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By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By Charles R. Fettke

The Bradford and Richburg oil fields are the only pools where artificially conducted water drives on an extensive scale have been economically successful. Field practice has progressed from the original accidental or intentional circle flood, through the line flood development plan, to the intensive complete development plan, which is the most-recent and generally considered to be the most successful. Of the intensive development plan the five-spot arrangement of wells is the one that has been used most extensively. A further development associated with the latter method is the application of additional hydraulic pressure to that of the hydrostatic head of the column of water in the intake well. In conjunction with this method is the practice of delayed drilling of the oil wells until the water from the intake wells has entered even the less permeable portions of the sand and developed a "bank" of oil at which time all oil wells are drilled as nearly simultaneously as possible. The five-spot pressurc flood with delayed drilling gives more rapid return on investment than any other method. The seven-spot and nine-spot patterns are rarely used. No chemicals, such as sodium carbonate and other so-called flooding agents, are being added to the water at present since the field tests carried on in 1926 gave no positive results. All air and gas drives have been discontinued.

Jan 1, 1930

By H. M. Chance

Stretching from New York southwestwardly to Georgia is a great range of hills and mountains consisting of pre-Palæozoic schists, slates, .and gneissic and granitoid rocks, known locally by many different names; in Pennsylvania as the South mountains, the Berkshire or Durham and Reading hills, and in Virginia and farther south as the Blue ridge. To the northwest of this range lies the " Great Valley," underlain by Lower Silurian limestones, and known as the Lehigh valley, Cumberland valley, Shenandoah valley, valley of Eastern Tennessee and Georgia and by other local names, but all these are parts of one valley, geologically and geographically continuous from New Jersey to Georgia. Lying upon and along the northern flank of this range of mountains, and dipping northwestwardly under the limestone of the valley, is the Potsdam formation (Primal or No. 1 of the Pennsylvania Geological Survey), which consists of sandstone or conglomerate overlain by slates. The latter are sometimes arenaceous and occasionally are replaced in part by sandstone. This formation varies from a few feet to several hundred feet in thickness. At the outcrop the slates are completely decomposed, oxidized or disintegrated, forming a belt of clay several hundred feet wide occupying the interval between the outcroppings of the sandstone and limestone. This clay-belt includes a more or less continuous series of iron-ore (brown hematite) deposite, which have been, and still are, extensively worked. The belt is more or less continuously milleralized with iron throughout its length, and hundreds of large deposits of ore have been developed and worked, producing many millions of tons of ore.

Jan 1, 1909

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By Charles Austin

IT has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A, critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publications1,2 have shown that the factors controlling graphitization below the A, are different from those operating above the A, inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemi-cal analyses. Many years ago it was recorded' that the rate of graphitization at subeutectoid tem-perature is not a maximum just below the A, critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is im-possible to spheroidize certain steels in the temperature range of 650° to 710°C. with-out the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A, (720°°C,) these same steels may be completely sphe-roidized at constant temperature. In previous studies1,2,4 on 1 per cent plain carbon steels graphitization was en-countered during prolonged tempering. The limited number of steels studied did not provide sufficient data to permit adequate study of the factors controlling this graphi-tization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, fur-nished by four steel companies, who also supplied information regarding the history of manufacture.

Jan 1, 1940

Edward Keller, Baltimore, Md. (communication to the Secretary*) :—The authors of this paper are to be commended for their industry and congratulated upon the many interesting results which were the fruit of their researches. While thoroughness has marked their work in general, yet on a few points in particular they have touched but lightly, for which reason, it would appear to me, they have hit wide of the mark in their respective conclusions. The work alluded to pertains chiefly to the occurrence of magnetic iron oxide (ferroseferric oxide) in copper-mattes. Because the authors find that the magnetic residue, left by the dissolved sulphides, varies largely in quantity according to the strength of nitric acid used (with potassium chlorate) in dissolving the mattes, they conclude :— "It appears, therefore, that the ferroso-ferric oxide is the result of precipitation by the oxidizing agent, rather than an original constituent of the matte." In this part of their investigation, Messrs. Gibb and Philp have ignored some well-established data,. In the first place, they have overlooked the fact that there are mattes which are strongly magnetic and others which scarcely show any magnetic property. There is nothing in their work tending to explain this variation. They Seem to have tested none of their products for magnetism. Secondly, they have overlooked the fact that magnetic iron oxide probably exists in all ore-charges in the copper-matting furnaces, and, under the given conditions, that this oxide is very difficult to reduce and to combine with silica to form slag. Thirdly, they pay no attention to the varying specific gravity of the several grades of copper-matte, which may exceed, equal, or fall below that of the magnetic oxide. These are .essential points which, I believe, clearly in-

