Search Documents

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By R. C. Wilcox, R. V. Lawrence, P. A. Calhoun

The V-Rh-Si, Nb-Rh-Si, and Cr-Rh-Si systems were investigated to evaluate the extent of solid solubility between binary Cr3O structures. All Cr3O components lie within the favorable atomic size range1 for the formation of the Cr3O structure. Previous studies indicated complete solid solubility between V3Si and V3Sn2 and no solubility between Sn and cr3si3 or Si and Nb3Rh.4 The Cr3O structure is not found in the Cr-Sn and Nb-Si binary systems. Powder compacts were are-melted under argon, homogenized in a vacuum at 1000°C, and water-quenched. Alloys containing greater than 15 at. pet Si were annealed 100 hr. X-ray diffractometer methods were used to study all systems utilizing copper radiation for the Cr-Rh-Si system and chromium radiation for the other two systems. V-Rh-Si System. The alloys prepared in the V-Rh-Si system and the measured lattice parameters for the Cr3O structure found in each alloy are listed in Table I. The characteristic Cr3O diffraction pattern was found in all binary alloys. The measured lattice parameter of V3Rh (VRS-1) is in agreement with the reported value5 while the value for V3Si (VRS-5) is only in fair agreement.' In

Jan 1, 1965

By C. E. Cottrell, G. W. Preckshot, N. D. Delisle, D. L. Katz

Most crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir. mechanisms. Asphalt has been the subject of widespread investigation but, owing to the complexity of the substances being considered, progress has been slow. Investigators working primarily with the asphaltic substances have treated the subject from the colloidal standpoint and have developed theories that picture the asphaltic particles as surrounded by adsorbed materia1s.14,15,17,24 The deasphaltization of lubricating oil by the use of solvents treats the subject primarily from the standpoint of liquid-liquid equilibria.'' A complete understanding of asphaltic substances would make possible the following of the material from its initial state in the crude oil through precipitation processes to the final plastic stage, the most common form of which is used in asphaltic pavements. Since these asphaltic particles are very small, it appears 'hat the electron microscope4 might be a useful tool in studying the precipitation processes. Specimens are examined by the electron microscope in a vacuum and as very thin films, requiring special techniques in preparation of samples. A brief description of the electron microscope and its operation will bring out the difficulties and advantages of its use for this problem. The first work was done with crude oils that had been diluted with solvents for the preparation of the film to be examined. Later a technique was developed by which the undiluted oil film could be made thin enough for direct examination. These two techniques show vastly different results Asphaltic particles have been precipitated from crude oils by a variety of

Jan 1, 1943

By G. W. Preckshot, C. E. Cottrell, D. L. Katz, N. D. Delisle

Most crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir. mechanisms. Asphalt has been the subject of widespread investigation but, owing to the complexity of the substances being considered, progress has been slow. Investigators working primarily with the asphaltic substances have treated the subject from the colloidal standpoint and have developed theories that picture the asphaltic particles as surrounded by adsorbed materia1s.14,15,17,24 The deasphaltization of lubricating oil by the use of solvents treats the subject primarily from the standpoint of liquid-liquid equilibria.'' A complete understanding of asphaltic substances would make possible the following of the material from its initial state in the crude oil through precipitation processes to the final plastic stage, the most common form of which is used in asphaltic pavements. Since these asphaltic particles are very small, it appears 'hat the electron microscope4 might be a useful tool in studying the precipitation processes. Specimens are examined by the electron microscope in a vacuum and as very thin films, requiring special techniques in preparation of samples. A brief description of the electron microscope and its operation will bring out the difficulties and advantages of its use for this problem. The first work was done with crude oils that had been diluted with solvents for the preparation of the film to be examined. Later a technique was developed by which the undiluted oil film could be made thin enough for direct examination. These two techniques show vastly different results Asphaltic particles have been precipitated from crude oils by a variety of

Jan 1, 1943

By E. J. Haug, M. M. Fine

FOR several years work has been carried on by the U.S. Bureau of Mines at Rolla, Mo., to develop improved methods of concentrating the oxidized ores of lead and zinc. Various samples have been investigated, and results on some have been published 1,2 lished.l, 2 Details of the progress to date are given in a mineral dressing study now being conducted for an extensive oxidized lead-bearing tract in southeast Missouri, property of St. Joseph Lead Co. These oxidized ores present problems typical of many encountered in modern mineral dressing research in that recovery of very fine particles is of

