Search Documents

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By Y. C. Kim, C. B. Manula

This paper is concerned with the details of the derivation of an operations research model, specifically linear programming, to solve production scheduling problems. While some results are presented for an actual study, the calculation of cases of a more general nature have not yet been completed. Production managers from those segments of the mining industry that experience a seasonal or highly variable sales demand find it rather difficult to develop overall producing plans for their organizations. In an attempt to solve this technical problem, demands are usually met by keeping production corresponding exactly to sales. This results in a fluctuating production schedule which is costly to maintain because of overtime premiums in periods of high requirements and because of costs associated with an idle mine plant during slack periods. An alternate solution may be to produce part of the desired amount and make up any deficiencies by using overproduction in previous time periods. This tends to smooth the production pattern through the use of a stockpile. However, because of associated storage costs, the solution may again be undesirable if it yields comparatively large surpluses. In general, this type of scheduling problem has an infinite number of solutions which satisfy the requirements. These are largely dependent on the extent to which an operation is geared to changes in production and on the size of its stockpiling facility. The determination of an efficient schedule is implied, therefore, as one lying between two extreme solutions, i.e., one that minimizes surpluses and one that minimizes output fluctuations. These conflicting objectives result in an economic balance problem between the costs of carrying surpluses forward from slack periods versus the cost of high production levels during peak demands. Various methods of operations research have been developed to handle problems whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. Those who are familiar with mining operations know that most managers have not progressed satisfactorily in this area. Production planning systems which most mines employ today are often no more than rough records of management's mental planning. For small mines these means are normally sufficient; but as operations grow larger and become more complex, this type of planning ability is no longer adequate. Managers may find themselves losing control of cost relationships, taking longer to outline production sequences, and becoming forgetful of certain resource availabilities. ORIGIN AND SCOPE OF A SCHEDULING PROBLEM The more fundamental aspects of the production scheduling problem can be brought into focus by demonstrating how it exists in a bituminous coal mine* located in southwestern Pennsylvania. This mine, operating in the Pittsburgh seam, uses a definite room-and-pillar block system of mining, which is planned and carried out with only slight variations to meet local conditions. The coal seam, which is firm and varying in thickness from 8 to 9 ft with the bottom 6% ft being extracted, is under 500 ft of cover and opened by a shaft. The bulk of the coal (60%) is obtained from the pillaring activity with the mains and sections, which are considered primarily as development activities, contributing the balance of 12% and 28%, respectively. All coal is won by a ripper-type continuous miner in conjunction with shuttle-cars directly behind a loading machine. Track haulage is employed to move coal from these machine centers to the shaft bottom. The coal, thus mined, is shipped to one destination as part of a mixture of coals to be used in the making of steel. A material flow diagram of this distribution scheme is illustrated in Fig. 1. PROBLEM STATEMENT From the above types of shipments and mining limitations, the basic problem is to determine an economic means of producing and stockpiling a single coal product produced in three different machine centers (main, section, and pillar). Fig. 2 shows total demand for coal as a function of time. Because of the extremely high peak demands, slack period production must be stored and then distributed

Jan 1, 1969

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.' On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.' In this paper the terms "size broadening" and "strain broadening'' are used in the general sense adopted by warren.' In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.' The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7'8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.'l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

THE turn of the century was marked by the appearance of a series of greatly important pieces of research that became the foundations of modern physical metallurgy. It is, of course, some- what misleading to ascribe the growth of a science, or a branch of engineering, to the work of a few men, as it is to write history generally in terms of great men, for this approach neglects back- ground development, and tends to overemphasize the importance of immediately subsequent events; the correlative and steady growth of the basic sciences added to the resources of the new science of metals--developments in basic science .years later were to appear in their application to metal systems. Yet it is useful to emphasize the importance of these relatively few pieces of research. THE PHASE RULE The work of Willard Gibbs on heterogeneous equilibria, which included the derivation of the phase rule, was published obscurely in the journal of the Connecticut Academy.30 Unearthed by the German physical chemists (evidently by van der Waals, to use Ostwald's phrase, "aus dem staubigen Fundort"), its importance to the study of alloys was pointed out by Jüptner31 and by Le Chatelier; its application to polycomponent systems, and to metal systems in particular, was developed by Rijn van Alkemade (1893), by Le Chatelier;8a and especially by Roozeboom (1899-1900). The work of Raoult on the depression of the freezing point by solutes led to the study of the phenomenon in amalgams and shortly to metal systems. Work was done, by Roberts-Austen and others, on the initial freezing temperatures of binary alloys-the liquidi, data applicable to Raoult's work. Van't Hoff in 1890 had pointed out