Jan 1, 1906

By V. R. Garfias, H. J. Hawley

FoR a number of years the senior author has been interested in the various geologic and engineering problems involved in the development of the petroliferous districts of northeastern Mexico, having in a previous paper* endeavored to present a summarized statement of the information relating to the geology and soil resources of this region. Of the many interesting geologic phenomena, perhaps those which have been the object of most speculation relate to the igneous intrusions which, in places, have a controlling influence on the accumulation of oil in commercial quantibies, a relationship which has been tentatively explained by various observers with as many interestingly different views. The authors of the present paper aim to record, in the course of a general discussion of the various viewpoints, some additional data, and present further tentative conclusions with a view to rounding out an up-to-date summary of the subject. The greater part of the area in question lies in the State of Vera Cruz, only a northwest fraction being in the State of San Luis Potosi. Vera Cruz is bounded on the north by the State of Tamaulipas, the northernmost of the Mexican States along the Gulf. The topography of the States of Tamaulipas and Vera Cruz and of Texas and Louisiana to the north, is controlled by the Gulf coastal plain which in northern Vera Cruz has an average width of about, 60 miles, the transitional topography between that of the rugged Banks of the Sierra and the lowlands of the coast being made up of a series of terraces and irregular hills and valleys. Geology and StRucture The greater part of the mainland of Mexico is made up of Tertiary and later effusive rocks and of sedimentaries of Cretaceous age. The igneous rocks form a belt from 150 to 300 miles wide, spurs of which shirt

Jan 1, 1918

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 David Baker

When the skip-hoist was first tried as a means of filling the blast-furnace it made a great many enemies and very few friends among furnace managers. This state of affairs continued until the Duquesne furnaces were built, which demonstrated not only the possibilities of a furnace-stack in the way of production, but also the ability of the skip-hoist to charge the materials necessary to produce the large tonnlage obtained. Every furnace manager, who has operated stacks fitted with the vertical hoist and the hand-barrow system of filling, remembers that the momentous question about the furnace, particularly during a good run, was: "Are you keeping her full ?" and many a good run has been spoiled by the furnace " getting away from the men." With the new birth of the skip-hoist this trouble was eliminated ; but alas! Other and more important difficulties arose. The distribution of the stock, the importance of which is never learned until many different ores and fuels have been tried, demanded closer attention. With all the defects of the hand-barrow system, the distribution—When the top fillers were conscientious in carrying out the scheme of filling arranged after thoughtful consideration by the manager—mas above criticism. It is said that the modern skip-hoist, equipped with an elliptical hopper and receiving-cylinder, and discharging over a small bell into the main hopper, will give just as good results as those obtained with hand-barrow charging, but I cannot agree with this statement. I grant, that under very favorable conditions, the mechanical furnace-top will do apparently as well as the

Jan 1, 1905

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.' Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.' He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.' However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.' In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By R. B. Sosman, J. C. Hostetter

We have shown in the preceding paper that practically all natural oxides of iron contain a determinable percentage of ferrous iron, and in many cases the percentage approaches that in magnetite itself. Some of these oxides are true homogeneous solid solutions. Others are not homogeneous, and can be separated magnetically into fractions. The nature and cause of this inhomogeneity in certain special cases form the subject of the present paper. Magnetic FRactionation of Oxides of Iron The magnetic fractionation of a sample of oxide can be conveniently carried out by powdering the material very fine, and exposing it at various distances from the poles of an electromagnet. The magnet that we used was specially designed1 to give a strong field together with a steep gradient outside of the poles. It is set in a frame, with the pole pieces directed downward. A glass plate can bc adjusted at various distances beneath the poles. If the fine iron oxide powder is placed just beneath the glass plate, successive portions of the powder are picked up by the magnetic attraction and are caught against the glass plate, the most magnetic portions being taken up at the greatest distance from the poles. Some natural oxides can thus be separated into several fractions of different magnetic susceptibilities. Among other natural iron oxides, we examined the powder obtained by crushing some crystals of hematite from Elba.2 We found that

Jan 1, 1918

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.' EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.' A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

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 J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By L. J. Howell, H. H. Kellogg

AN a previous paper' the phase diagram and vapor pressure of melts in the systems NaC1-ZrCl,, KC1-ZrCl,, and NaC1-KC1 (1:1 molar)-ZrC1, were reported. This note supplements the earlier paper with the results of electrical conductivity measurements on NaC1-ZrC1,and NaC1-KC1 (1:l molar)-ZrC1, melts. The design of the conductivity cell is shown in Fig. 1. Tungsten electrodes, A, were sealed into the Pyrex cell, C. That portion of the electrodes in contact with the melt was covered with a tight-fitting platinum cap. The electrodes were sur-

