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By L. E. Welch, C. W. MacGregor

THE past 20 years has seen a revolutionary change in the testing of materials at elevated temperatures. This has largely been brought about by the practical importance of the creep problem in the design of equipment for operation at high temperatures. The short-time tension test carried out at elevated temperatures has consequently assumed in many cases only a secondary role compared to the long-time creep test. In many problems, however, a knowledge of the short-time high-temperature properties of a metal is essential. To mention a few cases in which this is so, we might include all hot-forming operations such as rolling, forging, etc., the welding problem if residual stresses are to be computed, the development of new alloys for high-temperature service where, in the initial stages, time does not permit of long duration creep tests, and others. Usually a knowledge of the short-time properties is desired, if only to serve as a background against which to compare creep behavior. In conducting short-time high-temperature tests, it has been almost the universal practice to determine stresses based on the original area and strains referred to the original gauge length which is usually chosen as 2 in. It has been pointed out 1,2 that one of the reasons that the true significance of certain tensile properties is not understood, which perhaps curtails their usefulness, especially when the material is applied [ ] under conditions differing considerably from the test conditions, is that true physical stresses and strains are not determined. It is essential to have a knowledge of true stresses and strains in order to correlate the values present in the tension test with those existing, for example, in hot metal-forming operations and in the general problem of the yielding and failure of metals under combined stress conditions. Stress and strain values based on the original dimensions of the test piece do not exist physically except in the early stages of the test. Since at the present time there is very little information in the literature on true stress-strain relations in the short-time high-temperature tension test it is proposed in the following pages to describe a

Jan 1, 1942

Discussion of the paper of Robert R. Abbott, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2389 to 2400. ALBERT SAUVEUR, Cambridge, Mass.:-Mr. Abbott has certainly made a strenuous effort to ascertain the influence of the various elements on the absorption of carbon by steel-a subject of great importance to those dealing with the case hardening of that metal. Because of the extensive and careful character of Mr. Abbott's experiments, one is all the more disappointed that his results, as he himself recognizes, are not more satisfactory; for, indeed they leave us just about where we were,-still entertaining uncertain views in regard to the carbon-absorbing power of various alloy steels. It might be asked whether Mr. Abbott's method of estimating the amount of carbon absorbed-namely, by weighing the specimens before and after the carburizing treatment-was the best one to select. Are not serious sources of error. inherent to such procedure because of the difficulty of satisfactorily removing the earburizing material attached to the specimen ? The method of least squares has certainly failed to solve the problem satisfactorily. By manipulating Mr. Abbott's results in a different manner I have obtained the following expression: P = 100 - 50 C - 7 Ni + 20 Cr, in which P represents the carbon-absorbing power; C, the percentage of carbon; Ni, that of nickel; and Cr, that of chromium. It is assumed that the carbon-absorbing power of pure iron, or what might be called its carburizability, is represented by 100. Applying the formula, for instance, to a steel containing 0.15 per cent. C, 3 per cent. nickel, and 0.50 per cent. chromium, its carbon-absorbing power would be 100-50X0.15-7X3+20X0.50=81.50; that is, 81.50 per cent. of the carbon-absorbing power of pure iron.