Jan 1, 1948

By Leonid V. Azároff, H. N. Murty

In the course of investigating the soft X-ray absorption spectra of Ni-A1 alloys, Das and ~zfiroff' observed an anomalous brittleness in solid solutions containing 3 to 5 at. pct Al. The brittle alloys also had anomalously larger lattice constants' and the fine structure at the nickel K edge of an alloy containing 3.96 at. pct A1 unexpectedly resembled that of NiA1 more closely than that of a solid solution containing 5.51 at. pct Al. This led them to suggest the possibility that short-range ordering was produced during the homogenization anneal to which each specimen was subjected, similar to that observed in dilute solutions of vanadium and of chromium in nickel: as the principal cause of embrittlement. It was decided to repeat the above measurements on several alloys in this composition range in order to test the above hypothesis and to establish the effect of heat treatment on the alloys' properties. Three solid solutions in this range were prepared containing, respectively, 3.16, 4.00, and 4.54 at. pct Al, in addition to alloys containing 6 and 9 pct. All samples were annealed in vacuum at 1800°F for 100 hr and then furnace-cooled to room temperature, as in the original study. The lattice constants of these alloys are shown by open circles in Fig. 1 and can be seen to fit quite closely the curve established by the previously measured values, indicated by solid circles. (The experimental errors are of the order of the size of the circles, +o.oo~R.) The three alloys containing 3 to 5 at. pct A1 were found to be quite brittle, as previously reported. In order to test the possibility of ordering, these three solid solutions were again heated to 1800°F and, following a few hours at that temperature, were quenched directly to room temperature. All three alloys lost their brittleness. In order to verify the proposed ordering hypothesis, it was decided to subject each sample to several cycles of quenching and annealing (disordering and ordering). After some experimentation, it was established that reproducible results could be obtained by anneal-

Jan 1, 1968

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.' It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

The early Spanish adventurers found but little gold or silver on the American mainland, and the aborigines in the country that is now the United States were not as submissive as those of the West Indies, so the conquistadores obtained no foothold north of the Caribbean sea. Their later exploration north- ward had Mexico as a base-and wild yarns as a basis. The friar Marcos, a member of Estevanico's unfortunate expedition, brought the story of the Seven Cities of Cibola to Mexico City in 1539. Except as Indian hovels,* they existed only in a disordered imagination, but when Váquez de Coronado's expedition pricked the glittering bubble, there appeared an enticing mirage in the northern desert: the glorious land of Quivira, where even-the common pitchers and bowls were made of solid gold. Coronado proceeded northward and found only enormous herds of buffalo on the plains of Texas. It was a melancholy land. No gold or silver was to be seen among the poor Indians. Coronado reached the country of the Wichitas, in Kansas, before he abandoned his quest and turned home, which he reached, with only a third of his party, hungry and tattered, in 1542. So long as greed stimulates the imagination there will be no lack of tales such as those that repeatedly led the Spaniards to the rainbow's end. In 1860 an expedition was organized in San Francisco by Dr. Darwin French to explore the desert country near Owens lake on the news that the Indians in those parts shot golden bu1lets.t The fact that the savages were known to possess few guns did not discredit the tale, which

Jan 1, 1932

In 1803 the purchase of the immense territory called the province of Louisiana wm arranged between Thomas Jefferson, President of the United States, and Napoleon Bonaparte, First Consul of France. This central portion of what is now the United States was claimed in 1682 by the explorer Robert de La Salle for France, who continued to hold her title to the vast domain until 1762, when it passed by treaty to Spain, only to be retroceded to France in 1802, in consequence of Napoleon's military domination of Spain. Jefferson did not care to see New Orleans and its extensive hinterland pass into the hands of France. Spain did not matter so much; she was quiet and feeble, whereas France was restless and aggressive under Napoleon, who had dreams of founding a French colonial empire on the American continent. The expression of American feeling that Jefferson elicited came as a surprise to Napoleon, who concluded that a contest was not worth while, for his navy had been shattered by the English, and it was evident that only maritime supremacy could enable him to retain this trans-Atlantic possession; so he resolved to put it out of the grasp of England and at the same time replenish his military chest by selling Louisiana to the United States. The price was 60 million francs. By the terms of the Louisiana purchase a magnificent territory was added to the national domain; it covered more than a million square miles, or more than the total area of the United States at that time. Louisiana included the present States of Louisiana, Arkansas, Missouri, Kansas, Iowa, Nebraska, South Dakota, North Dakota, Wyoming, Montana, Oklahoma, with parts of Colorado, Idaho, and Minnesota; but

