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By W. O. Philbrook, A. H. Jolly, T. R. Henry

In the course of a study of slag-control methods, the authors devised a laboratory technique by which the basicity of basic open-hearth furnace slags could be estimated with sufficient accuracy to make the method of possible interest for slag-control purposes. The process consisted of measuring the slight basicity of an extract of the powdered slag in water. The procedure was presented, for the benefit of those who might care to experiment with it, in a paper submitted in the 1944 McKune Award Contest and presented at the 1944 Open-hearth Conference in Pittsburgh.' Interest expressed at that meeting and favorable operating experience with the method at a neighboring plant, as described in a related paper by Michael Tenenbaum and C. C. Brown,; have encouraged us to present further details of the development, technique, and pitfalls of the method and some additional data not included in our first report. At the outset it must be admitted that this method of estimation of slag basicity is not perfect; neither is any other that we know of. It is subject to somewhat greater errors than would be desirable, but compares favorably with other techniques in this respect. It has the disadvantage that it places the final determination of slag basicity in the hands of a laboratory technician rather than the furnace oper- ator, although it can be operated in a control laboratory adjacent to the furnaces. It requires close attention to certain details, as do most laboratory procedures. On the favorable side, it eliminates the "human factor" of personal judgment inherent in estimation from pancakes or powdered samples. The procedure can be placed in practice much more rapidly and presents much less of a training problem than visual methods of estimation. The principle and operation of the method are so simple that it would not be surprising if others have experimented with the same or similar procedures, but we are not aware of any prior publication of details. Our own shop has been operating fairly successfully for several years with the aid of slag pancakes. Since the past year or two have not been favorable for the expenditure of time and energy where the need was not urgent, we have not introduced the new practice for actual slag control and hence do not have extensive operating data. In presenting this method, therefore, we make no claims as to theoretical justification nor guarantees as to practical applicability, but offer it as an empirical observation. We believe it has sufficient merit to warrant its investigation by those just instituting a slag-control program or in search of supplementary methods for judging slag basicity Principle of the Method It is well known that when burnt lime or slaked lime is shaken up with water it

Jan 1, 1945

By Elwood G. Haney, R. N. Parkins

Stress corrosion cracking of two heats of 18 pct Ni maraging steel in rod form immersed in an aqueous solution of 0.6N NaCl at pH 2.2 has been studied on un-notched specimens stressed in a hard tensilf machite. Austenitizing temperature in the range 1830 to 1400 F has been shown to have a marked influence on the propensity to crack, the loulest austenitizing- temperature producing the greatest resistance to failure. In the nzosl susceptible conditions, the cracks followed the original austenile grain boundaries; but when tlze steels zcere heal treated to inproze their resistance to stress corrosion, the cracks becatne appreciably less branched and slzouqed significant tendencies to become trans granular. Electron metallography of the steels indicated the presence of snzall particles, possibly of titanium carbide, along- the prior austenite grain boundaries and these particles u:ere