Jan 12, 1913

By J. Doig, A. A. Bauer, F. A. Rough

AN investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems was conducted by studying alloys ranging in composition from uranium-31.5 at. pct Mo to uranium-34 at. pct Ti. A ternary cut showing these phase relationships is presented upon the basis of thermal-analysis data obtained and upon the basis of metallographic and X-ray examination of heat-treated and quenched specimens. Isothermal ternary sections, inferred from phase relationships determined between the two 6 phases, are presented for the uranium-molybdenum-titanium system. In the compositional range investigated, a y-ura-nium solid solution exists at elevated temperatures. At about 900°C the 6-U2Ti phase, with limited molybdenum solubility, forms. Epsilon, a molybdenum-titanium-rich solid solution appears at the same temperature and appears in all phase regions that exist below this temperature except in the terminal 6-phase regions. The y phase is stable to approximately 660°C in titanium-rich alloys; the y and 6-U,Ti phases decompose at this temperature to a uranium in a peritectoid reaction. The y phase in molybdenum-rich alloys of the ternary cut studied decomposes in an apparent eutectoid reaction, at about 593°C, to the 6-uranium-molyb-denum and a-uranium phases. The e phase while present, presumably plays a negligible role in these reactions. Titanium was found to markedly decrease the stability of retained y in these alloys. Age-hardening characteristics developed in titanium-contain ing uranium-molybdenum alloys quenched from 900°C and aged at 500°C are ascribed to decomposition of Y to the a and E phases. INTRODUCTION Alloys of uranium with molybdenum, titanium, and zirconium, respectively, are of great interest because of their potential use as reactor fuels. As a result, this interest extends to the constitution of these alloys, particularly in view of their uniqueness of constitution. In these systems, alone, among known uranium-alloy systems, an intermediate phase forms by direct decomposition of the high-temperature y-uranium phase. As a prelude to possible future alloy development, an investigation has been undertaken of the phase relationships that occur between the intermediate phases of these systems. These phase relationships have already been reported for the intermediate 6 phases of the uranium-zirconium and uranium-titanium systems.' The results of an investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems are reported here. The phase relationships that occur in the binary systems pertinent to this investigation are shown in Fig. 1. Phase nomenclature appearing throughout this report is as shown in these diagrams; the crystal structure of the phase is given in Table I. EXPERIMENTAL PROCEDURE Alloys were cast and fabricated to flat plate. Specimens were heat treated and examined metal-

Jan 1, 1959

By J. Paces, E. Miller, K. L. Komarek

The resistivity was determined as a function of temperature over the composition range from pure cadmium to 40 at. pct Cd. Melts with cadmium contents less than 85 at. pct had negative temperature coefficients of resistinity. On cooling below a transition temperature close to the liquidus temperature, the slope of the resistivity-temperature curve changed sharply. The activation energy calculated from the slope was 0.07 ev above the transition temperature and 0.14 ev below. The resistivity vs composition curve shows two maxima corresponding in composition approximately to CdSb and Cd3Sb2. THE relationship between the structure of a liquid and that of the crystal formed on solidification is at present not well-under stood. Various experimental determinations of the properties of liquids indicate that deviations from random atomic arrangements in liquids occur and that the properties of a solid and of its melt are closely related. Thermody-namic activities of liquids usually show negative deviations in systems where compound formation occurs in the solid,' and X-ray data indicate that close-packed solids and their melts frequently have nearly the same coordination number. Electrical resistivities and viscosities of liquids frequently exhibit maxima at compositions corresponding to compounds in the solid state. It should be of interest to study systems which have both stable and metastable compounds in the solid, and to determine if the short-range order in the liquid is affected by the existence of the metastable solid phase. The Cd-Sb system exhibits such a metastable phase. The phase diagram is shown in Fig. 1.3 The stable system has one intermetallic compound, CdSb, crystallizing in the orthorhombic crystal structure, with a melting point of 456°C. The metastable system also has one compound, Cd3Sb2, melting at 420°C and crystallizing in the monoclinic structure. Metastable alloys transform to the stable crystal structure in the temperature range from 250o to 350°C. Several distinct indications of very strong short-range order in the liquid phase have been reported in this system, with a close relation between the ordering in the liquid and the existence of both the stable and metastable solid phases. Scheil and Baach4 have observed distinctly different vapor pressures for liquid Cd-Sb alloys depending on whether the liquid solidified to the metastable- or stable-phase configuration. They observed an unusually sharp increase of the activity in a limited temperature interval immediately above the liquidus temperature of stable alloys, followed by a sudden decrease in slope to what they considered normal values. On cooling, the activity data reproduced the values in the normal range but then deviated from the values obtained on heating. They also observed that specimens of the stable phase upon melting and resolidifying always crystallized in the stable crystal structure as long as the melt was not heated to more than 485° to 525°C; otherwise solidification to the metastable phase occurred. However, in a later investigation, these results were not reproduced (13). The resistivity of liquid Cd-Sb alloys has been investigated by Matuyama 5, Oleari and Fioram, 8 and Belaschenko (141, but only above 500°C, the temperature region where Scheil and Baach observed no vapor-pressure anomalies. The data of Matuyama and of Oleari and Fiorani are reproduced in Fig. 5 and show a maximum in resistivity at 50 at. pct Cd. The data of Oleari and Fiorani, however, show the maximum as being rounded, and their values in general are slightly higher than those of Matuyama.