Jan 1, 1956

Alfred Stansfield, Montreal, Canada:—In Professor Howe's paper on the position of Ae3, he shows its industrial importance in determining the temperature to which steel should be heated for " grain refining." Several years ago I carried out a research on the " burning " of steel and found that while hypo-eutectoid steel should be heated to Ae3, hyper-eutectoid steel that has been very much overheated must be reheated to the curve Sa on the carbon-iron diagram, in order to redissolve the pro-eutectoid cementite and thus to obtain recrystallization and grain-refining. This treatment was necessarily only partly successful, and I should like to ask whether the conditions of heat treatment for refining overheated high-carbon steels have been ascertained. Speaking of the &'Persistence of Solidificational Segregation " Professor Howe quotes an experiment made by Mr. Stead in which a bar of 1.2 per cent. carbon steel was immersed in a large mass of molten blast-furnace slag and allowed to cool with it. The steel was heated ; above the solidus (curve An on the carbon-iron diagram), but below the liquidus (curve AB). A drop of eutectic carbon-iron alloy, rich in carbon, had liquated out and hung below the bar. This agrees exactly with my own observations on the burning of steel, but my interpretation differs somewhat from that of Professor Howe. Professor Howe considers that the fusion of a part of the metal (rich in carbon) shows that the solidificational irregularities of composition had persisted through the rolling and heat treatment of the steel, as otherwise no part of the steel would have been sufficiently fusible to melt. It does not appear to me that such an explanation is necessary. A piece of steel represented in temperature and composition by any point within the area ABa will ultimately resolve itself into a solid phase and a liquid phase in equilibrium with each other. It may appear that if the steel were absolutely uniform no fusion could take place, but, the smallest nucleus of high-carbon, fusible alloy would ultimately bring about this separation into liquid and solid phases, by diffusion of the carbon from the solid to the liquid areas. A nucleus sufficient for the purpose might be provided by an area of pro-eutectoid cementite which had not become diffused during the

Jan 1, 1914

By Alfred Boyles

The experiments described below are a continuation of work on the graphitization of cast iron conducted as part of the program of fundamental research at Battelle Memorial Institute. In previous work it was found that melting in hydrogen increased the amount of eutectic carbide appearing in certain alloys and in others produced marked changes in the size of the graphite flakes. These effects seemed to be closely related to the amount of sulphur and manganese present in the material studied. Iron-carbon-silicon alloys did not respond to hydrogen in the same manner as cast iron and there was no evidence to show that hydrogen was able to stabilize the carbide in such alloys unless additions of sulphur were made. The two alloys examined contained about 2 per cent of silicon. The present paper is concerned with alloys of lower silicon content and describes the structural changes produced by melting in various atmospheres at pressurcs ranging from a partial vacuum up to 300 lb. per sq. inch. Experimental Method The experimental technique was similar to that previously employed, so that direct comparison might be made with earlier work. Alloys were

Jan 1, 1939

By Alfred Boyles

The experiments described below are a continuation of work on the graphitization of cast iron conducted as part of the program of fundamental research at Battelle Memorial Institute. In previous work it was found that melting in hydrogen increased the amount of eutectic carbide appearing in certain alloys and in others produced marked changes in the size of the graphite flakes. These effects seemed to be closely related to the amount of sulphur and manganese present in the material studied. Iron-carbon-silicon alloys did not respond to hydrogen in the same manner as cast iron and there was no evidence to show that hydrogen was able to stabilize the carbide in such alloys unless additions of sulphur were made. The two alloys examined contained about 2 per cent of silicon. The present paper is concerned with alloys of lower silicon content and describes the structural changes produced by melting in various atmospheres at pressurcs ranging from a partial vacuum up to 300 lb. per sq. inch. Experimental Method The experimental technique was similar to that previously employed, so that direct comparison might be made with earlier work. Alloys were