more readily detectable in the structures that were most susceptible to cracking. Crack propagation rates, which appeared to be dependent upon applied stress and structure, were usually in tlze reg-ion of 0.5 mm per hr and may, therefore, be e.xplained on tlze basis of a purely electrochetnical ,nechanism. However, there is some ezliderzce from fractography that crack extension may be assisted by ttlechanical processes. Anodic stit)zulation reduced the tiwe to fracture, although cathodic currents of small magnitudes delayed cracking-; further increase in cathodic current resulted in a sharp drop i,n fracture litne, possibly due to the onset of hydrogen ewbrittlement. THE use of the high strength maraging steels, with their attractive fracture toughness characteristics, is restricted because of their susceptibility to stress corrosion cracking in chloride solutions. Although this limitation has resulted in investigations of the stress corrosion susceptibilities of these steels, there have been few systematic studies aimed at defining the various parameters that determine the level of susceptibility. It is the case that the usual tests have been performed with the object of defining some stress or time limit, on unnotched or precracked specimens, within which failure was not observed,' but while such results may be of some use in design considerations, they are necessarily concerned only with the steels as they currently exist and not with their improvement to render them more resistant to stress corrosion failure. This omission may be considered unfortunate because the indications are that stress corrosion in maraging steels shows dependence on structure in following an intergranular path, and since experience with other systems of intergranular stress corrosion crack- ing is that susceptibility may be varied by modifying heat treatments, a similar effect may be expected with maraging steels. It is sometimes from such observations that a fuller understanding of the mechanism of stress corrosion crack propagation begins to emerge, leading in time to the development of more resistant grades of material. The present work was undertaken to study only one aspect of the influence of heat treatment upon the cracking propensities of the 18 pct Ni maraging steel, namely the effect of austenitizing temperature, although certain ancillary measurements and experiments have been undertaken. EXPERIMENTAL TECHNIQUES Most of the measurements were made on a steel, A, having the analysis shown below, although a few results were obtained on a steel, B, having a slightly different composition. Both steels were supplied in the austenitized condition, A as 3/8-in-diam rod and B as 1/2-in.-diam rod. Cylindrical tensile test pieces were machined from the rods: the overal length was 2 1/2 in., the gage length 1 in. and the diameter 0.128 to 0.136 in. The stress corrosion tests were carried out with the specimens strained in tension in a hard beam testing machine, the necessary total strain being applied to the specimen over a period of about 30 sec, after which the moving crosshead was locked in position and the load allowed to relax as crack propagation proceeded; the load relaxation was recorded. The load was applied after the specimen had been brought into contact with the corrosive solution, the latter being contained in a polyethylene dish having a central hole through which the specimen passed, leakage being prevented by the application of a film of rubber cement. The specimen was in contact with the solution for over half of its gage length and the solution was exposed to the air during testing. The solution was prepared from distilled and deionized water to which NaCl was added, 0.6N, and the pH adjusted to 2.2 by HCl additions. The composition of the solution

