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By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.' There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By Gerhard Derge

The rapidity of oxygen steelmaking has created renewed interesl in the mechanisms and kinetics of the various processes involved. These studies can now be approached with increased confidence because of the more adequate thermodynamics, physical chernislry, and relevant engineering infornzation available. These combine to offer promise of useful control and automation if the details of each specific problem can be sufficiently well-defined. The hot filament microscope provides new insig-hi into many of these problems by direct observation at temperature, allowing the appraisal of the relative importance of thermal gradients, convection, and intermediate phases. All of these have a direct bearing on the overall rates and control of most pyrometallurgical processes. It is one of the special privileges of the Howe Lecturer to become better acquainted with this distinguished man. All of us interested in the metallurgy of iron and steel have developed some sense of his widespread influence by the annual reference to his work in these Memorial Lectures. Each lecturer since 1923 has been able to identify his personal specialty with the broad interests of Professor Howe. This has become even more rewarding with the background information from Professor Gensamer's monograph, "Henry Marion Howe's Contributions to Metallurgy, which brings out his happy combination of intellectual and professional activities. Beyond this, I found my personal bond with Professor Howe in his book on The Metallurgy of Sleel first published in 1891.' After a detailed discussion of the dephosphorizing action of slags, he relates the mineral species identified in the frozen sample to the chemistry of the fused slag with the question, "Is it not most philosophic to hold that these independent entities were wholly integrated in the initial magma; that their presence in it was wholly

Jan 1, 1968

By W. W. Mason

The US began exporting coal in the late 1800s, at first in very small quantities to Canada and, beginning in 1897 and 1898, to the east coast of South America. Shipments to European countries began on a very limited basis in 1902 and these shipments increased gradually until World War I when shipments overseas increased from 7.3 Mt/a to 20 Mt/a. After the war exports dropped as fast as they had increased and, with the exception of exports to Canada, remained at very low levels until just after World War II when the US again emerged as a major coal exporter. World War II left the coal industries of Europe in ruin. As the US was the only country able to supply large quantities of coal at reasonable prices needed for reconstruction of the European economy, the US coal exports overseas expanded rapidly to 38.6 Mt in 1947. Additionally, we shipped 23.8 Mt of coal to Canada in that year for a total export of 62.3 Mt. Unfortunately, that level was not reached again until 1957 when exports reached an all-time high of 69.3 Mt - a high that has not been reached since. Over the years the level of US coal exports has fluctuated fairly widely. Approximately 80-90% of all US coal exports are high quality metallurgical grade coal so our exports level depends directly on world-wide economic conditions and world steel production levels.

Jan 1, 1982

By W. R. Crane

The effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. Drainsge in these mines has been discussed in papers on mining practice,' but the fact that water, varying from 0.16 to 3.46 and averaging 1.43 times the amount of ore mined, has to be pumped from the mines daily, indicates the importance of the problem and the advisability of making a thorough investigation of the source of mine water, its mode of entry into the mines, its effect upon mining conditions, and consideration of means of improving the conditions.

Jan 1, 1927

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-'. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.' The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By D. O. Ehrenburg, R. J. Watson

During the earlier period of electrical prospecting, the search for orebodies was by far the most important application of this method of geophysical prospecting. In the past few years, however, increasing attention has been paid to the possibilities of this method in the investigation of subsurface structures. Not only have fault zones been located, but attempts have been made to determine the depth to certain strata and thus contouring on some bed which proves to be a good "electrical marker." Many workers have published the results of field tests showing how their particular interpretations have agreed with the actual field conditions, but very few have stated their method of interpretation. Weaver, Hummel and Stefanesco and Schlumbergerl have given a more theoretical discussion of the resistivity methods. Hummel and Stefan-esco and Schlumberger have published mathematical solutions for the flow of electricity in a medium involving four layers. In this paper the authors present a solution for the flow of electricity in a medium of any number of horizontal strata. By means of this solution, curves showing the relationship between the apparent resistivity and the electrode spacing can be computed for ideal cases. Point-source in an Infinite Homogeneous Medium In resistivity measurements the current is conveyed to the earth by means of two electrodes, which can be mathematically treated as point-sources of equal and opposite strength. A point-source of strength I is defined as a point at which electricity is being generated at the constant rate of I coulombs per second, or I

Jan 1, 1932

By Murray Kaufman

Using en; 41 for a base alloy, 15 modifications were made in sheet form. The elements Al, Ti, C, Mo, Co, and Cb were varied. The effects on the phases formed and their temperature dependence, the aging characteristics, tensile and stress-rup- ture properties, and weld cracking were determined. The A1-Ti content and balance is the most important factor influencing the major sCrengthening phases [Ni,Ti and Ni,(Al, Ti)] and, consequently, mechanical properties. THE mechanical properties, fabricating and joining characteristics, dimensional stability, and so forth, of alloys containing secondary phases are largely determined by the phases present, their distribution, and their temperature dependence. The phases in the basic ternary and quaternary Ni-Cr-Al-Ti combina- tions have been investigated thoroughly.'* The phase behavior of many commercial nickel-base alloys has been determined also. In some cases, for example U500, 5 the effect on mechanical properties has been found. However, little systematic work has been done to clarify the action of each of the important alloying elements in controlling the phases formed in complex commercial alloys and their behavior. The effect of molybdenum on the carbides formed in M252 was investigated by Beattie and verSnyder.6 Application of the results provided by that work

