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By A. S. Richardson

THe conditions that make necessary the mechanical ventilation of the Butte mines of the Anaconda Copper Mining Go. are due to a number of causes, all of which are incidental to the depth at which mining operations are now carried on, The main object to be accomplished, of course, is the reduction of the temperature and humidity of the air in the working places. Ventilation fans, both surface and underground, have been used for many years, but increasing depth has made the problem much more difficult. Further improvement in both ventilation equipment and methods, therefore, became necessary; and it is the purpose of this paper to describe the work planned and done under the improvement program. The mines of the district have been frequently described in various technical publications, so a description is unnecessary here. From a mine-ventilation viewpoint, compared with coal-mine ventilation systems, the problem is complicated by the fact that the workings to be ventilated are situated on a large number of steeply dipping veins which frequently intersect and are faulted, and also by the fact that the extent, or existence, of orebodies is not definitely known in advance of actual development work. For these reasons ventilation work cannot be planned in advance of actual operations, nor can such regular systems of ventilation as are used in working the more uniform and continuous bodies of coal be developed. When operations are conducted at a normal rate, about 10,000 miners are employed on two shifts, so that about 5000 men will be underground at one time. But as ventilation is necessary to reduce high temperature and humidity due, mainly, to natural causes, the quantity of air per man per minute is not a governing consideration in determining ventilation requirements. Most important among the numerous sources of heat and humidity in the mines are: heat generated during decay of mine timber; heat and humidity given off by mine rock and water; heat generated by oxidation of sulfide minerals; heat given off by electrical equipment; heat generated by mine fires (in certain localities).

Jan 1, 1923

By Giovanni Barla, Stefan H. Boshkov

This paper examines the application of gelatin mixture models to the study of factors such as gravity effects, tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space. The technique of calibrating gelatin mixtures proposed by Richards and Mark in 1966 is applied to the particular problem considered. Similitude relationships between model and prototype are discussed with reference to the constitutive equations describing the physical behavior of the rock mass. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example with the view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The prediction of the displacement, stress field and mode of fracture associated with a given rock structure, its initial stress field, and its physical properties is essential to rock mechanics and ground control. The basic approach is to assume the rock mass to behave as a continuous, homogeneous, and isotropic medium. The classical theory of elasticity is the simplest theory based on such a concept. Specification of the elastic constants, the initial state of stress in the ground, and the boundary conditions on stress and displacement allows one to predict stress and displacement within the body. Subsequently, provided that a criterion which governs rock fracture under various stress conditions has been established, a stability analysis of the rock structure can be performed. A natural extension of the present knowledge consists of removing some of the simplifying assumptions which characterize the analytical solutions based on the classical theory of elasticity. Complex geometry, the significance of tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space are some of the important factors which are neglected in the classical approach. A better insight into the real problem can be attained with either the finite element method of stress analysis or an experimental technique. The former has already been applied with success on several occasion 1-4 and is destined to render great service in the field of rock mechanics and ground control. The latter, which will be considered in this paper, has been used extensively in applications too numerous to be enumerated. Experimental technique involves either prototype testing, if the area to be studied is accessible, or model testing. Two- and three-dimensional photo-elastic analyses are very convenient means of obtaining the stress distribution in models of complex geometry. In general, such analyses are confined to studies of stress fields around openings which are sufficiently far removed from the surface boundary so that the stresses in their neighborhood are practically equal to those produced by an initial uniform stress field; i.e., so that gravitational effects are negligible. There are, however, many rock structures where these effects must be taken into account to attain a more realistic representation of the problem. Surface and near surface rock structures, systems of openings interacting with one another, and structural components loaded only by their own weight are some of the obvious examples. This paper was written to show how factors neglected in the usual analysis based on the classical theory of elasticity, can be taken into account when gelatin mixture models are used inconjunction with photoelastic methods. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example, with a view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The birefringence of gelatin mixtures has been known for some time. A series of experiments were carried out by Rossi in 1910,5 but after that very

Jan 1, 1970

By A. C. Heath, E. H. Dix

The importance of aluminum-silicon alloys in thc light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and likc silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminurn and alurninum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. Part I.—Aluminum-silicon Alloys The early work on this system was largely confined to determining the general form of thc diagram and in this respect the results are in good agreement. Briefly, alulninunl and silicon form a simple eutectifcrous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Ipraenkell (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solu-t'ion. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility docs not appear

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400'F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y' precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y' precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10' to 10' cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975'F for 4 hr.