Jan 1, 1939

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H20, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H20, FeO¬Fe-CO-C02 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By Clarence Merritt

STAINLESS iron, as mild stainless steel is usually called, an alloy ranging from 11.50 to 15.00 per cent chromium with carbon under 0.12 per cent, has been considered to be not appreciably affected in respect to corrosion resistance by heat treatment. This metal, while one of the most widely used of the "straight" chromium stainless alloys, has failed in many applications because of insufficient information regarding heat treatment. These failures have been attributed to many possible causes from an inherent lack of resistance to corrosion and misapplication to mysterious electrolytic effects or comparatively minute non-metallic inclusions. Many uses for a steel with such excellent physical properties is are latent in this alloy have been lost on account of corrosion failures which could have been avoided by applying proper heat treatment. The alloy has not received the recognition or attention it should because of the fact that' the details of its metallurgical behavior were not thoroughly understood. Response to heat treatment of the steel is well known as regards tensile properties, 1,2 but its application has been for improvement in tensile characteristics or on account of machining considerations rather than for corrosion prevention. The potential user of this steel has not been clearly advised in papers, either technical or commercial, that have been written about it in the last 10 years or more, of particular features that are of prime importance in developing the excellent properties of this metal. The data to be presented in this paper are concerned mainly with the effect of heat treatment on the corrosion resistance, but a study has also been made of the concurrent microstructural changes and an explanation developed for the phenomena revealed, as well as a correlation to the other physical properties-hardness, tensile characteristics and impact strength. Stainless steel, largely used for cutlery purposes, an alloy of approximately 13.00 per cent Cr with 0.30 per cent C, must be hardened and the surface prepared by polishing or pickling for best resistance to staining and corrosion.3 Monypenny reports that a loss of hardness is

Jan 1, 1932

By Arthur Smith

THE Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district-the United Verde and the United Verde Extension-lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., . a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to? the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Wood chute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the . smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. This strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the vicinity of Allen Springs, at the south end of Mingus mountain and all within the boundaries of the Prescott national forest reserve.

Jan 3, 1924

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By I. R. Kramer

Studies of the effect of size of the specimen on the change of slopes of Stages I and 11 by surface removal showed that the change of Stage I was independent of size with respect to the polishing rate; however, the change in the slope of Stage 11 with polishing rate increased directly in proportion to the surface area. The removal of the surface during the test affected the plastic deformation characteristics of gold, aluminum, and zinc single crystals and polycrystalline aluminum. The apparent activation energy of aluminum was found to be decreased markedly by removing the surface during the deformation process. In previous papers1-3 it was shown that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing during tensile deformation, it was found that the slopes of Stages I, II, and III were decreased and the extents of Stages I and II were increased when the rate of metal removal was increased. By removing a sufficient amount of the surface layer after a specimen had been deformed into the Stage I region, upon reloading, the flow stress was the same as the original critical resolved shear stress and the extent of Stage I was the same as if the specimen had not been deformed previously. The slope of Stage I was decreased 50 pct and that of Stage 11 decreased 25 pct when the rate of metal removal was 50 X 10"5 ipm. These data show that in Stage I the work hardening is controlled almost entirely by the surface conditions, while in Stages 11 and III both surface conditions and internal obstacles to dislocation motion are important. It appears that during the egress of dislocations from the crystal, a fraction of them becomes stuck or trapped in the surface regions and a layer of a high dislocation concentration is formed. This layer would not only impede the motion of dislocations, but would provide a barrier against which dislocations may pile up. In this case, there will be a stress, opposite to that of the applied stress, imposed on the dislocation source and dislocations moving in the region beyond this layer. It has been found convenient to refer to this layer as a "debris" layer. The "debris" layer may be similar to the dislocation tangle observed by thin-film electron microscope techniques.4 Reported in this paper are the results of studies on the effects of removing the surface during plastic deformation on aluminum crystals of various sizes. The effects of the surface on the yield point behavior of gold and high-purity aluminum crystals as well as the creep behavior were also determined. The effects of surface removal on polycrystalline aluminum (1100-0 and 7075-T6) are also reported. EXPERIMENTAL PROCEDURE For those portions of the investigation involving creep and tensile specimens, single crystals, having a 3-in. gage length and a nominal 1/8-in. sq cross section, were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The single crystals were prepared from materials which had initial purities of 99.997, 99.999, 99.999, and 99.999 pct for Al, Cu, Zn, and Au, respectively. The aluminum specimens for the size effect studies were prepared through the use of a three-tier mold in which crystals having a cross section of 1/8, 1/4, and 1/2 in. were grown from a common seed. The mold design was arranged so that one 1/2-in. crystal, two 1/4-in. crystals, and four 1/8-in, crystals of the same orientation could be cast. With this technique, it was possible to obtain only one set of crystals with the same orientation. Because of this limitation, it was not possible to determine both the changes of extent and slope of the various stages since a large number of crystals of the same orientation would have been required. Instead, only the change of slope as a function of the rate of metal removal was studied by abruptly altering the current density of the electrolytic polishing bath at various strains within the regions of Stages I and 11. The experimental techniques used for the tensile studies were essentially the same as those used previously.1,3 The specimens were deformed in a 200-lb Instron tensile machine, usually at a rate of 10-5 sec-5. A methyl alcohol-nitric acid solution was used as the polishing bath for aluminum. The temperature was maintained constant within ±0.l°C by means of a water bath. The tensile machine was

