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By A. J. Weinig

THE Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short, periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield almost an hopeless "mess" it a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by amore scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general.

Jan 3, 1916

By GEO H. DEIKE

NOT much activity has been evident during the past year in the establishment of co-operative scholarships but the interest among the coal-mining companies is more pronounced than ever. This is apparent from the replies received to a letter sent out by the Committee on the Promotion of Student Interest in Coal Mining to over 120 coalmine operating officials. With that letter was forwarded a bulletin issued by the school of mineral industries of The Pennsylvania State College entitled ?Industrial Scholarships ? a Partnership of Industry and Education.? In that circular was outlined the need for trained men in the war and postwar world, and particularly as such demands pertain to the growth of the mineral industries.

Jan 1, 1943

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115' C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg's investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,' using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960

By O. Lietard, J. Yvon, R. Mercier, J. F. Delon, J. M. Cases

INTRODUCTION Fineness is one of the main characteristics of powders and this parameter is the object of several definitions based on criteria connected with their uses as well as their determination methods. In trying to obtain the best reaction surface, fineness is characterized by the determination of the specific surface, but in other cases, particle size analysis is used. These two main methods are not, in fact, entirely independent and their complementary nature provides information concerning the morphology of the particles. In the case of a product formed by isodimensional spheres, the relationship between the specific surface and the diameter is well known: [S = 6 spd] where p is the specific weight of the material and d the diameter of the spheres. With no monodimensional spheres, but rather a granulometric distribution whose occurrences follow a mathematical law (1), the relationship is more complicated. The relationship between the specific surface measured by gas adsorption and the data of the particle size analysis is much more difficult to predict in the case of asymmetric porous particles, whose particle size distribution curves do not correspond to a known statistical law.

Jan 1, 1980

By A. E. Gorum, I. Cornet

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

Jan 1, 1961

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.' The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.' Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others' found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer' found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE

By A. L. Jr. Pozzi, A. O. Garder, D. W. Peaceman

A new numerical method is proposed for the solution of multidimensional miscible displacement problems. Besides the usual stationary grid associated with numerical procedures, the method uses moving points for which positions and concentrations are computed each time step. Based on the method of characteristics for treating combined transport and dispersion, the method applies equally well to any number of dimensions and, in contrast with other numerical procedures, properly takes into account the physical dispersion, no matter how small. Extensive tests show that accurate solutions of one-dimensional problems can be obtained over a wide range of values of the dispersion coefficient, including zero. They also show that the moving points do not need to be uniformly spaced, and that increasing the number of moving points beyond 2/grid interval does not significantly improve the accuracy of the solution. Two-dimmsional calculations using the new method were carried out to simulate laboratory model displacements in which gravity caused overriding of solvent. Good agreement between observed and computed profiles and measured and computed concentrations of produced fluid was obtained for a viscosity ratio of 1.89; at higher viscosity ratios, fair agreement was obtained Computed results were found to be significantly affected by vertical dispersion, and negligibly affected by dispersion in the direction of flow, in agreement with conclusions based on experimental observations. INTRODUCTION Although miscible displacement processes are potentially of great economic significance, limited progress has been made in developing mathematical methods for predicting the outcome of a solvent flood. Because of the complexity of the partial differential equations which describe multidimensional miscible displacement, numerical methods are a natural approach to their solution. The task of finding suitable numerical approximations to one of the partial differential equations, which involves both dispersion and convective transport, has been particularly difficult. Dispersion in the absence of transport is described by the heat flow equation, a second-order equation of parabolic type. This equation has been very successfully treated by numerical methods. Transport in the absence of dispersion is described by a first-order equation of hyperbolic type. This equation has been treated numerically with some success in one dimension, both by Lagrangian and Eulerian techniques, 1.2 but extension to two or more dimensions has not been satisfactorily accomplished. Usually one of two things happens: either the numerical solution develops oscillations or it becomes smeared by artificial dispersion resulting from the numerical process. When transport and dispersion are considered simultaneously, this numerical dispersion may dominate the low physical dispersivicy that generally characterizes miscible displacement. Stone and Brian2 have developed a new difference equation for treating combined transport and dispersion in one dimension. By suitable choice of certain parameters, they succeeded in markedly reducing both oscillation and numerical dispersion. However, a satisfactory extension to higher dimensions has not yet been found. Peaceman and Rachford3 presented a centered-in-time and centered-in-distance difference equation combined with a 1,transfer of overshoot" procedure which was demonstrated to work well in one dimension. The technique was applied to the two-dimensional miscible displacement problem, but subsequent calculations with zero dispersivity showed little change in results compared with the calculations they presented. This indicates that their method involved a numerical dispersion of the same order as the physical dispersion. The present paper describes an alternate method for solving the combined transport-dispersion

