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By R. A. Bosch, F. V. Lenel, G. S. Ansell

RECENTLY, Ansell and aenel' proposed a dislocation model to account for the yielding behavior of dispersion-strengthened alloys. The criterion for yielding used in this model was that yielding occurs when the shear stress due to arrays of piled-up dislocations fractures or plastically deforms the dispersed second-phase particles. Calculations based on this model predict that the yield strength, uysof a dispersion-strengthened alloy containing particles whose geometry permits them to be considered as straight, i.e. not curved, barriers to dislocations follows the relation where and are the shear moduli of the matrix and dispersed phase respectively, b is the Burger vector of a dislocation in the matrix, A is the mean free path between dispersed phase particles and C is a constant. This yield stress, ys, is closely approximated in polycrystalline alloys by the proportional limit. The offset yield stress, uoy, is the yield stress, uys, plus the increase of stress due to strain hardening in the offset strain increment. Previous investigation1 has shown that Eq. [I] describes the yielding behavior of several different dispersion-strengthened alloys as a function of the mean free path between dispersed phase particles at a constant temperature. The purpose of this investigation was to investigate the temperature dependence of the yielding behavior of dispersion-strengthened alloys. The alloys studied, MD2100 and MD5100, are SAP-type alloys containing flake shaped aluminum oxide particles dispersed in a matrix of commercial purity aluminum. The proportional limit and 0.2 pct offset stress of both of these alloys were determined as a function of temperature over the temperature range from -190" to 500 C. All tests were conducted on an Instron tensile testing machine. Stress was measured by means of the Instron load cell. Strain was measured by means of SR-4 strain gages attached to the tensile specimens. Stress sensitivity was 80 psi. Strain sensitivity was 2 x 10F Fig. 1 shows the values received for the proportional limit and 0.2 pct offset yield stress plotted as a function of homologous temperature for both the MD2100 and MD5100 alloys. Inspection of Eq. [I] shows that of the terms which determine the theoretically predicted yield stress, uy,, only the shear moduli have an appreciable temperature dependence. From Eq. [I] the yield stress at any temperature T, UT, may be predicted from the yield stress at any arbitrary reference temperature, in this case 25 OC, u25, by the relation where the subscripts T and 25 refer to the values of the property at test temperature and at 25"C, respectively. The temperature dependence of the yield stress predicted by Eq. 121, based on the observed value for the proportional limit at 25OC, is also shown in Fig. 1. In evaluating Eq. [2] the following data was used. The values for the shear modulus of

