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By Frederick N. Rhines, Robert F. Mehl

Relatively few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZnz, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.* Fundamentally, methods for the determination of the state of molecular aggregation in solution depend upon the kinetic behavior of the particles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecular solid solution would be afforded. Freche5 examined the rates of

Jan 1, 1940

By Frederick N. Rhines, Robert F. Mehl

Relatively few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZnz, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.* Fundamentally, methods for the determination of the state of molecular aggregation in solution depend upon the kinetic behavior of the particles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecular solid solution would be afforded. Freche5 examined the rates of

Jan 1, 1940

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By Zay, Jeffries

THE effect of thoria (ThO2) on grain growth in tungsten was discussed in some detail in a paper presented before this Institute by one, of the authors in 1918.1 In that paper it " was assumed that the, thoria was present in the tungsten entirely as a mechanical mixture. There was no indication in the experiments described that even a trace of the thoria was in solid solution in the tungsten. Langmuir,2 however, observed that thoriated-tungsten filaments under certain conditions showed electron emissions many thousand times greater than unthoriated tungsten at the same temperature. He concluded from his studies that a slight amount of the thoria had dissociated on heating the filament to a temperature near 220°. C. At this temperature and higher, part of the thorium diffuses to the surface of the filament where it evaporates at. a much faster rate relatively, than the tungsten, and also at a rate, nearly as fast as it is brought to the surface by diffusion: If the temperature is lowered to say 1800°,. C., diffusion of the thorium atoms to the surface is more rapid than evaporation, sown adsorbed film of thorium atoms is produced on the surface of the tungsten filament. The electron emission is governed by the outside layer of atoms so the emission from such a filament might be expected to approxi¬mate that of a thorium filament at the same temperature. PRESENCE OF METALLIC THORIUM IN THORIATED TUNGSTEN If the filament containing the adsorbed film of thorium. is heated to a sufficiently high temperature, the thorium atoms evaporate: rapidly and the electron emission becomes more nearly that of tungsten. On cooling again to 1800° C., or thereabouts, the emission 'builds up gradually to a maximum. The filament containing the adsorbed layer of thorium atoms is said to be "activated." By studying the rates of activation under different conditions of prior thermal treatment and at different temperatures, Langmuir was able to arrive at an estimate of the

Jan 1, 1927

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By Walter R. Hibbard

THE term lineage was first introduced by Buerger1 to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imperfections in alignment of the order of 10-1 [ ] to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig 11. Buerger etched zinc single crystals made by the Bridgman2 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [100] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5-8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {100} planes but somewhat uncertain because they were never straight (i.e., apparently lineage). Greninger10 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation includes metallographic, X ray and property studies of lineage in large grain and single crystal specimens of copper. PREPARATION OF SPECIMENS Specimens 10 in. long and ½ in. diam of oxygen-free copper (O.F.H.C.) (99.985 pct) were melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chlorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for ½ hr, the furnace was turned off and the specimens cooled at a rate of about 150°C an hour. This method of direct solidification was used by Greninger10 to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1947