Jan 1, 1964

By Fathi Habashi

Nickel, copper, and elemental sulfur can be recovered from a low-grade pyrrhotitepentlandite type concentrate by leaching with HNO3 in a pressure reactor at moderate temperature and pressure. The bulk of iron is converted to an oxide. Same results can be achieved by leaching in an open vessel under a reflex condenser for an extended period of time.

Jan 1, 1974

By C. R. Breck

THERE has been a running discussion over the past several years with respect to the life and adequacy of our natural gas reserves. Some of the experts agree on one phase of the subject at least-that eventually it will be necessary to augment deliveries of natural gas in the northern markets by the development of a more or less comparable synthetic gas made from coal. The purpose of this paper is to point out: 1. It may be later than a good many people think-the demand for addi¬tional domestic and commercial pipeline gas in at least one section of the North will probably be felt rather keenly before an adequate synthetic pipe¬line-gas project, developed on economic lines, could be completed, even if initiated in the near future. 2. The evidence is considerable that such a project would be technically sound and economically self-supporting, although the margin of profit at first might be so small and the magnitude of an economic enterprise so great -that financing would be impossible without Government aid in some form or other. The part of the country referred to is the heavily populated section in the northeast of the United States. To simplify an examination of the situa¬tion, let us take the potential marketing areas within range to the north and east of the three pipelines: 1. Tennessee Gas Transmission Co. as it enters Erie County, New York state. 2. Texas Eastern Transmission Corporation just before the tap that sup¬plies the general Philadelphia area. 3. Transcontinental Gas Pipe Line Corporation as it enters the state of New Jersey. The sources of gas for these three pipelines are in Texas and Louisiana. The ultimate maximum combined capacity of the three lines at the points stated is approximately 1,200,000,000 cu ft per 24 hr at the maximum load factor probable of attainment in normal operation. The areas supplied by the three lines north and east of the points stated, or assumed as eventual markets, are: 1. Central New York state, from Buffalo to Albany (both inclusive).

Jan 1, 1953

By W. L. Remick

The hydrotator coal-cleaning process was developed as an economic necessity to meet the ever-increasing demand for an inexpensive method of cleaning coal down to the sizes ordinarily referred to as "dust." As the most urgent demand seemed to be in the anthracite field, all experimental work has been conducted in that territory during the past two years, with the exception of a few months during the strike of 1925-26, when some experiments were performed in the Alabama bituminous fields. The first commercial plant was constructed at the Middle Creek Colliery of the Philadelphia & Reading Coal & Iron Co.,. Pottsville, Pa. This plant is now operating. Application The field of application of the process is: 1. Cleaning anthracite fines, ordinarily described as "slush" or "silt." Slush contains all sizes from 3/32 in. down to and including I(dust." (Anthracite passing a 3/32-in. mesh is also referred to as No. 2 Barley and No. 4 Buckwheat.) 2. Cleaning sizes too fine for recovery by other methods. 3. Removal of coal from sand circulated in the Chance sand-flotation process. 4. Cleaning of bituminous sizes from % in. down to "dust." 5. As equipment for the performance of the froth flotation process. 6. Other separating, extraction and washing processes which may be considered outside the realm of coal cleaning. Principle of Operation Fig. 1 shows the method of classification practiced under the Hydrotator patent.' In coal cleaning the machines are operated as "hindered settling" classifiers, the flow of solids and liquids being so controlled that the units may be combined in series.

Jan 1, 1927

The rich Tiller seam in southwest Virginia averages 10 to 15 ft in thickness. But because it is separated into two benches, mining engineers for years considered it neither physically nor economically feasible to mine. Profitable recovery of this coal has been made possible only by: full-seam mining with automatic machines; and the largest and most highly automated coal preparation plant of its kind-a plant ten stories high which washes, screens, and dries at the rate of 1500 tph, and produces both metallurgical and steam coal products. The Moss No. 3 preparation plant of Clinchfield Coal Co. Div. of Pittston Co. is located at Clinch- field, Va., only a short distance from the 450-tph Moss No. 2 plant, and was designed, built and erected by Link-Belt Co.