Jan 1, 1970

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.' The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By T. F. Baily

DURING the period of the War, in both this country and Canada, a number of attempts were made to make pig iron from steel scrap in the FIG. 1.-EXPERIMENTAL FURNACE. 5000 KW. CAPACITY: 150 TONS 2 PER CENT. SILICON PIG IRON PER DAY. electric furnace, and a considerable tonnage of white pig iron was produced, the silicon and manganese additions being made with ferroalloys; but it is believed that the experiments conducted at Canton, Ohio, in

Jan 1, 1930

By Cyril Stanley Smith

Although alloys of copper and silicon were examined several years ago,' and their excellent mechanical properties were shown, it was not until C. B. Jacobs 2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. Review of Previous WORK on the BinaRy Systems There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described," which indicate that there is a change in solubility with temperature. Copper-silicon System The copper-silicon system has been studied in detail by the author and is described in two papers published in 1928.V he portion of the diagram up to 8 per cent. silicon, as determined by this research, is reproduced in Fig. 1. The author's previous papers include a complete review of the work of other investigators and it is not necessary to deal further with this system here. Copper-manganese System The copper-manganese system has been investigated by several workers, notably Lewis,5 Wologdine,6 Sahmen7 and Schemtschuschny,

Jan 1, 1930

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By Harry A. Wahl

Precent fracture design procedures are bared on the total fracture area created. A method to distinguish beI,,.ecn total area and [he propped or effective fracture area has not been available. This paper presents a solution to this problem, applicable to horizontal fractures. The difierences between effective fracture area and torn] area are demonstrared in example calculations. This work is hayed on experimentally determined transport efficiencier of solids in sand-liquid slurries. Newtonian and non-Ne~vtoninn systems are considered. INTRODUCTION Fifteen years after commercial introduction, hydraulic fracturing remains the most successful stimulation technique in the oil field. This success is primarily due to ability of induced fractures to penetrate and alter permeabilities deep within formations. Many fields producing today could not have been developed without the hydraulic fracturing process. Because of wide usage, fracture-treatment design has received a great deal of engineering and research effort. This work, resulting in improved equipment and materials, has increased the benefits from fracture treatments as well as the applicability of the process. A major contribution was the development of fluid-loss additives. Necessarily, the number of parameters to be considered in treatment design has steadily increased, resulting in more complicated design techniques. Almost all present design procedures are based on the precepts set forth by Howard and Fast. Relating the fluid volume lost into the formation, the volume required in extending the fracture, and the total slurry volume injected, they developed an expression for the total fracture area created in terms of pertinent treatment parameters. Fluid loss during treatment was expressed as a function of time for three flow mechanisms. Although modifications of fluid loss equations have been made, the total fracture area concept has remained unaltered. A vast amount of field data indicate that induced fractures must be propped and held open to be effective. A notable exception is the Mesa Verde formation in the San Juan basin. However, analysis of these treatments shows that improved well productivities are obtained when propping agents are incorporated in the treating fluid. Although propped fracture area has been recognized as an important design parameter, a method to distinguish between total area and effective fracture area has not been available. The necessary information on slurry-sand transport in fractures has been lacking. Interest in the propped region of induced fractures is not restricted to areal extent alone. The distribution of sand within fractures is important from the standpoint of fracture flow capacities. Flow capacity affects the increase in well productivity after stimulation. The work of Huitt and Darin4 hows that partial monolayers of sand have large flow capacities compared to thick* dense sand packs. It has been postulated that gelled fluids have the ability to transport sand within the fractures at the deired low concentrations. An early contribution in the area of sand placement in fractures was made by Kern et al.' They studied sand movement in a transparent vertical fracture model. It was observed that the sand tended to settle out in the bottom of the model before moving very far. When the fluid velocity exceeded a certain critical value, all of the sand injected began moving through the crack even though it settled to the bottom. This critical velocity was determined under several flow conditions. Some work on sand movement in horizontal fractures has been reported in Russian publications. Sand movement was studied by Izyumova and Shan'gin' using a transparent "pie-shaped" flow model to simulate a horizontal radial flow system. However, the data were limited, especially in a quantitative sense. Dorozhkin, Zheltov and Zheltow studied the behavior of sand-liquid slurries in a horizontal linear flow model. The quantitative data were restricted primarily to the thickness of sand deposits formed at the bottom of the fracture. An earlier paper provided basic data on the flow of sand in horizontal fractures. This study was designed to yield specific quantitative information on rate of advance of sand particles and pressure behavior under various flow conditions. A comprehensive photographic study was undertaken in a 10-ft windowed flow cell to provide the necessary qualitative and quantitative data. Since the number of potential variables far exceeded the capacity of the initial study, emphasis was placed on the effects of sand concentration, oil viscosity and oil flow rate. A detailed description of these experiments and the results are described in Ref. 9. However. the implications of this work on the fracture design calculations were not discussed. An analysis of these data as well as new data is provided in the following sections. EXPERIMENTAL RESULTS The primary objective of the experimental investigation was to provide information on the rate of advance of the solids in sand-liquid sturries. A 10%-ft long transparent