Jan 1, 1969

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.&apos; More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.&apos; This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,&apos; or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough &apos;0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough &apos;0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By L. M. Cathles, H. R. Spedden, E. E. Malouf

Fluid flow through an igneous rock formation will occur mainly through fractures. A non-diffusing or slowly diffusing tracer (such as .5µ silica spheres identifiable under electron microscope) will arrive at a monitor well when enough fluid has been injected to displace the volume of water in the flow fractures between the injection and monitor wells. A rapidly diffusing tracer (such as NaC1)-will diffuse into the matrix blocks and so a volume of tracer nearly equal to the total fluid volume contained in the rock formation between injection and monitor wells must be injected before significant diffusing tracer arrival will be noted. The flow fracture porosity is typically one hundred times smaller than the total porosity of an igneous formation. The shift between diffusing and non diffusing tracer arrivals, together with the diffusional characteristics of the tracers, can define the diffusional accessibility of the matrix blocks of an igneous formation. A field test of these concepts and the problems encountered will be described.

Jan 1, 1974

By J. D. Rice, P. L. Wearden, W. L. Hensou

Solutions to the unsteady-state partial water-drive reservoir performance problem can be obtained through the use of analogue computers or high-speed electronic digital computers. The solutions that have previously been resolved for use on digital computers, however, demand a knowledge of the aquifer parameters. Generally, the analogue computers now in use do not require this knowledge. A solution is presented herein where the aquifer performance, expressed in terms of difference equations, is related to the reservoir performance as expressed by the modified Scbiltbuis material-balance equation. A numerical procedure for a medium-sized digital computer also is presented in which a solution to the set of equations defining the aquifer and reservoir performance is obtained and the aquifer parameters (permeability and sand thickness) are automatically optimized while simultaneously matching the known pressure behavior. Predicted pressure behavior can be calculated using rates from any assumed future production practice. The procedure provides an output format which presents the cumulative, incremental and average rate of natural water influx, the per cent gas-cap expansion, the calculated reservoir pressure, the measured reservoir pressure, and the difference between the measured and calculated pressures. Results of a test problem are presented in comparison with results obtained by the Bruce Analyzer, Ohio Oil Co. &apos;s Pace General Purpose Analogue Computer, and Sun Oil Co.&apos;s Single-Pool Electronic Reservoir Analyzer. These results indicate that unsteady-state reservoir perlormance for a single-pool system can be adequately simulated by a numerical method employing a digital computer and that the special-purpose analogue computer can be supplanted by this method. INTRODUCTION The numerical approach to the unsteady-state partial water-drive reservoir performance problem heretofore has been limited in that solutions have been resolved only for certain fixed parameters. Also, prior to the advent of high-speed electronic digital computers in the last few years, calculations were so tedious and time-consuming that they ordinarily were neglected, or some other means of obtaining the solutions were used. The analogue approach had been used for obtaining solutions to the transmission-of-heat problem and, consequently, means were developed for applying the electrical analogue to the unsteady-state reservoir performance problem. Bruce submitted a paper for AIME publication in Sept. 1942, in which he described an electronic device (now called the Bruce Analyzer) for analyzing the water-drive performance of any reservoir, based on either steady or unsteady-state flow characteristics. 1 Sun Oil Co. adopted the analogue approach in 1949 and now has two special-purpose high-speed electronic reservoir analyzers in use.2,3 Two main features of Sun&apos;s analyzers are (1) the high repetitive rate of reproducing the entire history of reservoir performance cyclically a number of times per second, and (2) the elimination of the necessity of knowing the properties of the associated aquifer. Since the advent of larger and faster digital computers, the possibility of incorporating this second feature into a numerical approach appeared feasible. Previous work has been done and material published covering the application of numerical methods to the behavior of the pressure with respect to time at any point in an associated aquifer? However, the aquifer parameters must be known from some source. The material presented in Ref. 4 has been used to a great degree in developing the numerical method described herein. DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS The problem of simulating the performance of a reservoir and the associated aquifer is to determine the characteristics of the aquifer such that the

By Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (d) of the liquid-to-solid transfer at each temperature has been derived: d = ZLXL(XL - P) + Zsxs(P- ZL(XL - P) + Zs(P - Xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, XL and xs are the composi-tions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under considera-tion. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d -versus-temperature curves for two alloys Pl and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid FIG. I.-GENERAL SOLID SOLUTION DIAGRAM SHOWING S CURVES FOR ALLOYS P1 AND P2. phase only at the temperature of the be-ginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate tem-perature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1940

By G. Willard Quick

TENSILE tests of rail steels at elevated temperatures&apos;&apos; have shown that certain rails, in addition to having low ductility in the well-known bluebrittle range in the neighborhood of 200° C., have marked reduction in elongation and reduction of area in the temperature range from 400° to 700° C. This range of low ductility was called "the secondary brittle range" and the phenomenon, "secondary brittleness." The question naturally arises as to whether this property of the steels would be shown by impact tests performed in the same range of temperature. If so, the impact test, as suggested by Gillett3 would be a simpler and quicker method for the routine examination of steels at elevated temperature than the tensile test. A number of investigators have reported results of impact tests on steels at elevated temperatures, in which the energy absorbed decreased with increase of temperature above 200° or 300° C. Langenberg4 performed Charpy impact tests on several steels at temperatures ranging from room temperature up to 1000° F. (538° C). His results showed an increase in the energy absorbed in specimens tested in the range from room temperature to 200° or 300° C. and then a gradual decrease in the range, 300° to 538° C., the maximum temperature used. Greaves and Jones5

Jan 1, 1932

By C. S. Barrett, O. R. Trautz

Previous investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air.1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4.5 has remarked that the low value of the elastic modulus (C11 — Cl2)/z of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. The Nature of the Transformations Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in theLi-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig -I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete—an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1949