Jan 1, 1932

By Lee Hillard Meltzer, Ralph E. Davis

INTRODUCTION During the past few years emphasis has been placed upon methods of estimating the future expectancy of gas production from natural gas fields. Before technical methods were applied, the production expectancy over future years was based upon the knowledge of gas well behavior, learned through long experience and embedded in the "know-how" of men long in the gas producing business. It is doubtful that a technical study of future expectancy of a gas field or a group of fields was ever prepared for the preliminary planning of a natural gas pipe line system built prior to about five years ago. The decline in well production capacity was naturally recognized by all familiar with the business since its earliest beginnings more than 75 years ago. In 1953, the Bureau of Mines published Monograph Number 7, "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices," which gave to the industry the first technical analysis of the decline in production of individual gas wells. This method affords a means of estimating the future production in relation to decline in reservoir pressure. The demand for technical determination of expectancy of future gas productivity from fields or a group of fields led technical men to the application of the knowledge of well behavior to the problems. The decline in a well's ability to produce as pressures declined could be estimated by the use of the curve known as the "back-pressure potential curve" as developed by the Bureau of Mines. A field containing few, or even numerous, wells could be analyzed on the basis of the sum of potentials of all wells. In most studies of this nature, the problem is to estimate the rate of production that can be expected, not only from present wells but also, from wells that will in the future have to be drilled into the reservoir being studied. The "back-pressure potential" method requires that the following data be known or estimated: (1) Proved gas reserves. (2) Current shut-in pressures and rate at which shut-in pressures change with production. (3) Back pressure potential data on wells in the source of supply. (4) Ultimate number of wells which will supply gas, and their potential. (5) Limitations on productivity such as line pressures against which the wells will produce, friction drop in the producing string, and so forth. It is evident that the resulting estimate of gas available in each year for a future of say, 20 years, contains many uncertainties. While the method may have considerable merit for a field that is fully developed, it cannot be completely dependable in fields that are only partially developed. In such cases, some of the data upon which it is based can only be estimated or assumed. In the study of this problem during the past few years, a method has been developed which we believe has great merit, especially when applied to fields subject to substantial future drilling, and when applied to the study of fields which, on the average, appear to have characteristics similar, in general, to the average of the fields used in the development of the "yardstick" outlined herein. From an analysis of the production history of 49 reservoirs which are depleted, or nearly depleted, a curve has been constructed which shows the average performance of the reservoirs during the declining stages of production. When properly applied, this "average performance curve" can be used to determine the stage of depletion at which a reservoir or group of reservoirs will no longer be able to yield a given percentage of the original reserves. "AVAILABILITY" AND "AVAILABILITY STUDIES" The rate at which. a reservoir will yield its gas depends basically upon physical factors, such as the thickness and permeability of the sand, the effect of water drive, if any, and other conditions, and upon economic factors, such as the number of wells drilled. Within the ranges set by the physical conditions, a rate of delivery tends finally to become established. The rate (or range of rates) represents a balance between the interests of the operator, who desires the maximum return from his property and of the pipe line owner, who desires to maintain a firm supply for his market. This balance, which is influenced by the terms of the contract, determines the capacity which will be developed by the operator, and the time and rate at which the decline in production is permitted to occur. Thus the "availability" of gas