Jan 1, 1966

By Eckley B. Coxe

Having been appointed, on February 19th, 1890, a member of the Commission created by the Legislature of Pennsylvania for the purpose of investigating the " Waste of Coal Mining, with the View to the Utilizing of the Waste" (waste in this case referring specially to the small sizes of anthracite heretofore thrown away), my attention was naturally directed to the mash economical method of burning these small sizes.* Although I had been Familiar with the burning of anthracite for • many years, I found when I came to study the matter carefully that I was far from thoroughly understanding it, particularly with reference to the hurning of the smaller sizes, and that the literature of the subject, which was not very extensive, had more of a tendency to confuse than to enlighten me. I began therefore to investigate the subject so as to arrive if possible at some definite principles applicable to the question. With the aid of my assistant, Mr. John R. Wagner, I began at Drifton a series of experiments upon the burning of small anthracites. We first erected a small furnace with a grate 3 feet long and 2 feet wide, with which we experimented about two months. From the information thus acquired, we designed and built another furnace of about the same size, which gave us facilities for extending our investigations still further. After experimenting several months with the second furnace, we built a third one, which was much larger, having a grate area of about 68 square feet, which was exactly the size of the grate used in the boiler-plants of' Coxe Bros. &

Jan 1, 1894

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.' Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By M. Baeyertr

Since 1915 many papers and books have covered industrial applications of X-rays from various angles. Two of the more recent are a paper by Fink and Archer, which describes in detail the technique of radiography, and a paper by Clark2, which embraces the whole field of X-ray metallogmphy. This paper, therefore, is confined to work of the X-ray Laboratory of the Western Electric Co., which naturally divides into two categories: radiography and diffraction patterns of various types. Radiography Radiography is the field in which the application of X-rays has had most general appeal among the industries which produce or use metals and alloys. Equipment permitting the examination of heavy sections of metals less permeable than aluminum or other light alloys requires apparatus capable of generating hard X-rays over a considerable period of time. The equipment used in the work presented in this paper is practically identical with that described by Fink and Archer in their paper on radiography in industry and is easily capable of penetrating 1/8 in. of lead. Radiography is used in two major groups of problems: (1) in the development of cquipment and tools and (2) in studies of materials. So far there has been no instance in which the use of radiography for routine inspection is justified. This is partly due to the fact that the manufacture of telephone apparatus involves the production of many identical parts by standardized procedures and equipment that has had development and trial before being put on a regular production basis. It is during this stage of development of equipment and tools that radiography has been used to particular advantage.

Jan 1, 1931

By A. S. Richardson

THe conditions that make necessary the mechanical ventilation of the Butte mines of the Anaconda Copper Mining Go. are due to a number of causes, all of which are incidental to the depth at which mining operations are now carried on, The main object to be accomplished, of course, is the reduction of the temperature and humidity of the air in the working places. Ventilation fans, both surface and underground, have been used for many years, but increasing depth has made the problem much more difficult. Further improvement in both ventilation equipment and methods, therefore, became necessary; and it is the purpose of this paper to describe the work planned and done under the improvement program. The mines of the district have been frequently described in various technical publications, so a description is unnecessary here. From a mine-ventilation viewpoint, compared with coal-mine ventilation systems, the problem is complicated by the fact that the workings to be ventilated are situated on a large number of steeply dipping veins which frequently intersect and are faulted, and also by the fact that the extent, or existence, of orebodies is not definitely known in advance of actual development work. For these reasons ventilation work cannot be planned in advance of actual operations, nor can such regular systems of ventilation as are used in working the more uniform and continuous bodies of coal be developed. When operations are conducted at a normal rate, about 10,000 miners are employed on two shifts, so that about 5000 men will be underground at one time. But as ventilation is necessary to reduce high temperature and humidity due, mainly, to natural causes, the quantity of air per man per minute is not a governing consideration in determining ventilation requirements. Most important among the numerous sources of heat and humidity in the mines are: heat generated during decay of mine timber; heat and humidity given off by mine rock and water; heat generated by oxidation of sulfide minerals; heat given off by electrical equipment; heat generated by mine fires (in certain localities).