Jan 1, 1963

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By Frank A. Crossley

The work described has one serious shortcoming: grain size was not monitored during heat up to the temperature (1675°F) of isothermal anneal. The chief obstacles to p grain growth in titanium a-ß structures are the a grains. Heating a structure such as that shown in Fig. 1 to a temperature close to ß transus causes dissolution of a grains in order to adjust the a/ß ratio, compare Figs. 1 and 2. During this process there is a concomitant growth of the ß grains—otherwise ß grains would have to be nucleated in order to adjust the a/ß ratio. When the annealing temperature is reached the a/ß ratio stabilizes and this initial phase of ß grain growth ceases. After an incubation period growth resumes as described. Some 0 grain boundaries can be clearly seen in Fig. 1. (Skilled metallography commonly produces photomicrographs which show more structural detail than direct observation.) These boundaries suggest that the average ß grain size is approximately 0.002

Jan 1, 1970

By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963

By Gerhard Derge, Harold Markus

The introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be dcscribed. For most of the additions, solutions containing 0.001 and 0.01 moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-l,ol~ate as follows: pH 0.1 M NaHC0............................................ 8.4 2 parts 0.1 M XaHCOr, 1 pa.rt 0.1 M NaZCO?................. 9.5 1 part 0.1 M NaHCOs, 2 parts 0.1 M iVa.,C03. ................ 10.0 0.1 M Na2C0............................................. 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves—sulphnte, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only -fuoridc, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also—phosphate, pcrborate, and chromate. Potential Measurements f The time-potential curves represntative of group 1 are shown in Fig. 1. These are the curves for 0.005 M sulphate ion and their similarity

Jan 1, 1939

By Harold Markus, Gerhard Derge

The introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be dcscribed. For most of the additions, solutions containing 0.001 and 0.01 moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-l,ol~ate as follows: pH 0.1 M NaHC0............................................ 8.4 2 parts 0.1 M XaHCOr, 1 pa.rt 0.1 M NaZCO?................. 9.5 1 part 0.1 M NaHCOs, 2 parts 0.1 M iVa.,C03. ................ 10.0 0.1 M Na2C0............................................. 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves—sulphnte, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only -fuoridc, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also—phosphate, pcrborate, and chromate. Potential Measurements f The time-potential curves represntative of group 1 are shown in Fig. 1. These are the curves for 0.005 M sulphate ion and their similarity

Jan 1, 1939

By Robert H. Chapman

During the past two years the writer has been traveling in the Lewis and Clarke timber reserve, locating the boundaries and reference-monuments for the Geological Survey. The Lewis and Clarke reserve lies in northwestern Montana. The region is very mouutainous, the main range of the Rocky mountains passing through it, dividing the waters of the Columbia and Missouri rivers. The mountains do not rise in one important and well-defined backbone, but in a series of parallel ridges, striking nearly northwest and southeast. Between these ridges, and, in general, parallel to them, are the drainage-systems. Beginning at the west, the rivers are the Swan, emptying into the Flathead lake, the South fork and the Middle fork of Flathead river, both emptying into the main Flathead river, which, in turn, empties into the lake of that name. The continental divide passes through the reserve from the southeast corner to the middle of the northern boundary, and the stream of most importance east of it is the Sun river, which heads well toward the north, and flows southeasterly and then eastward, and, emerging from the mountains, flows across the great plain of' the Missouri river. The southern boundary is drained by the Big Blackfoot river, flowing westward; the northern boundary, by the several branches of the Flathead river. The accompanying map (which is only a sketch, and does not represent the final work of the Geological Survey in this forest-reserve) shows clearly the parallel systems of drainage and ridges. The westernmost mountain range, the Mission, divides the great valley of the Flathead from the Swan river valley. The

Jan 1, 1900

By G. Thomas, O. Johari

MEIERAN and Richman' have proposed a method for the determination of electron-diffraction patterns from twinned bcc crystals. It is the purpose of this note to present a general method capable of predicting the positions of all reflections from both matrix and twin regions for all possible orientations of cubic crystals. The method has been verified for twinning in explosively deformed copper, and is found to be a very useful tool when used in conjunction with stereographic projection, and dark-field electron microscopy. Let an isometric crystal be twinned in any (hkl) plane. The twinning can be considered either as a reflection in the twin plane or as a 180-deg rotation about the twin axis. In reciprocal space, the 180-deg rotation about the twin axis would place a given point p, q, Y to a new position P, Q,R, such that both will be equally inclined to the twin axis. This is represented in Fig. 1. If the coordinates of three such pairs of points are determined, the matrix of the transformation can be obtained.' It is also seen that such pairs would satisfy another condition, i.e., the vector [p,q,r] plus the vector [P,Q,R] will yield a multiple of hkl, i.e., the indices of the twin plane, because in isometric systems the axis [hkl] is perpendicular to the plane (hkl). This can be simplified by taking the points along the three axes. If a point h2 + k2 + 12, 0, 0 is taken along the x axis, it is seen that its new indices should be so as to yield a sum 2h2, 2hk, 2hl,i.e., 2h(h,k,1). (Also the points h2 - k2 - 12, 2hk, 2h1, and h2 + k2 + 12, 0, 0 are equidistant from the origin and both points make equal angles with the twin axis, i.e., cos-' h/dh2 + k2 + l2.) Similar operations for the points yield respectively, after the 180-deg rotation about the twin axis. Following the method due to Buerger,' the matrix of the transformation is obtained as follows: Using this matrix the indices of any other point in reciprocal space can be determined. This matrix is much simplified for (111) twinning commonly encountered in fcc metals, since are each equal to —1; hence

Jan 1, 1964

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962