Jan 1, 1962

By H. I. Aaronson, C. Laird

The kinetics of thickening and of lengthening of ?' plates in an Al-3.93 pct Cu alloy in the temperature range 203" to 300" C were determined by means of transmission electron microscopy. The rate of thickening was found to be less than that allowed by volume diffusion control at all temperatures, by amounts which increased with decreasing temperature, in agreement with the predictions of a general theory of precipitate morphology.1 Thickening was treated on the basis of the ledge mechanism. Ledges were deduced to spread across the broad faces of ?' plates at volume dzjrfusion-controlled rates, as anticipated from the disordered structure of their edges. Lengthening of 8' plates, on the other hand, took Place more rapidly than allowed by volume dzjrfusion. This occurred despite clear morPhological evidence of a bmrier to growth at the edges of these plates. It was concluded that the misfit dislocation structure comprising the barrier requires that lengthening take place by a jog mechanism. The tnisfit dislocations, however, also serve as diffusion short circuits, and allow high overall lengthening rates to be achieved. In Part I' it was shown that, within the range of aging temperatures and times studied, the broad faces of 8' plates formed in Al-4 pct Cu are fully coherent with the a, matrix. Virtually .all of the dislocations present in these faces were found to have developed as a result of plastic deformation in the a phase. Such dislocations are thus "intruders", rather than the more usual misfit-compensating variety. The edges of 8' plates were confirmed, by extension of the earlier studies of Mat-suura and Koda,3 to be made up of edge-type misfit dislocations, in sessile orientation with respect to lengthening of the plates. These interfacial structures should cause 8' plates to thicken and to lengthen at rates less than those allowed under the condition of volume diffusion control, such as would be expected if the interphase boundaries had disordered structures.' The narrow width of 8' plates, the reproducible crystallography of their broad faces, and the appearance of these plates in cross section as octagons rather than as circular discs2 provide qualitative support for these deductions. The present study of the rate of thickening and the rate of lengthening of 8' plates was undertaken in order to examine them on a quantitative basis. I) THICKENING KINETICS OF THE BROAD FACES OF?' PLATES A) Literature Review. The measurements now available on the thickening kinetics of single-phase precipitate plates consist of one plot of the thickening of a proeutectoid ferrite plate in an Fe-C alloy,' showing (as predicted) thickening rates less than those allowed by volume diffusion control. B) Experimental Procedure. Details of the preparation of the 4-3.93 pct Cu alloy used in this study have been previously reported.4 As in Part 1,' transmission electron microscopy was the observational tool employed. A general description of the apparatus and procedures of the electron microscopy studies is given in Section I of Part I. In thin foils, 0' plates tend to form at and parallel to the foil surface.' A direct investigation of the thickening process by means of hot-stage transmission electron microscopy was therefore not feasible. It was thus necessary to use the conventional method of aging individual bulk specimens for a wide range of different times at the various temperatures studied. In each specimen, the thicknesses of a number of plates were measured. Since thin foils prepared from "bulk-aged" material contain a large proportion of grains with orientations near (001) , it was relatively easy to find, near the edges of the foils, the characteristic multifold patterns of intersecting extinction contours which indicate regions where the foil is exactly at an (001) orientation. The thicknesses of large numbers of plates were measured along the (200) branches of the "stars" so that the 8' plates were precisely parallel to the optical axis of the microscope. Wherever possible, intersecting extinction contours were adjusted with the parameter s > 0 to improve the visibility of the plates in bright-field illumination. These precautions, in combination with taking the measurements at the thinnest parts of the foils, minimized the errors in the measurement of the thickness of the plates resulting from inexact parallelism to the electron beam. Since the plates were very thin, it was not easy to measure their thickness on the photographs. The techniques of enlargement and of microdensitometry were employed to minimize errors from this part of the measurement. A further source of possible error, that the plates can appear thicker because of contrast associated with mismatch normal to the plane of the plate, was also considered. The images of the plates were usually thinner than those of dislocations, however, and no anomalous changes in apparent plate thickness were observed when regions of foil containing plates were tilted through various diffracting conditions. Any error from this cause must therefore be small. Other sources contributing errors were: a) the microdensitometer traces per se and the subjective estimates of their peak limits, and b) slight fluctuations in magnification associated with small changes in the current of the objective lens of the electron microscope. The overall error probably amounted to no more than 5 to 10 pct. In order to obtain readily interpretable data on thickening kinetics, it is essential that the diffusion fields of adjacent ?' plates not be allowed to overlap. Calculations'-' showed that this condition is definitely not ful-

Jan 1, 1969

By R. L. Curfman

WHEN the Uranium Reduction Co. mill was put on stream in October 1956, one of the many operational problems was that the sand-slime separation circuits could not produce a satisfactory RIP feed, inasmuch as production greatly exceeded de- sign capacity. The original cyclone portion of the circuits consisted of two stages of three 14-in. cyclones in each circuit, as shown in the condensed flowsheet. The high percentage of +325 mesh material in the over- flows of these 14-in. cyclones was not consistent with good operation, and flow rates per ton of ore were high, indicating that not enough of the total solids in the ore was being rejected as sands. It was inferred by members of the metallurgical department that returning the underflows, or sand fraction, from these cyclones back into the drag classifiers was the primary reason for dirty feed.