Jan 1, 1960

By Derek J. Fray, John Chipman

THE solubility of graphite in y-iron has been determined by several workers'12 with reasonable agreement. With the increasing use of more complex steels, it is necessary to understand more fully the thermodynamics of the austenite phase. The activity of carbon in a number of alloys is known but the maximum solu- bility of graphite has only been measured by Sohnchen and piwowarsky3 for Fe-Ni and Fe-Si alloys. Recently, Chipman and Brush reviewed the published data on the activity of carbon in binary and ternary austenite and also obtained expressions for calculating the solubility of graphite in Fe-Ni, Fe-Co, and Fe-Si alloys. On comparing the theoretically derived solubilities with the limited results of Sahnchen and Piwowarsky, it was found that the agreement for Fe-C-Si was excellent but there was considerable discrepancy for Fe-C-Ni and no data for Fe-C-Co. It was therefore decided to measure the solubility of graphite in a series of Fe-Ni and Fe-Co alloys. The alloy samples were made up by induction melting a high-purity master alloy under an inert atmosphere in an alumina crucible and drawing the molten metal into four-bore alumina tubes. Using this technique, it was possible to form alloy rods approximately 2 in. long and 1/18 in. in diam. Sixteen lengths of fine rod could be made without solidifying the master alloy. These were then allowed to cool under the inert atmosphere before being sectioned. The samples were packed in a graphite crucible with spectroscopic graphite powder, together with a piece of pure iron foil. Dry hydrogen, which had been saturated with isopropyl alcohol at room temperature, was passed over the crucible at 1000°C for 72 hr. At the end of the 72 hr argon displaced hydrogen in the reaction tube and the crucible was quickly pushed to the water-cooled end. The samples were thoroughly cleaned of the adhering graphite and analyzed. The pure iron samples always contained 1.5 0.02 pct C, which compares favorably with the data of smith2 and

Jan 1, 1970

By Donald E. Garrett

The processing of brines from Searles Lake, California, yields one of the world's largest supplies of borax and boron chemicals, second probably only to the massive deposit at Boron, California. Two companies produce from this deposit, the American Potash & Chemical Corp. and the West End Chemical Co., a division of the Stauffer Chemical Co. Two processes are employed in recovering borax from the brines; one is used by both companies and consists of carbonating the brine to form sodium bicarbonate, removing this, and then cooling the liquor to crystallize a crop of borax. Only American Potash uses the second process, evaporating the brine to concentrate it and remove (crystallize) much of its NaCl, Na2CO3, Na2SO4, and NaLi2PO4 content, quick cooling the remaining liquor to remove KCI, and then seeding the filtrate to remove borax. Both methods will be briefly described. Searles Lake is a large evaporite body formed during the most recent two Sierra Nevada ice stages, the Tahoe and the Tioga. Runoff waters from the Sierra Nevada Mountains collected in the large Owens Valley drainage basin and from there overflowed into the Indian Wells basin and then into Searles Lake. In each Lake, evaporation took place. To a large extent the Owens and Indian Wells lakes acted as settling basins, for much of the mud, and insoluble calcium and magnesium precipitates were deposited there. Recent volcanic activity in the mountains to the north and east of Owens Lake had scattered considerable mineral-rich volcanic ash and debris throughout the drainage area, and several hot springs were formed that contained boron and other salts. The present flow rate and concentration of several springs, and the known age of at least the Tioga zone, can fairly well account for all of the boron present in Owens and Searles Lakes.1 The tungsten content can be accounted for in a similar manner.2 Most of the salts thus originally present in the fresh water runoff-from ice, snow, and rain-accompanying these two ice stages were ultimately deposited in Searles Lake. During the Tahoe period, from 25 to 40 ft of massive, mixed salts were deposited, along with six interspersed layers of mud (four inches to two feet thick) representing comparatively brief interglacial periods. Before the final desiccation of the lake, from 10 to 14 ft of new mud was deposited, representing the Tioga stage. The crystals subsequently deposited were from 70 to 90 ft thick, and form the present lake surface. The extent of the salt body is about 34 square miles, of which 12 square miles are exposed salt; the remaining area is covered by recent alluvial deposits (chiefly mud). The present lake is generally dry on the surface but floods to a shallow depth following heavy rains. The crystal body of both zones consists of continuous clusters of salts, and the voids between crystals (about 45 pct of the total volume) are occupied by brine. The level of this brine never recedes more than several inches below the salt surface. The brine pumped to the plants for processing is generally saturated with all of the solid phases present in that area, and thus is a complex mixture containing about 35 pct solids (see Table 3). The brine composition varies somewhat at different areas of the lake and from upper to lower structures, so wells are drilled in the areas and to the depths desired. A casing is cemented in the hole to within a short distance from the bottom, and pumps with about 14-ft suctions are mounted on the casing to pump the brine into the plants. The evaporation process of the American Potash & Chemical Corp. treats upper structure brine, evaporating all of the water from

Jan 1, 1960