Jan 1, 1953

By M. I. Jacobson, M. L. Hammond

The solid solubilities of high-purity silver, aluminum, chromium, copper, and iron in zone-refined beryllium have been determined. Diffusion couple sandwiches of beryllium with aluminum, copper, and silver foil and diffusion couples of beryllium with two-phase alloys in the Be-Cr. Be-Fe, and Be-Ag systems were analyzed by electron beam micro-probe techniques. This paper describes the material used, the experimental methods for preparing the diffusion couples and the alloys, the analytical techniques, and the results obtained. The results are compared with those of previous investigators who used materials of lower purity. ~NVESTIGATORS of beryllium phase diagrams have often been hampered in their interpretations of certain phase boundaries because of the relatively low purity of the beryllium used. This has sometimes resulted in the appearance of three phases in the regions where only two should exist. Advances in purification methods, specifically zone refining, have made available beryllium that is considerably purer than the material previously used for phase diagram studies. The primary object of this investigation was to reex-amine portions of the beryllium-rich end of the binary systems of beryllium with silver, aluminum, chromium, copper, and iron to determine more accurately the limits of terminal solid solubility. The five elements—silver, aluminum, chromium, copper, and iron—include some which are commonly found as the major impurities in beryllium, some of which are being used as solid-solution alloying elements, and some of which are used in ductile matrix alloys. They are thus of considerable importance to physical metallurgists who must work with beryllium but who must rely on the present inaccurate or incomplete diagrams. The determination of more reliable diagrams would aid researchers concerned with the problems of alloying, heat treatment, and ductility. MATERIAL The beryllium was acquired from the Franklin Institute in the form of a single-crystal, 6 in. long by 1 in. in diam, zone-refined in three passes from Pechiney SR-grade beryllium bar. The principal impurities, as determined by mass spectrography at Battelle Memorial Institute, are shown in Table I. Vacuum-melted copper, silver, and aluminum, and electron-beam zone-refined iron were obtained from the Materials Research Corp. in the form of 1/2-in.- diam bars. Iodide chromium was obtained as flakes from the Chromalloy Corp. Analyses supplied with these metals are shown in Table 11. EXPERIMENTAL PROCEDURE Preparation of Diffusion Couples. Two types of dif-fusion couples were used in this study. For the copper, silver, and aluminum systems, the couples were sand-

Jan 1, 1969

By R. A. Liddle

Intermitt'en'I'ly during the past 10 years showings of oil and gas in tests drilled in the eastern part of Texas have stimulated the search for production. Tests on the flanks of the long-known salt domes, principally Keechi and Butler, have found oil in small quantity in the Woodbine formation of the basal part of the Upper Cretacrous. In the central part of Cherokee County, Colliton et all in 1926, in their Clapp No. 2 found a good showing of 37" B6. oil at about 3500 ft. Several wells were drilled in 1926 and 1927 as a result of this showing. On Jan. 22, 1927, Humble Oil & Refining Co. wildcatting on Carey Lake salt dome, obtained commercial production in its Clark No. 1. This inaugurated intensive exploration both for salt domes and for other types of structure. As a result several new domes and a few promising structures of other types have been discovered. Development in East Texas durinG 1927 Carey Lake Dome Location.—On the Neches River in Anderson and Cherokree counties, 10 miles west of Jacksonville, Cherokec (lounty. (Fig. 1.) date of Discovery.—During 1925 geologisls of the Humble Oil & Refining Co. working in the Neches River valley discovered slight surface fracturexs, cratic dips, and slickensided clays and sands in green-sands of the Mount Selman formation north of Carey Lake. A number of core tests were drilled by the Humble Oil & Refining C'o. during 1925 and 1926, some more than 1500 ft. deep, to check their surface obsuvations of faulting, and the possibilities of a salt dome. On May 16, 1927, solid rock salt was reached at 2142ft. in the first deep test on the prospect. Surfacc Indications.—Surface indications of the Carey Lake dome, though not as evident as manifestations at the previously known domes of Palestine, Keechi, Butler, Grand Saline, Steen and Brooks, are more noticeable than on any of the domes discovered in 1927. F. E. Poulsen, of the Pure Oil Co., who examined the area before the deep tests were drilled, noted the alignment of erratic surface dips which suggested faulting, especially in conjunction with slickensiding, and the local deflec-