Jan 7, 1959

By E. F. Poncelet

Forty years ago A. A. Griffith developed a theory explaining why brittle materials displayed such low tensile strengths.' He based his views on two points. First, he found himself compelled to assume that all brittle materials are replete with flaws, cracks, and other defects that act, although quite invisible, as large stress raisers. Second, he applied the "theorem of minimum potential energy," which says that the total potential energy of a system must pass from the unbroken to the broken condition by a process involving a continuous decrease in potential energy. By this means he satisfactorily accounted for the noted low strength of such solids and also for the wide spread obtained in experimental measurement of these strengths. So successful has the theory been that it is favored by some to this day. Unfortunately this theory is of limited use beyond the explanation of these two noted phenomena and it is keenly felt that a better theoretical insight into the physics of the fracturing process is needed as the volume of experimental evidence accumulates. The author proposes in the following to build on the fundamentally sound concepts of Griffith and, with the help of increased theoretical knowledge over that available to Griffith, develop a mechanism for frac-ture which will provide far greater understanding of the experimental evidence accumulated to date than is possible from the original Griffith idea. THE GRlFFlTH THEORY Very little progress indeed can be made without accepting the first postulate of Griffith which supposes all brittle solids to be full of microcracks. It would be difficult indeed to find a better mechanism for the small strength of such brittle materials, in conjunction with the fact that the energy that must be expended for comminution is by no means small. The postulate of the existence of the microcracks permits the breakup of the various bonds a few at a time by concentrating the stress at the tip of the progressing crack, while the total energy expended is the same as if they all had been ruptured simultaneously. The only flaw in the argument is that no reasonable explanation has been proposed to account for the genesis of such cracks. Indeed their very presence is in violation of the Griffith second postulate, the potential energy theorem. This theorem is straightforward for isothermal processes, and, in spite of Griffith, there is some doubt that treating the problem isothermally is legitimate. The surface energy of bodies is a free energy, not a potential energy as stated by Griffith, and the production of new surface free energies is not necessarily an isothermal process. There is ample evidence to the contrary. Generally speaking, if heating a body increases its surface area, then, by virtue of Le Chatelier's principle, any increase of that area by other means will tend to lower its surface temperature. Lord Kelvin calculated the actual cooling that resulted in drawing out a film of liquid.2 R. A. Houston calculated the surface cooling that resulted in stretching a metal wire.3 These calculations were made by applying the Carnot cycle to the process and evaluating the thermodynamics thereof. IRREVERSIBILITY OF THE FRACTURING PROCESS While Griffith was very careful not to say so, the impression gained from studying his papers is that he considered the fracturing process as reversible, that is, a succession of quasi-equilibrium states. There is ample evidence that it is not. The indication that the new surfaces produced by the propagation of a crack are cooler than the original body points to an irreversible heat flow from the interior to the new surfaces to equalize the temperatures. If the process be reversible, any crack accidentally formed should immediately close up as, in the absence of any strain energy, the potential energy would thereby be lowered. The fact that they do not, constitutes a paradox. Such paradoxes are nothing new where certain phenomena that propagate from minuscule nuclei are assumed to be reversible. Such is, for instance, the condensation of a pure saturated vapor that is suddenly chilled by adiabatic expansion. At the beginning the tiny droplets that are formed should be only a few angstroms in size, but the vapor pressure at such droplets is so high that they should evaporate at once. A similar situation arises if a saturated pure solution becomes super-saturated upon cooling; the first tiny crystal nuclei should dissolve as fast as