Jan 7, 1958

By J. C. Bartlett

The following discussion was suggested by an experiment of Mr. Krom, the Manufacturer of air-jigs, to illustrate the superiority of air over water as a medium of concentration. The paper is written in the interest of no system of concentration, but simply to test the experiment, and, perchance, to add something to the general fund of information on the subject. To speak of testing an experiment by a theoretical discussion, may seem a misuse of terms, but the theories concerning falling bodies and the resistance of fluids are pretty well crystallized into laws, which may properly be used to show where experiments which seem to refute them were improperly performed, and that instead of refuting they only corroborate. It is well known that a sphere of galena & inch in diameter, and a sphere of quartz 1/2 inch in diameter, are equal falling in water ; that is, these two spheres, being placed together in a column of water at rest or in motion, will practically remain together, filling or rising together, or remaining in suspension. Mr. Krom, to show that these

Jan 1, 1879

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By C. W. Hill

IN a previous article preliminary experiments were described, indicating the possibilities of a quantitative spectroscopic method for the determination of small amounts of lead in copper, which would be accurate and rapid, and could be carried out in the refining plant by one not skilled in chemical analysis. The present paper deals with the development of the method in the factory, giving the details of apparatus and its standardization, and presenting a comparison of the accuracy of the method with that of the standard electrolytic determination. (For variations and other applications of the method, the reader is referred to the first article.) FIG. 1.-STEPS IN THE ELIMINATION OF LEAD. (The lead line, at point 105.8 in the violet portion of the spectrum, is seen between the two copper Lines,-102.29 and -106.29, lying close to the latter. The crowded faint lines are due to the carbon are.) 1. OUTLINE OF METHOD A carefully weighed sample (0.4 gm.) of the copper to be tested is placed in a cavity in a graphite positive electrode. An arc capable of

Jan 10, 1918

By J. L. Rodda

The desirability of a uniformly sized abrasive for metallographic polishing has probably been recognized in a general way for a long time. Certainly all metallographers have recognized the damage that can be done to a polished surface by a piece of grit, especially if one of the softer metals, such as zinc or aluminum, is being polished. It is to be doubted, however, whether many metallographers have had any adequate idea of the particle size of the abrasives they were using or of the range of sizes encountered in any given grade of abrasive. At any rate, the descriptions of abrasives for metallographic work found in the literature are generally very meager. It was with the idea of securing an abrasive with a limited range of particle size that a study of this problem was commenced. Commercial abrasives, even when recommended for metallographic work, are made up of particles of varying sizes. One such abrasive contains some particles so fine that they remain in suspension for days and other particles so coarse that they settle at the rate of 3 in. per minute. It is evident that the coarsest particles are over 100 times the diameter of the smallest ones, or over 1,000,000 times the volume. The hopelessness of avoiding scratches under these conditions is evident. Vanderwiltl has described a laboratory method for grading abrasives in which the elutriator is used. Le Chatelier's method, described by Goereq2 also makes use of an elutriator. However, the elutriator is too slow for this purpose and requires too delicate a control for the range of sizes desired. The method of stirring up the abrasive in water, allowing it to settle for a given time, then drawing a measured depth off the top of the suspension, has been finally adopted as the simplest procedure. The largest particle in a given portion is then determined by Stokes' law:3

Jan 1, 1932

By David H. Browne

(Pittsburg Meeting, March, 1910.) NICKEL has always been a fruitful mother of problems. Previous to the year 1906 nickel was regarded as an element replacing iron in copper-mattes, and it was believed that the same laws which governed the elimination of iron could be applied-to nickel. This conception has lately undergone a complete change, and nickel in all its stages is now regarded as an element replacing copper; in other words, copper-nickel is considered now as two elements, but as one metal. When we commenced our investigations on Monel metal we made a great many experiments on the conversion of mattes, both high copper and high nickel. We studied closely the composition of the mattes and the changes produced by the blow. We found in all cases certain agreements which we believe are due to some law. Briefly stated, our conclusions are as follows 1. Nickel is not an element replacing iron in matte. 2. Nickel-copper alloys act in the matte-blow like one metal. 3. Nickel-copper alloys follow, during the matte-blow, exactly the same laws as govern. the behavior of copper alone. This brings up the question : What are the laws governing the production of metallic copper, and what are the relations copper to sulphur and iron during the Bessemer blow ?