Jan 1, 1928

By I. M. Bernstein

The steady-state creep behaviov of zirconium and zivcaloy-2 was examined in the temperature vatlge 520° to 620°C A1 low stresses the creep rates were cimracterized by a linear stress dependence; at highev stresses the stress dependence was much more pronounced. Temnperature-cycling tests yielded values for the aclivation enevgy for creep. Various tlzeories were examined in the ligltt of- the experimental re-sults and it mas concluded that the low-stress creep behavior is the result of the stress-direcled diffusion of vacancies along gain boundaries. It has been observed,"&apos; usually under conditions of high temperature and low stress, that creep deformation can occur for which the steady-state creep rate is linearly dependent on the applied stress. For magnesium and certain magnesium alloys, Harris and ones&apos; and ones&apos; have argued that this type of creep occurs by mass transfer as a result of the stress-induced generation and migration of vacancies, along a gradient defined by the stress direction. Jones&apos; demonstrated that the rate-controlling diffusion path is sensitive to grain size and temperature, and that by suitable control of these variables creep could occur by vacancy diffusion either predominately along grain boundaries or through the lattice. Recently, Jones3 suggested from an examination of limited high-stress data for zircaloy-2, composition in Table I, that significant diffusion creep could occur at low stresses, at least between 375" and 500°C, controlled by grain boundary vacancy diffusion. This process could have an important implication in assessing the role of zirconium alloys as a structural or cladding material in certain classes of nuclear reactors, since it predicts creep deformation far in excess of any estimates based on extrapolating slip creep data from higher stress levels. If the diffusion creep process occurs it should be possible to describe the total steady-state creep rate of zirconium and its alloys as the sum of two terms, Eq. [I]; the first term relates to a slip creep process important at high stresses and which is manifested by a much more pronounced dependence of creep rate on stress4 than diffusion creep and the second to a process controlled by mass transfer,5&apos;6 dominant at low stresses: where A and BI are parameters which can depend on structure, Ql and Q2 are the activation energies for the particular creep process occurring, and n describes the sensitivity of the creep rate on stress. It is the purpose of this paper to present some direct experimental evidence in support of this view. It is recognized that other analytical approaches have been proposed to explain data of this kind and these will also be discussed. 1) EXPERIMENTAL PROCEDURE Flat creep specimens (gage length 1 by 0.25 by 0.02 in. approx) were prepared from cold-rolled, argon-remelted, crystal bar zirconium and cold-rolled commercial-grade zircaloy-2, the analyses of which are given in Table I. The specimens were annealed at a pressure of < 10-5 Torr at temperatures from 625" to 675°C for 2 hr and slow-cooled. This treatment produced stable grains of average size (defined here by the average linear intercept) of for zirconium and -4xin. (-10 p) for zircaloy-2. The specimens were tested in a dead load tensile creep rig. The stress was maintained constant by adjusting the applied load after approximately each 1 pct of strain. The specimen temperature was controlled to better than +1°C. This system had a small thermal lag, so that rapid temperature changes were possible. To minimize corrosion, the specimens were tested in high-purity (99.95 pct) argon, further dried,

Jan 1, 1968

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,&apos;&apos;&apos; who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

No records have been found of coal in the old Spanish documents, although some mention of it probably exists in manuscripts. Coal was found in Mt. Diablo, in Contra Costa County, about five miles south of the San Joaquin River in 1852, but the first mine, the Teutonia, was located in 1858. The deposits are located on both sides of a high ridge, and vessels of 1,000 tons burden could ascend the river to the nearest point to the mines.1 In 1854, coal was found about four miles from Oroville, on the Feather River, in Butte County. Development work was started and in 1856 a mine was opened. From the description the coal was likely a variety of lignite and probably never amounted to anything commercially, as it does not appear again in the records 2 The more valuable mines at Mt. Diablo were opened in 1859 and 1860. By 1867 there had been 11 mines started and at that time five were in operation. The seam conditions were much disturbed and lack of knowledge of them caused much waste of effort and money. All of the coal excepting that used locally and in nearby towns, was shipped to San Francisco, and largely used for steam purposes. The first receipts were in 1861-6,620 tons. A railroad to the river had been constructed and opened in February 1866. The Corral Hollow field in Alameda County was found and prospected to a small extent in 1862. Two mines were opened but little work was done and the field was then abandoned. Good exposures were rare and the cost of underground exploration was then prohibitive. The Commercial mine produced coal in 1869 and 1870, but a fire in the latter year destroyed the tipple and communications to the mine. The Livermore mine was abandoned after 18 months operation in 1875 and 1876 and no other work was done here until the nineties. In 1867 Hyne reported the presence of coal in workable thickness, and of good quality, on the property of the Pacific Coast Petroleum Company,