Jan 1, 1965

By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:' Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N's are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By M. Hoch

Equations are derived from statistical considerations to represent the activities of each component of an interstitial solution, and of a compound with a wide homogeneity range as a function of composition and temperature, based on the interaction energies between the various components, Eij. The equations are checked on the binary systems Fe-C, Ta-H, and Y-H, the ternary systems Ti-O-H, liquid Fe-C-0, and the compounds TiO, MnO, COO, and YH,. In all cases the present model represents the experimental data well. THE aim of this paper is to derive from statistical considerations the thermodynamic behavior of non-substitutional solid solutions. "Nonsubstitutional solid solution" means either an interstitial solid solution (carbon in iron, oxygen and hydrogen in hexagonal and bcc titanium, and so forth) or deviation from stoichiornetry in compounds (introduction of vacancies—removal of atoms in one or both lattice sites of compounds FeO, MnO, TiO, NbO, YH2). wagnerl and Fowler and Guggenheim considered the theory of compounds with small deviation from stoichiometry; Anderson includes larger deviations from stoichiometry, the defect being present in one component only, as vacancy and interstitial. Rees considers only vacancies in one of the components and introduces various kinds of sites for the component where the defect occurs; the various sites interact with different energies, thus giving isotherms with two or more plateaus. Both Rees and Anderson are mainly occupied in determining the limits of two-phase regions, and the defect interaction energy is determined from the critical point. Darken and Gurry5 gave a brief treatment of carbon solution in iron; Speiser and spretnak calculated the configurational entropy for binary interstitial solid solutions by assuming that each interstitial atom in the solution excludes a certain number of neighboring interstitial sites from occupancy. Use will be made of this concept later. Hoch et al treated transition metal oxides of the NaCl-type structure, and also oxygen solution in titanium.' The main aim was to determine the behavior of the activity of one of the components as a function of the composition in the single-phase region. In the present paper, the various interaction energies are discussed in detail and the similarity between interstitial solid solutions and deviation from stoichiometry in ionic compounds is shown. Both types of systems have in common that at least on one kind of lattice site only one kind of atom occurs; this gives a fixed frame to the system, permitting a much easier statistical treatment than for the substitu-tional solid solutions. (The theory is also applied to ternary systems.) The difference between an interstitial solution and deviation from stoichiometry can be explained as follows. In an interstitial solution in the pure or standard state the host atom or host structure is present alone and all the interstitial sites which are going to be filled when the interstitial atom is introduced are empty. The interstitial solution is now created by introducing atoms into this empty lattice. In the deviation from stoichiometry, both kinds of lattice sites are already occupied in a special fashion (all lattice sites occupied, or the same fraction of lattice sites empty, or one kind completely filled, the other only two-thirds). Deviation from stoichiometry removes atoms from lattice sites, adds them, or removes atoms from one kind of lattice site and introduces them on the other lattice site. Though both cases (interstitial solution and deviation from stoichiometry) lead almost to the same equations, they are treated separately. The treatment given below corresponds to the "regular solution"10 treatment of substitutional solid solutions. Speiser and spretnak's6 treatment is similar to the athermal solution in the substitutional use. a) INTERSTITIAL SOLID SOLUTIONS Theory. It will be assumed that there are N lat-tice sites occupied by the host atom (denoted by 1). Corresponding to those N lattice sites there are N octahedral and EN tetrahedral interstitial sites. If only one kind of interstitial atom is added, this in-