Jan 1, 1964

By F. J. Smit, S. C. Sun

Flotation variables were investigated for the re-clamation of phosphate from a Florida washer slime. Under optimum conditions, 92% of the phosphate was recovered. Further cleaning of the rougher flotation concentrate resulted in a product containing about 30% P2O5 with a phosphate recovery of 65%. The enormous amount of slimes rejected in the Florida pebble phosphate fields, containing roughly one-third of the phosphate in the pebble matrix,1 has long been considered as a serious problem to the industry. The mere disposal of these slimes has posed an almost insurmountable task for several investigators.2-5 Some companies still resort to huge surface dams, some covering 1800 acres, for slime disposal.6 Information on the recovery of fine phosphate from these slimes is scanty. Dry separation8 and electrostatic beneficiation8 were suggested, but would necessitate radical changes in the present mining and concentration methods. Haseman10 proposed the selective flocculation of colloidal phosphate with starch, while Ralston11 suggested the removal of clay from the matrix by amine flotation. Leaching of the slimes for recovering the small amount of uranium was attempted by the Battelle Memorial Institute12,13 but proved to be economically unfeasible. The purpose of the present investigation was to determine the optimum fatty-acid flotation conditions for reclaiming the phosphate discarded with the Bartow washer slime. Prior to the flotation experimerits, however, the size distribution and the minera-logical composition of the employed slime had to be determined.

Jan 1, 1963

By RALPH HAYES SWEETSER

IRON ore and bituminous coal are the two basic raw materials for the whole iron and steel industry. The ore furnishes the iron and is absolutely necessary-all iron and steel products come directly or in- directly from the iron ores. The bituminous coal furnishes the carbon needed for the smelting of the ores and for the fuel used in all the processes of iron and steel manufacture. The necessary carbon could be furnished in some other form besides bituminous coal. In fact, it is only since the Civil War that bituminous coal has been the chief source of the carbon for metallurgical fuel. For many years only charcoal made from the forests furnished the carbon for smelting iron ores. About 90 years ago, anthracite coal was first used as blast-furnace fuel and for many years continued to be the chief blast furnace and steel making source for carbon. Even in my own blast-furnace experience, I have used charcoal in Canada and anthracite in Pennsylvania for smelting ores in an iron blast furnace. Bituminous coal, now almost exclusively the source for the carbon used in smelting iron ores, also furnishes most of the heat used in the steel-making processes. It is seldom used in blast furnaces in its natural condition, hut is first coked in beehive, or in by-product coke ovens; such bituminous coal is called "coking coal." Bituminous coal that is suitable for making the producer gas used in the open-hearth steel process is called gas coal. Any bituminous coals suitable for making blast-furnace coke or foundry coke, or that can be satisfactorily used for making producer gas, are classed as metallurgical coals and as such are to be considered in my proposed plan for the evaluation of metallurgical coals. According to Bureau of Mines Bulletin No. 449 these coals comprised 22 per cent of the bituminous coals mined in this country in 1923.

Jan 1, 1926

By Frederick C. Langenberg

IT has been shown1 that copper can be removed from iron-base alloys by solvent extraction with molten lead and sodium sulfide slags. In these processes copper removal is favored by a positive deviation of copper in iron from ideal behavior. Chou' determined the distribution of copper between liquid silver and iron and obtained a value for the activity coefficient of copper in iron at 1600°C, y°, of 9.12. Chipman" calculated the activity coefficient from the Fe-Cu phase diagram to be 12 at 1600°C. More recent work by Koros and Chipman" yields a value at 1600°C for y V equal to 8.0. In this latter work, the distribution of copper between silver and iron was measured at 1600°C, while the activity of copper in the silver phase was determined from calculations based on the Ag-Cu phase diagram. The present work presents another value of based on calculations from the Cu-Pb phase diagram, on the heat of mixing data for the Cu-Pb system, and on an experimental study of the distribution of copper between iron and lead at 1600°C. These experiments were part of a larger research on the removal of copper from iron-base alloys conducted at The Pennsylvania State University. Experimental Procedure—The distribution of copper between pure iron and lead at 1600°C was made in the furnace assembly shown in Fig. 1. The melts were made in high purity alumina crucibles under an atmosphere of prepurified argon. Temperatures were read with an optical pyrometer sighted into a %-in. hole drilled in the inductor. Extensive calibration of the optical readings with immersion readings had been carried out previously. The initial charges consisted of 100 g of electrolytic iron and varying weights of copper. The melts were brought rapidly to 1600°C and 75 g of lead added. The temperature was quickly readjusted to 1600°C, and the melts were held for 10 min at this temperature. A sample was then drawn from the iron layer in a fused silica tube. This sample was analyzed to determine the copper content of the iron layer at equilibrium, while the copper content of the lead layer was determined from a material balance. The validity of the material balance was confirmed by a chemical analysis of the entire lead layer for one heat in which the crucible was removed and quenched after the iron sample was taken. The calculated copper content of the lead-rich phase was 1.18 pct; while the entire lead layer analyzed 1.20 pct Cu. The distribution results are shown in Fig. 2. The distribution constant, N,.'r'"/N, is equal to 3.95. Discussion—From the Cu-Pb phase diagram' it can be seen that lead-rich liquid Pb-Cu solutions

