temperature creep conditions is strongly influenced by the behavior of the grain boundaries present in the material. This has led to a number of investigations1-6 in which attempts were made to measure the properties of the grain boundaries themselves, both to determine their contribution to the creep process and to obtain further knowledge of their intrinsic structure and properties. The present investigation was undertaken to extend the observed data under more closely controlled experimental conditions and to attempt to clarify sonie of the discrepancies in the literature. A brief report of the preliminary results has been published.7 EXPERIMENTAL PROCEDURE For the present investigation, controlled orientation specimens were used having plane boundaries which terminated at the specimen surface. Trierys-tal specimens were used instead of the bicrystal type of Puttick and King,&apos; in order to simplify the gripping technique required to apply a shear stress along the boundary. The aluminum used was obtained from the Aluminum Francaise and was of 99.994 pct purity, containing 0.002 pct each of Cu, Fe, and Si. The aluminum tricrystals were grown horizontally from the melt, in graphite boats, and in an argon atmosphere, following the technique developed by Chalmers.&apos; The orientation of the tricrystals was controlled by using seed crystals separated by mica inserts. Thermal conditions were adjusted to produce tricrystals having boundaries which were macroscopically straight, parallel to the growth direction, and perpendicular to the top surface. Following growth, the tricrystals were carefully cut with a jeweller&apos;s saw to the test specimen shapes shown in Fig. l(a) and l(b). In Fig. 1(a), the boundaries subjected to shear stresses are indicated AB and CD: Points A and C are the ends of the mica inserts separating the seed crystals; points B and D are at lateral cuts made in the specimen. It was found that the slots left by the mica inserts at A and C had to be enlarged slightly, by cutting, to ensure that the boundary terminated freely at these points. A shear stress was applied to the boundarks by gripping the upper two legs in file-faced Inconel grips and suspending a weight from the lower part of the specimen held in similar grips, as shown schematically in the diagram. The test specimens shown in Fig. 1(b) were cut from long

Jan 1, 1959

By N. J. Grant, F. B. Cuff

DURING a recent investigation of high-purity aluminum,&apos; evidence was found for grain-boundary sliding and migration at room temperature. The investigation was concerned primarily with an electron-microscopic study of a fine (approximately 1 micron) network that appeared on the surface of chemically polished aluminum. The nature of the network will not be discussed since it serves only as markers showing relative displacements in this instance. The pertinent observation, shown in Fig. 1, was made on a flat tensile specimen which had been strained about 8 pct at room temperature. As can be seen in this electron micrograph, a grain boundary has undergone a certain amount of sliding. The reason for the existence of the two differently appearing networks is given in the foregoing reference. For present purposes, however, the transition region can be disregarded. A close study of this picture reveals that in addi- tion to sliding there is a narrow band adjacent to and above the grain boundary. Fig. 2 is a schematic drawing showing the essential features of this band.

Jan 1, 1959

By J. E. Hove

The high temperature physical properties of graphite are reviewed and interpreted in the light of present day knowledge of the mechanisms affecting these properties. The thermal and mechanical behaviors only are discussed and, whenever possible, comparisons are made with other refractory materials. Possible further studies are indicated, including some carbide work. AS long as the term high temperature implied only temperatures up to about 1000°C, the materials problems which arose could usually be handled by fairly conventional metal alloy types, such as the Co-Cr-Ni superalloys, for which there exists a great deal of technology. Perhaps this temperature can still be considered an upper limit for normal applications, but it is certainly true that the number of abnormal applications is increasing rapidly. The advent, in recent years, of ram-jet and rocket missiles and of high power nuclear reactor heat sources has raised a host of questions concerning the basic problem of what material to use in the temperature range up to 2000°C and higher. While there are, of course, many metals, in the second and third transition series, which melt at considerably higher temperatures than this, these metals are, at present, pretty well excluded from practical use by other considerations, such as re-crystallization, chemical activity, or excessive plastic deformation. The behavior of metals, from the standpoint of dislocation theory, is just beginning to be understood and thus there is some hope for the future development of very high temperature metals, but the immediate problems would most logically appear to have solutions involving the nonmetals, such as the refractory ceramics and graphite. For this reason, there is presently a great deal of engineering and experimental research being performed on the latter materials, much of this research being exploratory in the sense of gathering new property data. The situation, so far as graphite is concerned, is somewhat more fortunate than with the other refractory solids in the sense that a great deal is already known about its basic properties. This stems both from the fact that the carbon-carbon bond has been of interest to chemists for a long time (and graphite can be considered as a very large aromatic molecule, if desired) and the fact that its properties, both as a function of temperature and of radiation damage, are of critical importance to nuclear reactor designers. It is still true, of course, that such fundamental questions as why graphite remains solid to such a high temperature and why it has such a high thermal conductivity cannot entirely be answered at the present time. It is, nonetheless, meaningful and instructive to consider such problems in the light of existing knowledge. This is what the present paper will attempt to do. Before going on, it may be appropriate to classify graphite and justify its discussion before readers primarily interested in metals. Graphite is comparatively unique among materials in that there is always a property or group of properties which precludes calling it either a metal, a semiconductor, or a ceramic. It has the high electrical and thermal conductivities of a metal, but the artificial, poly-crystalline types show a negative thermal coefficient of electrical resistivity, generally characteristic of semiconductors. On the other hand, semiconductors, by definition, show an ever increasing resistivity as the temperature is lowered, whereas graphite approaches a finite, and, indeed, a rather low resistivity in the region of 10°K and, furthermore, a good single crystal of graphite has a positive temperature coefficient, as for a metal.&apos; On still another hand, its porosity and brittleness at lower temperatures would put graphite in the ceramic class although, unlike most ceramics, it is readily machinable and has a high resistance to thermal shock. All things considered, it is probably more nearly appropriate to call graphite a metal than anything else. Although certainly outstanding in some ways, graphite has its peculiarities and, especially if the reader is unfamiliar with the data, it is probably valuable to review some representative property variations at high temperature. This review is meant to be mainly illustrative and no attempt has been made to be exhaustive. Review of High Temperature Properties At ordinary pressures, graphite does not melt, but sublimes directly into the gaseous phase at about 3700°C. Although the phase equilibrium diagram is still in some doubt, graphite will melt, at a slightly higher temperature, at pressures in excess of about 100 atm. The chief difficulty of using graphite in an oxidizing atmosphere is that the reaction rate becomes quite high at fairly low temperatures. If a threshold oxidation temperature2 is defined as the temperature at which graphite loses 1 pet of its weight in 24 hr, the value in air is 450°, the value in steam is 700°, and the value in carbon dioxide is 900°C. Efforts are presently being made to raise this threshold temperature either by impregnation with a retardant of some type (sodium tung-state and phosphoric acid, for example) or by a suitable metal or oxide coating. It is probably fair to say that, to date, these attempts have not shown any outstanding success in all respects. Most commercial graphites are fabricated by impregnating a carbon flour (say of coke or lampblack particles) with some type of hydrocarbon

Jan 1, 1959

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin&apos; on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled&apos; at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,&apos; the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.&apos; This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.&apos; This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959