By Arthur F. Taggart, Herbert H. Kellogg, Nathaniel Arbiter

The experimental work herein described is presented in support of the following broad hypothesis: Conditioning of metals and metallic sulphides by amine collectors involves metathetic reaction at the solid surface between the collector and an oxidized metallic compound, to produce a coating comprising an amine-bearing compound of low solubility in the system. The type of reaction is different in acid and in basic solutions; both types may occur simultaneously in near-neutral pulps. Experimental The experiments comprise contact-angle tests with a variety of metals and metallic sulphides and extraction teats on ground chalcocite. Contact-angle tests were made principally on metals. Covellite paralleled metallic copper in amine solution at pH 8.8 (Table 3) and in alkaline water, but maintained an angle of about 70° in Io-3 HCl solution, where metallic copper lost its angle. The tests with anionic collectors (Table I) indicate that the behavior of metals in general is parallel to that of their minerals in anionic solutions. It is believed that this is generally true with cationic collectors also, but the covellite test is a warning against a broad assumption to this effect. All test specimens were mounted in Transoptic.* All tests in conditioning solution were preceded by a test in distilled water; cleaning and polishing were continued in every case until the angle in water was zero. Subsequent transfers into and out of solutions and test cells were made in such a way as to prevent exposure of the surface to air.1 The amine used was primary laurylamine, Armour and Co., AM-1120. It was used in the form of the hydrochloride, obtained by precipitation with gaseous hydrochloric acid from an ether solution of the amine, and purified by two recrystallizations from ether-alcoho1.2 Inorganic and other test reagents were standard laboratory grades. Temperatures were not controlled; the probable range of test-solution temperatures is 650 to 80°F.

Jan 1, 1943

By Herbert H. Kellogg, Nathaniel Arbiter, Arthur F. Taggart

The experimental work herein described is presented in support of the following broad hypothesis: Conditioning of metals and metallic sulphides by amine collectors involves metathetic reaction at the solid surface between the collector and an oxidized metallic compound, to produce a coating comprising an amine-bearing compound of low solubility in the system. The type of reaction is different in acid and in basic solutions; both types may occur simultaneously in near-neutral pulps. Experimental The experiments comprise contact-angle tests with a variety of metals and metallic sulphides and extraction teats on ground chalcocite. Contact-angle tests were made principally on metals. Covellite paralleled metallic copper in amine solution at pH 8.8 (Table 3) and in alkaline water, but maintained an angle of about 70° in Io-3 HCl solution, where metallic copper lost its angle. The tests with anionic collectors (Table I) indicate that the behavior of metals in general is parallel to that of their minerals in anionic solutions. It is believed that this is generally true with cationic collectors also, but the covellite test is a warning against a broad assumption to this effect. All test specimens were mounted in Transoptic.* All tests in conditioning solution were preceded by a test in distilled water; cleaning and polishing were continued in every case until the angle in water was zero. Subsequent transfers into and out of solutions and test cells were made in such a way as to prevent exposure of the surface to air.1 The amine used was primary laurylamine, Armour and Co., AM-1120. It was used in the form of the hydrochloride, obtained by precipitation with gaseous hydrochloric acid from an ether solution of the amine, and purified by two recrystallizations from ether-alcoho1.2 Inorganic and other test reagents were standard laboratory grades. Temperatures were not controlled; the probable range of test-solution temperatures is 650 to 80°F.

Jan 1, 1943

By J. H. Wernick, J. E. Kunzler

HIGHLY pure metals are needed for low-temperature electron transport studies in progress. Recent improvements in purification techniques, such as zone refining, have made it possible to obtain metals with improved purity. For some metals, the improvement has been to the extent that ordinary analytical techniques are inadequate and special methods are needed.1 For other metals purification is more difficult, so that simple but rapid analytical methods are desirable as an aid in evaluating the effectiveness of purification procedures. Furthermore, it is desirable to be able to determine the impurity level of the sample or ingot with the minimum of physical disturbance of the material. In order to aid in the preparation of purer metals, techniques involving the measurement of electrical resistance at liquid-helium temperatures have been devised for studying impurity distributions in zone-refined ingots and other bulk samples without destroying the ingot or its geometry. The method yields information on the variations in purity along the length of the ingot or sample and provides a measure of the overall purity of the material. Compared with ordinary analytical methods, the resistivity method is rapid, sensitive, and does not require significant physical disturbance of samples with reasonable shapes. It has the disadvantage that resistance measurements are not specific, i.e., they do not identify the impurity. However, this disadvantage is offset by the advantage of being able to establish a measure of the overall purity so far as electrically active" impurities are concerned. METHOD AND ITS BASIS The method is based on the well-known fact that the resistivity, at Liquid helium temperatures, of a reasonably pure metal containing no regions with additional phases decreases with increasing chemical purity or a decrease in the number of physical defects. It is convenient to separate the total resistivity into three parts: where is the resistivity due to the scattering of the conduction electrons by the lattice vibrations or phonons, p is the contribution due to physical defects, and originates from the effect of chemical impurities in the metal. Insofar as Matthiessen&apos;s rule is obeyed,2 pphys and pchem are independent of temperature. Except possiblyin the very purest metals, ptherm is negligible at liquid helium temperatures and For zone-refined metals, which normally are well annealed and consist of large grains, at the chemical purity levels thus far attained the available data indicate that pphys is negligibly small or at least constant throughout the ingot. Assuming that the effect of physical defects is negligible for isotropic metals, This assumption appears consistent with most of