Jan 1, 1923

By I. R. Kramer

The effect of the specimen diameter, d, on the flow stress, cra of polycrystalline aluminunz (99.997) was studied. The increase in the flow stress could be accountedfor by the increase in the surface layer stress, with decreasing specimen diameter. Both , and a, were found to be proportional to For the smaller-dianzeter specimen (< 0.033 in.) at strains less than aboul 0.1, the work hardening of the surface layer was greater than that associated with the bulk of the specimen. At higher strains the work hardening due to the bulk appears to be independent of the specimen diameter. THE increase in the strength of metals with decreasing diameter is well-known; however, an adequate explanation for the cause of the size effect is still lacking. The earliest systematic investigation of size effect appears to be that of Onol who reported that for aluminum monocrystals the resistance to slip at low strains increased as the specimen diameter decreased. A change in the stress-strain curve beyond 0.001 strain was not found. However, Suzuki et a1 .&apos; reported for monocrystals of a brass and copper having diameters in the range of 2 to 0.12 mm that the entire stress-strain curve was raised as the specimen diameter was decreased. The effect of size was most apparent when the diameter of the specimen was less than 0.5 mm. In the discussion of this paper Honey-combe reported a size effect in copper crystals as large as % in. diam. These results are in agreement with those of paterson3 and Garstone et al.4 While the majority of the investigations on size effects was conducted in terms of the variation in the diameter of the specimen, several investigators studied the influence of the specimen geometry. For example, Wu and smoluchowski 5 reported that in aluminum monocrystals the slip system was a function of the specimen dimension in the slip direction. King-man and Green 6 studied the influence of size on the compressive stress-strain relationship of aluminum monocrystals when the ratio of length to diameter was constant. Their specimen diameters ranged from to & in. For specimens oriented for single slip the critical resolved shear stress for the smaller-size specimens increased with decreasing diameter. No effect was observed in the large-size specimens. Specimens having an orientation near the corners of the stereographic triangle did not exhibit a size effect. Apparently, the increase in strength with decrease in the diameter of the specimen is a general phenomenon and has been observed in a brass |T and cadmium as well as in aluminum and copper.&apos; In a series of investigations (for example Ref. lo), it was shown that during deformation a surface layer was formed which imposes a back stress, a,, on the moving dislocations. It is reasonable to predict that this surface layer stress, as, should be a function of the specimen diameter and could possibly account for the flow stress size effect. In fact, experimental evidence will be presented to show that this is the case; i.e., the increase in flow stress with decreasing size is equal to the increase in the surface layer stress, as, with size. In addition, data will be presented on the variation with size of and a* where is the back stress associated with the generation of dislocation obstacles in the bulk of the specimen and a* is the net effective stress acting on the mobile dislocations. A limited investigation was carried out on gold specimens to determine the influence of an oxide film. EXPERIMENTAL PROCEDURE The aluminum specimens were prepared from -in. bar stock (99.997 pct purity). The 0.350- and 0.150-in.-diam specimens were machined directly from the bars while the specimens having a diameter of 0.033, 0.020, and 0.015 in. were prepared by swaging and drawing to 0.04 in. and electropolishing almost to final size. The specimens were prepared with a 2-in. gage length. The specimens were annealed in vacuum (-10-4 Torr) at 350°C for 8 hr. The grain diameter of the specimens in the various specimen diameter groups was 0.08 ± 0.02 mm. Gold specimens of two diameters, 0.14 and 0.03 in., were prepared in a similar way and annealed at 650°C for 8 hr. The grain diameter of the gold specimens was 0.2 mm. After annealing the specimens were electrochemically polished to the final size and tested in an Instron tensile machine at a strain rate, E&apos;, of 10- 3 per min. While it was possible to determine the surface layer stress, a,, in the larger-size specimens by measuring the difference, Aa, between the stress before unloading the specimens and the initial flow stress after removal of the surface layer as outlined in detail in Ref. 10, this method is not applicable for small wires because of the difficulty in obtaining a sufficiently accurate measure of the diameter. The values at the various strains were therefore determined by measuring after the specimen had been annealed at 35°C for 4 hr. It has previously been shown" that the two methods give the same results for a provided that the annealing temperature is low enough to affect only the surface layer and not the dislocation barriers in the bulk of the specimen. For the gold specimens a treatment at 150°C for 16 hr was found to be satisfactory for the determination of by the low-temperature annealing method. EXPERIMENTAL RESULTS Determination of a,, and a,. The stress-strain curves for the various diameter aluminum specimens, plotted in terms of the logarithms of the true stress, and true strain, are given in Fig. 1. These curves represent the average data taken from at least ten specimens at each size. Over the range of strains investigated the curves follow the empirical equation

Jan 1, 1968

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,&apos; obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson&apos;s data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle&apos;s data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By J. B. Cohen, S. L. Sass

The nucleation process for y&apos;, Ni3Ti, is shou&apos;n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y&apos; may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.&apos; For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y&apos; forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."&apos;5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y&apos; or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine&apos;" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y&apos; may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y&apos;. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker&apos; suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y&apos; acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y&apos; is thought to be responsible.&apos; At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.&apos;" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y&apos; and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970