Apr 1, 1910

By F. J. Longworth

FoR a number of years an intensive study has been made to improve the blast-furnace practice at Copperhill not only as to cost% but to provide a good grade of gas for the acid plants. This study took us back to the fundamentals of successful pyrite smelting; namely, a blast furnace working on a clean sulfide ore, free from fines, and the use of quartz high in silica as a flux. In 1919, the quality of the flux was improved and its effect on the metallurgy was very marked. To improve the practice further, it was necessary to work out some method of treatment for the sulfide fines and the siliceous and refractory ores, other than in the blast furnace. A series of milling tests indicated that these products could be successfully treated by differential flotation, and in 1922 plans were made and a flotation plant built. It was estimated that the flotation plant would deliver to the smelter 40 to 50 tons of concentrates per day; the problem was what to do with these concentrates. It was out of the question to attempt to smelt them in a blast furnace because of the dust losses and because our practice demands a charge free from fines for satisfactory operation. There is no custom smelter in the vicinity to which concentrates may be sold, pending the time when the tonnage will be sufficient to warrant roasters and a reverbatory furnace. Sintering and nodulizing were investigated but neither method fitted into our scheme of metallurgy. A close study of the converter practice was then made to see if some method could not be evolved to smelt this tonnage of concentrates in a converter without preliminary treatment. At that time, the converter installation consisted of two 12-ft. Great Falls converters, which were handling 12 to 14 per cent. matte. The heat balance of the converters working with 12 to 14 per cent. matte was more than sufficient to smelt the contemplated tonnage of concentrates but the mechanical difficulties of feeding fines into the Great Falls converter made the use of this type of converter impractical. While there was no opportunity to experiment with the Pierce-Smith converter, equipped with a Garr gun, theoretically it seemed practical

Jan 1, 1925

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.' It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12'13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By N. A. Ziegler

CONSIDERABLE work has been and is being done on the changes of physical properties that take place in alloys at elevated temperatures, and much information on this subject is published. Much less is known, as pointed out by Rickett and Wood,1 about reactions between the alloys and atmospheric gases and still less is known about changes within the alloy itself under the influence of heat and given atmosphere. Moreover, most of the work published has been done on the alloys of "heat-resist-ing" type, in which chromium is an essential ingredient, the behavior of all other alloys being quite unknown, except perhaps of decarburization produced at the surface by oxidizing atmospheres. It has been shown' that iron, with total amount of foreign ingredients not exceeding 0.01 per cent, if heated in an oxidizing atmosphere at above 900° C., may be saturated with oxygen to 0.1 per cent. It was suspected that something of a similar nature may take place in iron-silicon alloys (transformer material), the mechanism of such processes being either a direct diffusion of oxygen into the alloy, or oxygen combining with silicon to form Si02 or more complicated (silicate) inclusions. Another possi-bility to be considered was that during annealing in oxidizing atmos-pheres, when scale is being formed, silicon may oxidize preferentially at the surface, thus impoverishing the alloy in silicon. In collaboration with Dr. T. D. Yensen,3 the writer set out to investigate this problem about two years ago in order to settle these questions.