Jan 1, 1942

By K. T. Aust

The relative interfacial energies of symmetrical tilt boundaries in silver of greater than 99.999 pct purity were measured as a function of orientation difference 0 between 9° and 36° about <001>. The results are in good agreement with the dislocation model of the grain boundary. The energy vs H curve may be represented by the Shockley and Read equation in the form Eoe (0.55—In 8). READ&apos; has indicated that an ideal experimental method of testing the predictions of the dislocation theory of the grain boundary would be to measure the interfacial energies of symmetrical tilt boundaries between face-centered-cubic grains that have a common <001> axis, as a function of orientation difference 0. The misfit H should be defined by a rotation of each grain through an angle of H/2 away from the boundary. Such boundaries might be expected, from geometrical considerations, to be made up of a series of edge dislocations, at least for small values of 0. Energy vs H relationships for tin&apos; and lead:&apos; were previously obtained for an asymmetrical tilt boundary separating two grains in which generally only one grain was rotated about a <001> specimen axis through an angle of H away from the boundary, the other grain remaining fixed. It is possible, however, that the boundary atoms in tin and lead may have attained a symmetrical position, in relation to the orientations of the grains on either side of the boundary, during equilibrium annealing. The two sets of measurements on silicon ferrite&apos; were somewhat better suited for comparison with theory, since the boundaries were symmetrical tilt boundaries in which the axis of relative rotation was <110> in the first series and <l00> in the second; but this alloy has a body-centered-cubic structure. Although the grain boundaries in silver" were symmetrically tilted, the axis of relative rotation was not a simple crystallographic direction, and it varied from boundary to boundary. Although the above measurements were in good agreement with the Shockley and Read equation,"&apos;: it appeared desirable to carry out experiments under the ideal conditions specified by Read.&apos; Consequently, the relative energies of symmetrical tilt boundaries in silver between grains that have a common <001> axis were measured. The technique of equilibrating grain boundaries in oriented tricrystals was used rather than the less satisfactory thermal groove method previously employed for silver bicrystals." Experimental Details and Observations The solidification and seeding techniques, described previouslyh for growing tricrystals of controlled orientations, were used to prepare tricrystal specimens from silver of greater than 99.999 pct purity. The silver was obtained from American Platinum Works, Newark, N. J., in the form of poly crystalline rods 10 cm long and 7 mm in diam. These rods were then cold worked by rolling or drawing them into suitably shaped blanks. Single crystal seeds and tricrystals were grown in a high purity graphite boat by means of a movable furnace with globar heating elements. The graphite boat was enclosed in a Vycor tube, which was first evacuated to about l00/u Hg and then filled with a static argon atmosphere. The maximum temperature outside the Vycor tube was 1250°C. A typical tricrystal specimen of silver is shown in Fig. 1. Grains B and C were grown from seed crystals with a <001> specimen axis or longitudinal direction parallel to the direction of growth and with another <001> direction perpendicular to the surface. Each of the two seed crystals was rotated 18" about the <001> specimen axis but in opposite directions away from the boundary. A symmetrical tilt boundary, therefore, separated grains B and C with an orientation difference 8 of 36" about <001>. Grain A in Fig. 1 was grown from the middle seed with a <110> direction parallel to the specimen axis and with a <001> direction inclined at 45&apos; to the surface of the specimen. The interfaces sepa-