By E. R. Stover, J. Wulff

A tentative 870°C isothermal section, the solidus equilibria, and the solubility of Tic and graphite in the nickel solid solution have been determined with arc-cast specimens. Each of the Ni-Ti intermetallics forms two-phase fields with Tic; only Ti,Ni has a measurable solubility for carbon. A quasi-binary eutectic exists between Tic: and a titanium-rich nickel solid solution; ternary eutectics occur on either side, with TiNis or with graphite. Graphite is in equilibrium with a nickel solid solution containing a ratio of Ti/C which increases below the solidus. DURING the past decade, titanium-carbide cermets containing nickel or cobalt alloy binders have been widely studied for high-temperature and wear-resistant applications. Recent work has emphasized control of the carbide grain size and distribution2's and the thermal exparision match between the phases/ The present study was initiated to determine the phase compositions during the sintering or infiltration process, and during subsequent heating. Although the effects of additives and impurities in commercial compositions are important, it was necessary to consider first the pure ternary, Ni-Ti-C. Emphasis was placed on the nickel corner, since the nickel solid solution is the continuous phase in compositions having highest strength. Early metallographic work by Zarubin and Molkov- showed that solid solubility at either end of the section Ni-Tic is small. Edwards and Raine reported that nickel dissolves between 3 and 5 wt pct Tic at 1250° C, on the basis of microstructures of annealed, vacuum-melted powder mixtures. Although the solubility of nickel in Tic has not been measured, Tic formed by the menstruum process in liuid-iron solution contains as little as 0.06 wt pct Fe. BINARY SYSTEMS The most recent determinations of the three binary systems are summarized in Fig. 1. Titanium carbide (6) is predominant among the binary phases, and it melts above the boiling point of nickel. The Ni-C binary is based on separate liquid solubility' ) and solid solubilitylo measurements. The eutectic temperature, 1328OC, is taken from the solidus determination described below. However thermal analysis data by Morrogh and williams also show eutectic arrests in this vicinity in the absence of supercooling. The Ni-Ti binary is taken from the work of Poole

Jan 1, 1960

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."' Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.' Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.''' This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-'

Jan 1, 1969

By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By R. M. Hudson

A study has been made of the decarburization of low-carbon sheet steels at temperatures from 1100" to 1475°F in mixtures containing hydrogen, nitrogen, water vapor, and in some instances carbon monoxide. Decarburization occurs principally by the reaction C (in steel) + H20 = CO + H2 and follows a first-order rate law. The decarburization rate appreciably increases with an increase in temperature up to about 1325°F, but the increase in rate is small with fur- Use of a dry hydrogen atmosphere results in a relatively slow decarburization of steel and use of a wet hydrogen atmosphere results in relatively rapid decarburization. It is now generally recognized&apos; that the reaction C (in steel) + H2O = H2 + CO [l] accounts for most of the decarburization that occurs in wet hydrogen-containing atmospheres. The present article is concerned with the decarburization of low-carbon sheet steel in H2-N2 atmospheres ther increase in temperature. The limiting rate of decarburization can be predicted from a knowledge of the solid solubility and diffusivity of carbon and this rate is approached as the water-vapor content of an atmosphere is increased. Hydrogen contents above about 8 pct are beneficial only in that they permit higher levels of water vapor to be used without oxidation of the steel. A buildup of CO in the atmosphere lowers the rate of decarburization. containing various amounts of water vapor and carbon monoxide. The effectiveness of these atmospheres and the influence of temperature on decarburization rate will be considered. EXPERIMENTAL WORK The chemical compositions of the three steels used in decarburization-rate studies are listed in Table I. Steel A was a commercially hot-rolled rimmed steel that was cold-reduced at the Laboratory to furnish specimens 0.025, 0.041, and 0.059 in. thick. Most of the experiments in which this steel was used were made on the 0.041-in.-thick material. Steel B and Steel C were cut from 0.010-in.-thick commercially cold-reduced coils that were

Jan 1, 1963

By S. Wiederhorn

The energy and force of interaction between a crack and a slip band have been calculated. When the distance between the crack and the slip band is greater than the dislocation spacing of- the slip band, the force on the cgrack is perpendicular to the slip band. The energy needed to propagate a crack against this force can be lawe enough to pevmit crack propagation parallel to noncleavage planes. SEVERAL recent experiments have demonstrated the occurrence of crack-slip band interaction in ionic crystals having a NaC1-type structure. Stokes, Johnston, and Lil have studied the nucleation and growth of cracks in MgO. From their observations, they conclude that slip bands have the ability to halt and stabilize cleavage crack nuclei. Gilman2 has shown that a crack, propagating along a (100) cleavage plane in a previously deformed LiF crystal, tends, at certain points within the crystal, to switch to (110) planes. He reasons that plastic deformation reduces the cohesive energy of the (110) planes below that of the (1130) planes, making possible (110) crack propagation. Keh3 has demonstrated that when indentations are made in MgO, crkcks form along (110) planes at the indentations. Gilman2 attributes the formation of these cracks to plastic cieformation. There is some doubt as to the formation of cracks on (110) planes. Kuznetsov4 in his discussion of crack propagation in rock salt, shows that splitting along (110) planes requires 1.76 times as much energy as splitting along a stepped (100) surface. Therefore, the observed (110) cracking in LiF and