Jan 1, 1934

By Henry J. Miller, Marcella Linderman

During some experiments made by Henry J. Miller, partly in Germany and partly in the United States, in which it was found necessary to melt metals in quantities up to 60 kg. in a vacuum or under low pressures of hydrogen, molybdenum was tried as the resistor in the electric melting furnaces. Molybdenum ribbons 16 by 0.55 mm. and 18 by 0.45 mm. were used as resistors. The furnaces were of the type shown in Fig. 1. About the heating tube, Y, are wound parallel resistors of molybdenum ribbon from the water-cooled electrodes, El, Ez. The whole is within a copper container having outlets for the removal or introduction of gases and a window, W, for observation, the space about the heating tube and electrodes being filled with insulating material. The life of the molybdenum used as the resistor was found to depend very much on the manner of using it, its failure being due in some cases to thinning by evaporation or chemical reaction and in others to hardening, which prevented it from following the expansions and shrinking of the heating tubing without cracking. As such failures are often rather expensive in commercial work, it was thought worth while to determine the causes. The factors influencing the behavior of molybdenum resistors used in this manner may be briefly stated as follows:

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By R. Wild, F. A. Wright

When a blast furnace has a certain defined burden and is operated under fixed conditions of blast temperature, etc., the fuel efficiency is determined by the extent to which the reducing gases can remove oxygen from the burden in the furnace stack. This is determined by two distinct factors: 1) The uniformity of gas-solid contact, and 2) The ease with which oxygen can be removed from individual pieces of burden. This latter is often called burden reducibility. When burdens were poorly prepared the first factor was by far the most important and a study of the reducibility of individual lumps was of rather academic interest. In recent years good burden preparation with emphasis on uniformly sized material has led to greatly improved gas distribution in the stack, and thus the second factor has become much more important and there has been a marked increase in interest in methods of measuring reducibility. This paper explores the Linder method of measuring such reducibility. The measurement of reducibility of burden materials must be carried out under conditions duplicating, as nearly as possible, those of the blast furnace stack. This is very difficult since the blast furnace process is a counter-current one, and thus the initial conditions encountered by the solid (gas temperature, composition, etc.) are the result of heat and mass transfer occurring lower down the stack. Any method of burden testing which does not take this into account is, at least to some extent, based on arbitrary assumptions. In an attempt to study blast furnace reactions under non-arbitrary conditions BISRA adopted the SCICE technique as a method of investigation. This technique has been used with a measure of success.' The SCICE technique, however, was found to be too slow for use as a routine test for burden materials and it was decided to construct additional equipment for burden testing. A test was required which would: 1) Be as realistic as possible. 2) Be quick and easy to operate. 3) Give some indication of the breakdown likely to take place during reduction in addition to a reducibility index. After a critical assessment of the reducibility tests which have been proposed it was decided to adopt the Linder test equipment and procedure as a basis for burden testing. THE LINDER TEST APPARATUS AND PROCEDURE The apparatus which was constructed (Fig. 1) was the same as that described by Linder2 except for minor changes in design. Linder also laid down a test procedure which he had derived from the results of investigations on Swedish blast furnaces. The variations of temperature and gas composition during the test were defined; these are shown diagram-matically in Fig. 2. BISRA's intention was to use the standard temperature and gas composition programmes for testing a variety of burden materials and also to investigate the influence of different programmes on standard burden materials, making use of information from the SCICE apparatus wherever this is possible. Up to the present, effort has been concentrated on the first part of the programme, and work on the second part has only just commenced. For each test 200 g of coke and 500 g of burden material were used. Linder had recommended that the coke and burden material should be between 1 and 1 1/2 in. and this was adhered to in early experiments on ores and sinters. Since the eventual aim of this work was to relate the test results to blast furnace operation, it was decided to carry out subsequent experiments using burden material in the size range used in the blast furnace, as far as this was possible. If the main interest was, for example, a comparison of the products resulting from different methods of agglomeration, then there would be advantages in using burden materials as close as possible to a standard size. After the charge had been placed in the reaction tube and this had been connected to the gas supply, rotation of the reaction tube at 30 rpm was started and the reduction programme was commenced, the gas temperature and composition being manually controlled according to the programme shown in Fig. 2. After the reduction test the charge was cooled in a nitrogen atmosphere. It was then removed from the reaction tube, the coke and burden separated, and the extent of burden breakdown assessed by screening it at 10 and 30 mesh. The extent of reduction was then