Jan 1, 1957

By G. B. Craig, H. E. Rosinger, W. J. Bratina

NUMEROUS studies have been reported on how the mechanical properties of a bcc metal are affected by interstitial solute atoms in the temperature range where appreciable diffusion occurs in finite time. Only recently, though, has work on an "interstitial-free" iron been reported, this by Leslie and sober,&apos; on an Fe-0.15 pct Ti alloy. The data was limited to a maximum temperature of 296°K. This work presents a systematic study of the flow stress and the activation volume of a similar material as a function of plastic deformation over the temperature range 253" to 473°K. The material studied was Ferrovac E iron containing 0.01 wt pct C and 0.0002 wt pct N annealed at 870°C for 1 hr, and the same iron with an addition of 0.15 wt pct Ti annealed at 870°C for 80 hr; cooling rates being 75°C per hr. In the latter alloy depletion of interstitials in the a-iron matrix associated with the second phase formation was expected. The temperature dependence of the flow stress was measured at 6 = 3.33 x 10-5 sec-1 from 253" to 473°K as a function of the deformation in 0.01 intervals from 0.03 to 0.12 strain. Results for two strains, 0.03 and 0.09 are shown in Fig. 1. The flow stress increased and reached a maximum in the Ferrovac E iron with increasing temperature, but showed a consistent gradual decrease in the Ferrovac E-0.15 pct Ti alloy. A yield point and Luders region, observed in Ferrovac E, was absent in the Ferrovac E-0.15 pct Ti alloy. Also, the Ferrovac E exhibited a serrated stress-strain behavior in the temperature range 330" to 400°K; dynamic strain-aging characteristics were absent for the titanium alloy. The activation volume was determined over the same temperature range by the method of stress relaxation at constant strain. Results are shown in Fig. 2. At the temperatures of serrated stress-strain behavior in Ferrovac E the activation volume was found to increase toward infinity and, as the temperature rose, to decrease, to about 100 to 200 v/b3. By contrast, the activation volume for the Ferrovac E-0.15 pct Ti alloy tended to increase continuously from the initial value of approximately 300 at 300°K to more than 800 at 473°K. Above 400°K, then, the corresponding activation volume values of Ferrovac E were less than that of the Ferrovac E-0.15 pct Ti alloy. The activation volumes, Fig. 2, appear to depend on dislocation-interstitial interaction in Ferrovac E and on dislocation-dislocation interaction in Ferrovac E-0.15 pct Ti alloy. The gradual increase in the latter metal is associated with thermally activated motion of dislocation segments.&apos; The decrease of the activation volume in Ferrovac E above 400°K is probably related to the diminishing effect of interstitials on dislocations. Here, the interstitials can be moved along with a dislocation without appreciable drag. As indicated in Fig. 1, removal of interstitials

Jan 1, 1970

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano&apos; on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager&apos; in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.&apos; The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano&apos;s result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl&apos;s points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By H. D. Kessler, M. Hansen, R. J. Van Thyne

The phase diagram of the titanium-rich portion of the system Ti-Cr-Fe to 70 pct Ti was established by means of isothermal sections at 900°, 800°, 750°, 700°, 650°, 600°, and 550°C, using arc-cast alloys. An isotherm at 800°C was determined for the section bounded by Ti, TiFe2, and TiCr2. Micrographic analysis was employed as the principal method of investigation, supplemented by X-ray diffraction and incipient melting studies. A ternary eutectoid, ß ? a+ TiCr2 + TiFe, occurs at approximately 8 wt pct Cr, 13 wt pct Fe, and about 540°C. AMONG the first titanium-base alloys in commercial production were the Ti-Cr-Fe alloys. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the system. No information on the constitution of the titanium-rich corner was available. Vogel and Wenderott studied titanium-poor ternary alloys.&apos; As part of this program, the binary systems Ti-Cr and Ti-Fe have been determined previously by the authors.&apos; Other investigators have also studied the binary systems Ti-Cr,3-7&apos; Ti-Fe.³,8-10 Both of the binary systems are characterized by the eutectoid decomposition of the ß phase. Most of the effort of the present work has been concentrated on the titanium-rich corner with compositions of less than 30 pct total chromium and iron content. The determination of isothermal sections was the experimental approach used to obtain the ternary phase diagram. Vertical sections were used to check the consistency of the isothermal sections. While this investigation was in progress, a study of the Ti-Mo-Cr system at Armour Research Foundation disclosed the existence of a high temperature modification of TiCr2 above 1300 °C.11 This allotrope has a hexagonal structure of the MgZn2 type, iso-morphous with TiFe2, whereas the low temperature modification of TiCr2 is cubic," of the MgCu2 type. The existence of allotropy in TiCr2 of course means a more complicated set of phase relationships in this general region than if the phase were monomorphic, as was first assumed. Additional studies were made late in the investigation in order to clarify the part that the hexagonal TiCr2 phase plays in the ternary phase relationships. These will be discussed in a separate section. Because they are of greatest practical significance, the phase relationships in the titanium-rich corner will be presented first, omitting the equilibria involving the hexagonal modification of TiCr2 in an effort to simplify the presentation somewhat. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9 pct pure) produced by the New Jersey Zinc Co. High purity chromium and iron were obtained from the National Research Corp. Table I gives the analyses of these materials. Melting Practice: Over 100 alloy ingots weighing 10 to 20 g were melted in a nonconsumable electrode arc-melting furnace. As the techniques are identical to those reported previously,12,13 they will not be detailed here. The ingots were melted in the cavity of a copper melting block insert under a slight positive pressure of helium. No measurable hardness

Jan 1, 1954