Jan 1, 1964

By R. W. Smith, G. W. Delamore, J. A. Spittle

RECENT work by the authors1 has demonstrated that the crystals constituting the equiaxed zone in small ingots originate, on quenching, in the chilled liquid. Whether any partial remelting2 takes place of the den-drites nucleated in the chilled region was not examined. However, the claim3 that this normally occurs, leading to crystal multiplication, has been disputed.4 Thus, for an equiaxed zone to form in the central region of an otherwise columnar ingot, it is necessary to transport crystallites from the chill zone to this region. In view of the work of Uhlmann et al.,5 it was considered desirable to examine the transport process further. Experimental Technique and Results. In the earlier experiments by the authors.1 a stainless-steel crucible 17/8 in. diam, 41/2 in. high, ad containing an alloy of A1-4 wt pct Cu, was quenched from 660°C into a bath of Wood's metal maintained at 100°C. Under these conditions a central zone of equiaxed crystals was obtained. However, if a 2250-G unidirectional magnetic field was applied for 2 sec immediately following the instant of quenching, or subsequently, the equiaxed zone did not appear. Careful thermal analysis showed that the short application of the field had virtually no effect on the thermal conditions of the melt. It thus appeared that the crystallites which were ultimately to grow large enough to form the equiaxed zone existed in the liquid immediately ahead of the interface, occlusion being prevented by the convective fluid flow induced by freezing from the walls of the cylinder. When this relative movement was prevented by the Lorenz forces induced by the application of the magnetic field, the crystallites were caught up in the rapidly advancing dendrite solid-liquid interface. To test this assumption, a small ingot of super-purity aluminum was partially melted and poured into a heated stainless-steel mold which was then immediately quenched into molten Wood's alloy. The resulting structure is shown in Fig. 1, and consists of columnar grains with a central fine-grained zone. Thus the unmelted solid present at the beginning of solidification had been transported ahead of the columnar interface. Discussion. There appears to be little or no information available on the interaction of suspended particles with a metallic solid/liquid interface. However, some information is available for transparent organic sys-

Jan 1, 1969

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400' or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400' or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By K. G. Davis, P. Fryzuk

VALUES for the equilibrium distribution coefficient, ko, are required for solidification studies. The procedure generally adopted1-3 is to progressively solidify alloy rods over a range of growth rates, under conditions where a high degree of convective mixing is present in the melt. The measured effective distribution coefficients are plotted as a function of growth rate, and the extrapolated value at zero growth rate is taken to be the equilibrium ko. The method is limited by the experimental difficulty in obtaining steady growth rates less than approximately 10-4 cm per sec. Extrapolation from rates greater than this can lead to inaccuracy. In the present investigation, an alternative method for determining ko, previously used by the authors for the Ag-Sn system,' was applied to alloy of thallium in tin. Specimens were grown under conditions where convective mixing was absent, and experimental concentration-distance curves in the region of the initial transient were compared with curves calculated for trial values of ko. The ko which gave the best fit was taken as the correct value. To obtain the calculated curves, a value for the diffusion constant in the liquid near to the melting point was needed. This was determined by the capillary-reservoir method. Diffusion Constants. Details of the experimental procedure used by the authors in the capillary-reservoir technique have been described in previous papers,5'6 the only variation being in the use of Tl204, a ß emitter, as tracer, in contrast to previous work where ? emitters were used. The activity of a ß-emitting sample, as measured in a Geiger counter, is proportional to the surface area. To measure the concentration of thallium along the capillary after diffusion had taken place, the solidified capillary (1 mm diam) was cut into 2.5-mm lengths and each length compressed between parallel steel plates to form a disc approximately 5 mm in diam. The discs were placed in a flat-bottomed dish, covered by a thin lead shield with a central aperture, and counted in a 0 counter with fixed geometry. Each disc was etched lightly in a dilute solution of nitric and hydrochloric acids a short time before counting, to eliminate sur-

Jan 1, 1968

By F. H. Wilson

Copper base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pet silicon shows an attractive combination of high strength with excellent, machinability. Since there is no evidence ill the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. Alloys StVdied For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An excess of 0.05 pet silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 1/4 by 5 1/4 in. were cast using Durville type casting equipment. Ailalyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pet of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1949

The following is an extract of the Engineers' licensing law recently passed by the Colorado legislature; it went into force July 10. On the board of examiners are representatives of the four national societies. R. J. Grant, of Denver, represents the American Institute of Mining and Metallurgical Engineers; H. I. Reid, of Colorado Springs, the. American Society of Civil Engineers; H. S. Sands, of Denver, the American Institute of Electrical Engineers; and Frank E. Shepard, of Denver, the American Society of Mechanical Engineering. Within sixty clays after the taking effect of this act the Governor of the state shall appoint a State Board of Engineer Examiners, to be composed of five members, who shall be legal residents of the state of Colorado and who shall have been engaged in the practice of engineering for at least ten years. Upon the expiration of the term of any members other than the state engineer the governor shall appoint their successors for a term of four years, from a list of five nominees elected by the licensed engineers acting in a general assembly called together for this purpose by the president of the board. Such assembly shall be held in the month of January next preceding the expiration of the terms of any members. The Board of Examiners shall adopt all necessary rules, regulations and by-laws to govern its proceedings, not inconsistent with this act or the laws of the state or of the United States.

Jan 8, 1919