Jan 1, 1957

By J. B. Cohen

EARLY investigators1-4 reported that additions of beryllium to silver caused embrittlement. The in-termetallic phases which are now known to exist5,' were not known at the time. Solidification appeared to occur by a simple eutectic reation.4,7 (The primary beryllium-rich phase appeared globular, when the liquidus temperature was near the melting point of pure beryllium, and angular when the liquidus was much lower; in discussion of Sloman's work,4 it was suggested that this difference was due to an intermetallic compound which was not revealed by the polishing technique.) In the investigation reported here, it was found that if the compounds now known to exist were avoided, certain beryllium-silver alloys containing large amounts of the primary beryllium phase possessed sufficient ductility to be cold formed. Alloys containing 14 and 20 at. pct Ag were prepared from vacuum-cast beryllium containing 1.0 to 1.2 pct impurities and silver, 99.99+ pct pure. The elements were melted together by induction in beryllia or alumina crucibles under argon at less than 1 atm pressure. The cooling rate was adjusted by regulating the temperature of the melt and by reducing the power to zero without stopping the water flow in the induction coils, which were in contact with the crucible. Ingots were about 0.75 in. in diam with a grain size of 0.12 to 0.25 in. Microscopic investigation of transverse or longitudinal sections of an ingot cast from a temperature well above its melting point showed that, in general, the compounds did not form, presumably because of rapid cooling; the alloys consisted of beryllium-rich particles in a silver-rich matrix as shown in Fig. 1. A eutectic structure was not observed, probably .due to the low beryllium concentration of the eutectic composition and eutectic divorcement. Within a given grain, the small globules of the primary phase were all oriented in the same direction, as indicated by examination under polarized light; the orientation varied from grain to grain. This suggested that the globules were branches of the same dendrites. If cooling was too slow, a third constituent was observed in the microstructure; because it formed around the primary beryllium-rich globules it was Fig. 1—Ag-Be alloy, 18.6 at. pct Ag, as-cast. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction. probably the 6 compound. A thin ring around an ingot often contained this constituent. When this compound was present in large quantities, or the silver segregated so that large regions occurred with the beryllium-rich globules in contact, sections from the ingot were brittle. When the compound was initially absent, it was possible to carry out reductions in thickness of 50 pct by cold rolling with only limited edge cracking; failure did not occur until reductions of 80 pct. A typical cross section after cold rolling is shown in Fig. 2. After simple bend tests, microcracks were found; these apparently were difficult to propagate in the two-phase structure, as the specimens continued to behave in a ductile manner after the cracks appeared. Similar cracks would probably be closed during rolling. It is apparent in Fig. 2 however, that the primary beryllium particles undergo extensive plastic deformation. Hardness values of the alloys indicated that some work-hardening occurred during cold working. Fig. 2—Ag-Be alloy, 18.6 at. pct Ag, reduced 83 pct in thickness by cold rolling. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction.

Jan 1, 1961

By A. E. Gorum, I. Cornet

Fatigrle of ionic crystals has been studied primarily in magnesinm oxide. under cyclic stress dislocations move irrreversibly; they multiply; slip bands form and grow; cracks mucleate and propagnte, and failure occurs. The use of ionic crystals such as MgO is advantageorus in such investigations because they are optically transparent. Individual dislocation Intersections with {100} surfaces may be observed with a standard microscope, using etch-pit techniques. Slip, deformation, crack .formation, and fracture in MgO crystals under cyclic stress are compared with cotrresponditzg processes in metals. ThE effect of cyclic loading in metals has been studied for many years. The appearance of slip lines is readily observed and the ensuing fracture may also be seen. From these observations it is possible to predict the behavior of a material and make an educated guess as to what is happening internally, but the actual changes taking place within the structure are not readily apparent. If one could obtain a material in which the individual glide components could be observed, it would be invaluable in determining the actual slip distribution resulting from cyclic loading as well as the distribution of slip in the neighborhood of a growing crack. Such a material is magnesium oxide. Dislocation arrays may be observed by means of etch pits