Jan 1, 1963

1. List of Manuscripts Seen in America 2. List of Manuscripts Seen in England 3. List of Maps Examined 4. List of Newspapers Examined 5. General Bibliography - Numbered Reference List

Jan 1, 1942

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

By Rex B. McLellan, M. L. Rudee, T. Ishibachi

A modelfor dilute quasi-regular interstitial solid solutions is proposed in which the solute atoms can occupy both the octahedral and tetrahedral interstices in the bee solvent lattice. The distribution function, according to which the solute atoms are apportioned between the two kinds of sites, is calculated. The partial thermodynamic functions of the solution are calculated from the distribution function. It is shown that such a solution model can explain the deviation from linearity of the Arrhenius plot of the temperature variation of the diffusivity of carbon through a iron. The published difiusivity data is analyzed to obtain numerical values for the distribution function. Finally it is shown from the numerical values of the distribution function that the possibility of dual-site occupancy will have a negligible effect on the solution thermodynamics for this system. DeSPITE the large amount of experimental data available on the thermodynamics and diffusion kinetics of dilute solid solutions of carbon in a iron, many of the elementary properties of these solutions are not understood due to real or apparent discrepancies in the experimental data. Basically there is a lack of agreement between the solubility and diffusion data obtained by anelastic damping techniques and by bulk chemical thermodynamic methods. SPecifically the heat of solution of cementite in ferrite estimated from thermodynamic measurement1, 2 is about twice as high as that determined from anelastic damping measurements.3 Furthermore the diffusion coefficient D of carbon in a iron in the range -40" to about 150°C (covering about ten orders of magnitude) determined from anelastic damping techniques is such that an Arrhenius plot of In D vs 1/T is linear. However in the range of about 300o to 850°C where mass flow measurements of D have been made (covering about four orders of magnitude), although the data merges with the low-temperature data, the Arrhenius plot departs from linearity. The object of this paper is to present a more refined model of dilute ferrite solutions in which the solute atoms can occupy two kinds of interstitial sites. The experimental data is analyzed in the light of this model and it is believed that thereby some of the anomalies can be resolved. snoek4 explained the room-temperature internal-friction peak (usually referred to as the Snoek peak) in iron as the stress-induced ordering of interstitial carbon and nitrogen atoms occupying the octahedral (0, 0, 1/2) interstices in the bee lattice. From the consideration of a hard-sphere lattice model the (0, 1/4, 1/4) tetrahedral interstices are larger than the octahedrons but their symmetry would not produce the strain dipole necessary to give rise to the Snoek peak. Thus the presence of the Snoek peak is direct evidence that the octahedrons are occupied. Since the publication of Snoek's explanation, most workers have assumed that all of the carbon and nitrogen in the a solid solution was located in the octahedral sites. This assumption of universal octahedral occupancy has been implicit in the theory of wert5 for interstitial

Jan 1, 1965

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.' In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964