Jan 1, 1964

By W. A. Tiller

The unidirectional freezing of a semiinfinite liquid from one end has been treated by calculating the solute and temperature distributions in the liquid and solid phases with time, when the solid-liquid interface advances at a rate proportional to (time)lt2. The nucleation probability for new grain formation is calculated as a function of the constitutional and thermal properties of the alloy, the pouring conditions and the catalytic efficiency of the nucleating agents. The transition from columnar crystal formation to equiaxed crystal formation is assumed to occur at a critical nucleation frequency for a particular alloy and the quantitative dependence of the ratio (columnar zone length/equiaxed zone length) upon the freezing conditions has been predicted. The effects of (i) fluid flow in the liquid, (ii) heat transfer through a mold wall, and (iii) a finite ingot length, have been explicitly tveated as departures from ideality. These departures from ideality are found to have very important consequences on the ingot stmcture. In Part I&apos; of this series, a qualitative description of the general ingot structure was developed. The factors that determine i) the ratio of the equiaxed zone length to columnar zone length and ii) the grain sizes in these zones, were discussed. In the present paper, topic (i) will be treated quantitatively, and it is intended that topic (ii) will be treated quantitatively in Part 111. The complete treatment has been split in this manner for ease of development and coherency of presentation. The treatments are quite mathematical in nature and, although some of the conclusions to Part 11 depend upon the treatment presented in Part 111, it was felt that the intended audience would find the material more readable and more useful in its present form. To this same end, it seems worthwhile to reiterate some of the qualitative aspects of grain nucleation during ingot solidification before embarking on the mathematical description. QUALITATIVE ANALYSIS In the conventional method of casting, a liquid alloy with a certain degree of superheat is poured into a mold. The outer rim of liquid metal cools rapidly to the liquidus temperature of the alloy and begins to undercool. As the degree of undercooling increases, nuclei of solid begin to form in this chill layer, this nucleation being catalyzed by certain heterogeneous particles in the liquid. The grains in the chill layer which are generally of random orientation, begin to grow inwards because of heat conduction through the mold. The grains usually develop a columnar shape since the frequency of nucleation of new grains in the liquid ahead of the advancing interface is generally insufficient to seriously impede the growth of the original grains. Due to the slow diffusion rate of solute in the liquid, a solute distribution is formed in the liquid adjacent to the interface which is either an excess or a depletion if the partition coefficient, ko, of the solute is < 1 or > 1, respectively. Thus, the liquidus temperature of the liquid adjacent to the interface is a function of position. The actual temperature in the liquid is also a function of position and the temperature gradient at the interface decreases as the interface moves away from the mold wall. Since the rate of advance of the interface decreases with time, the equilibrium temperature distributions and the actual temperature distributions as a function of interface position, X, can be illustrated as in Fig. 1. Thus, a region of liquid may exist in which the actual temperature is below the liquidus temperature. This liquid is contitutionally supercooled and therefore unstable with respect to the nucleation of new grains. Now, since the supercooling in Fig. 1 increases as the interface moves further away from the mold wall, the nucleation rate of new grains will increase. When the nuclea-

Jan 1, 1962

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10&apos;3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey&apos; to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N&apos;s are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen&apos;s computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.&apos; The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By William Johnson

IT is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process, of freezing is a simple example of this, as Tammann pointed out years ago.1Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain,2-8 that the formation of pearlite from the eutectoid decomposition of the solid solu-tion austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Parnop and Sachs, and others&apos;-1 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decom-position by a number of investigators. Bain&apos;s2-8 work on the formation of pearlite from austenite is especially valuable in this respect-the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.&apos; Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o&apos;s, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some &apos;lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944