Jan 1, 1959

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark&apos;s papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark&apos;s papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.&apos; The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,&apos; the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By M. J. Pool, P. J. Spencer

Using liquid tin as the solvent metal, the heats of solution of silver and gold in dilute Ag-Au-Sn alloys have been determined at 723°K by solution calorimetry. From the values obtained, the various enthalpy interaction coefficients in the liquid solutions have been calculated. The self-interaction coefficients Au and Ag values of 2413 and -6322 cal per g-atom in binary Au-Sn and Ag-Sn alloys, respectively. For an alloy containing 0.04 mole fraction Ag, Au is equal to 2443 cal per g-atom, and in an alloy containing 0.04 mole fraction Au, Ag has a value of —8883 cal per g-atom. Ag Au has been determined as —2650 cal per g-atom. ADDITION of a second solute to a dilute binary alloy may cause striking changes in the thermodynamic characteristics of the alloy. As yet, such influences cannot be reliably predicted and it is only by accumulation and critical assessment of data that definite patterns can be established. Solute interactions in dilute solutions were first treated mathematically by Wagner,1 who derived expressions for the Gibbs energy interaction coefficients. For an alloy consisting of. two dilute solutes, i and j, in a solvent s, these coefficients are given by: where yi is the activity coefficient of component i and x represents the mole fraction of solute or solvent. Other interaction coefficients have since been established in terms of the various partial molar thermodynamic properties of an alloy; the definitions of these are summarized in a recent paper by Lupis and Elliott.2 Mathematical and experimental studies of such coefficients have received much attention recently, providing a very useful theoretical background to an understanding of the nature of solute interactions taking place in dilute solutions. One of the definitions to arise from such work has been the extension of Wagner&apos;s treatment by Lupis and Elliott4 to include an enthalpy interaction coefficient, defined as. where ?Hi is the relative partial molar enthalpy of component i. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hio, and to the enthalpy interaction coefficients by the expression: Values of ?Hi can often be obtained with a high degree of accuracy by calorimetry, and, if the composition of the alloy is carefully controlled by making calculated solute additions throughout a series of measurements, application of Eq. [2] will enable reliable enthalpy interaction coefficients to be determined. Partial heats of solution must be investigated as a function of solute concentrations down to xi = 0, and, since ? values are obtained from the slope of mi plotted against x, great care must be taken to obtain precise data. The data for binary systems which are presently available often require extrapolation of ?Hi values from compositions as great as xi = 0.05 or even 0.1 to obtain limiting heats of solution. Reliable enthalpy interaction coefficients are thus impossible to obtain from published data for most of the alloy systems already investigated. The aim of the present work was to determine values of Au, Ag, Ag, and Au in the limit xsn -1 for the relatively simple Ag-Au-Sn system and from these results to gain some insight into the possible influence

Jan 1, 1969

By M. R. J. Wyllie

In a recent publication1 wetting phase relative permeability was exvressed as: and it was stated that a similar expression applied, mutatis mutandis, to non-wetting phase relative permeability; i.e., In Equations (1) and (2), Sw and S0 are respectively the wetting and non-wetting phase saturations as a fraction of the pore volume; PC is the capillary pressure; I; the wetting phase electrical resistivity index; IN, the analogous non-wetting

Jan 1, 1951

By M. R. J. Wyllie

In a recent publication1 wetting phase relative permeability was exvressed as: and it was stated that a similar expression applied, mutatis mutandis, to non-wetting phase relative permeability; i.e., In Equations (1) and (2), Sw and S0 are respectively the wetting and non-wetting phase saturations as a fraction of the pore volume; PC is the capillary pressure; I; the wetting phase electrical resistivity index; IN, the analogous non-wetting

Jan 1, 1951