Jan 1, 1962

By Reno H. Sales

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By Sales, Reno

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By J. B. Wagner, B. Swaroop

The atomic ratios of oxygen to iron in zlarious corn-posilions of wustite in the vicinity oj the reported p to n transformation were determined in the temperalure range between 950" and 1250°C. For these conditions, equilibrium vacancy concenrations have also been determined at vatious mixtures of C0,-CO. The data show a continuos introduction of iron vacancies as oxygen is introduced into wuistite. No phase change is observed with in the wuustite field. However, the value of n in the isothermal oxygen pressure dependence, the weight change shifts to 1ower values as the concentration of oxygen increases. WUSTITE is a metal deficit semiconductor with the majority lattice disorder being cation vacancies. Using the notation similar to that of Kroger and ink,&apos; the dissolution of oxygen into wiistite using C02-CO mixtures is represented by, WHere v+! denotes a cation vacancy with k effective negative charges and kh • denotes k electron holes, h -. Applying the law of mass action and assuming a dilute solution of defects in the wiistite yields Where the square brackets denote concentrations. Furthermore, when k = 2 the cation vacancies are completely ionized, and both the concentration of cation vacancies and the concentration of electron holes are proportional to the third root of the ratio, PC /PCo. This analysis is valid for one particular mael based on an ideal solution at elevated temperatures (in this case t > 1000°C). At lower temperatures, it has been shown2 that the pressure dependence of the electronic conductivity changes in a manner which suggests that vacancies interact with or "trap" electron holes. At the very high concentrations of defects, 10&apos;&apos; to 10" per cu cm, these simple models no longer hold. Recently Tannhauser,3 Geiger et a1.&apos; Bransky and Tannhauser; and Hillegas&apos; have found an apparent p to n transformation in wiistite in the temperature range of 950" to 1300°C. This junction was found by thermoelectric and electronic conductivity measurements. Geiger eta1.&apos; found that the electronic conductivity became almost independent of the oxygen pressure at high temperatures and oxygen concentrations within the experimental error. In addition, Vallet, Raccah, and coworkers6&apos;7 have reported the existence of several "varieties" of wiistite which were reported to exist within what was heretofor presumed to be a

Jan 1, 1968

By Martin Coryell

EHRENBERG was the first to publish and direct attention to the peculiarities of the diatomaceous deposit of Richmond; but how and by whom he was supplied with the material for his microscopical investigations, is not generally known; but we may presume W. B. Rogers, formerly State Geologist of Virginia, furnished the material, and may have given the geological position or horizon. O£ these facts we have no available evidence, nor have we any estimate of the thickness of this stratum of diatomaceous or infusorial earth. At the request of a member of this Institute, I have investigated the subject, and offer the following facts as the result, derived principally from information supplied by Mr. John Ott, of the Southern Fertilizing Company, Dr. William Taylor, State Chemist, C. Peticolas, microscopist, Captain Robert H. Temple, civil engineer, Major C. M. Bolton and Mr. C. M. Smith, civil engineers, and formerly engaged in constructing the tunnel under Church Hill, in Richmond. The city of Richmond is generally described as being built on seven hills. This is not the fact, geologically speaking. Originally, there was an immense plateau of land, about two hundred feet above tide, in which a deep excavation was made from the west to east by the James River cutting down to the granite. Opening southward and meeting the valley of the James are various ravines and gullies, in the principal of which are Shockoe and Gillies Creeks. The formation is tertiary, subdivided into all the classified divisions, but at the present moment no one has been found to make this section a special study. Rogers&apos;s early classifications and diagrams, with all their imperfections, are the only published records, and the printed editions are long since exhausted. The city of Richmond is really situated in these ravines of the James, Shockoe, Gillies, and their connections. The profile marked A, Plate V, represents the section of the plateau

Jan 1, 1876

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery&apos; reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.&apos; They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963