Jan 1, 1961

By John Johnston

The actual amount of any metal volatilized from a mixture of metals depends on the magnitude of its partial vapor pressure under the specified conditions of temperature, and on the circumstances attending the heating—in particular, on the duration of heating, the volume of gas coming into actual contact with the surface of the metal, the extent of this surface, and the rate of diffusion of the volatile metal from the body of the melt toward the surface.' If two (or more) metals are volatilizing from the same mixture of metals, the several conditions are identical except for the difference in partial pressure and in rate of diffusion of the volatilizing metals; the second of these two factors is without doubt only of secondary importance as it is probable that the rates of diffusion of the volatilizing metals would be very similar. Hence, in order to gain an estimate of the relative amounts of two metals that may be volatilized from a given mixture, it is necessary to know the vapor pressure, or, more precisely, to ascertain for each metal its partial vapor pressure in equilibrium with the liquid (or solid) alloy under the particular circumstances. The partial pressure of each constituent depends on the effective concentration of that constituent in the alloy2 as well as on the vapor pressure of the constituent when pure, and it can be calculated when both of the above factors are known. The first step, therefore, is to ascertain the vapor pressure of the several pure metals. Vapor Pressure of Pure Metals The experimental data on the vapor pressure of the several pure metals with which we are here concerned are not so accurate as could be wished, nor have the determinations been made in general at temperatures such that the results can be used directly. In a previous

Jan 1, 1919

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By E. W. Johnson, M. L. Hill

The dijfusiuity D was determined at 25° to 780°C- from hyd?-ogen evolution rates. Anomalous evolution from air-melted iron was att~zbztted to residual hydrogen, which is interpreted as a hydrogen compound that decomposes at a strongly temperature-(Ieperzdent rate above 500°C. Above 200°C, D = 0.0014 cm2sec-1 exp (-3200 cal per g atom/RT). Below, 200°C the diffusivity is anomalously low and represented by D = 0.12 cm2sec-l exp (-7820 cal per g atom/RT). It is postulated that at low temperatures the hydrogen in the metal is "trapped" with an energy 4.8 kcaL per g atom below- that of the interstitial hydrogen. 1 HE purpose of the present experimental study was to determine the diffusivity of hydrogen in a-Fe over an extended temperature range. As certain anomalies were encountered, attempts were made to understand the anomalies themselves. This research was in progress both before and after a determination of the diffusivity of hydrogen in nicke1.l The latter system was found to exhibit none of the anomalies of hydrogen in iron, and its description was far simpler. The experiments on nickel also

Jan 1, 1961

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work&apos; the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,&apos; Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951

By F. L. Grammer

In these day, when anthracite is less extensively used as a blastifurnace fuel than it was a generation ago, and managers endeavor to maintain regular and known ore-mixtures, the " freezing " of tuyeres, cinder-notch or iron-notch is infrequeut; and, consequently, the oil-burner or " kerosene blowpipe "* is seldom employed; and furnace-foremen have, to a considerable degree, forgotten their former cunning and persistency in the use of the drill and sledge. Still, in starting new or abandoned plants with untrained labor, and in running some of our large 100-ft. furnaces, slips, resulting in very cold furnaces, may occur, even under experienced managers. During my superintendence of the Cleveland, O., blast-furnaces, such a misfortune, owing to a dearth of trustworthy foremen, was experienced; and our electrician, Mr. Thomas Martin, proposed to open the tuyeres and cinder-notch by means of the heat of the electric arc. We have heard that the surface-cracks or marks developed in rolling heavy plates have been closed by electric welding, as by a soldering-iron, and also that an electric burner has been employed at some German blast-furnaces; but the experiment was quite novel to us; and I think it constituted one of the first, if not the very first, successful application of this device, for the purpose named, in the United States. †

Jan 1, 1902

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958