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By Strathmore R. B. Cooke, Marcus Digre

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,12'3 and the method has been applied to the concentration of various iron ores4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Advantages are that a direct value for the amount of calcium adsorbed is obtained, and introduction of a collector which may affect the adsorption is avoided. The difficulty is to determine the extremely small differences in the calcium concentrations before and after the abstraction. The second method was to determine the activation of the quartz by observing the contact angle obtained on pressing an air bubble against the polished surface of a piece of quartz immersed in a solution of calcium chloride, sodium hydroxide, and sodium oleate. This is the well-known "contact angle" method. The third method was to determine those conditions under which an air bubble will pick up quartz particles immersed in a solution of the desired reagents. Disadvantages common to the sec- ond and third methods are that introduction of a collector is necessary to obtain bubble contact with the mineral; very small quantities of contaminant can give erroneous results; and no information is obtainable concerning the amount of calcium adsorbed. Advantages are that tedious analyses, which at best give approximate results, are avoided, and the conditions, especially for the third method, closely simulate those of actual flotation. Although the most consistent results were obtained with the third method, this paper describes the techniques used and the results obtained from each of the three methods. Distilled water and analytical grade reagents were used throughout except where otherwise stated. Between tests all glass articles were cleaned with a chromic-sulphuric acid mixture and sodium hydroxide. Abstraction Method The raw material for the tests was Ottawa sand sized between 14 and 28 mesh. Batches of 500 g of this sand were dry ground for 1 hr in an Abbe porcelain mill with 2700 g of quartz pebbles. The batches were split down to samples weighing approximately 30 g, and the weight of each sample was adjusted to exactly this value.

Jan 1, 1950

By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

By C. Gatlin, M. E. Chenevert

The effects of bedding plane orientation on the elastic constants and the yield strengths of three laminated rocks (one sandstone and two shales) and one isotropic rock (a limestone) were studied. The directional dependence of the elastic properties of these rocks was experimentally evaluated using a triaxial compression cell and auxiliary stress-strain measuring equipment. Symmetry of Poisson's ratios within the bedding plane suggested that horizontal isotropy exists, but the bedding planes do give rise to an appreciable difference between properties in the horizontal and vertical directions. For the three bedded rocks studied, Young's modulus was lower normal to bedding than along bedding. Yield strengths were determined at confining pressures from 0 to 12,000 psi in a triaxial compression cell. The rocks studied showed strength reductions as high as 40 per cent when the test specimen was oriented at 20°-30° to the bedding planes. The mechanical behavior of these rocks suggested that the rock properties of shear strength and/or coefficient of internal friction can vary with direction, depending on the particular rock tested. Tensile strengths were also measured and found to be lowest when failure occurred along bedding. This work shows that bedded formations exhibit sizable directional variations in both their elastic constants and yield strengths. It is suggested that these variations may be accounted for by using the "elastic laminate" model and the "variable coefficients" failure model. INTRODUCTION The nature of rock deformation at elevated pressures has been studied by many workers; papers by Handin,l,2 and Robinson3 illustrate the present state of knowledge. Most investigators have either chosen rocks which were as isotropic as possible (in order to avoid complications of data interpretation and analysis) or they have oriented their samples so that the effects of anisotropies (such as bedding planes) have been avoided. Of the studies performed, few were concerned specifically with mechanical anisotrop-ies. Griggs4 has presented limited data for specimens cut parallel, normal, and 45° to the bedding plane; he relates the strength anisotropy observed to the fabric (bedding) anisotropy. His tests were primarily concerned with large deformations (20 per cent strain); thus, no directional values of the elastic constants were reported. Handin has reported the results of similar experiments. Bott5has discussed rock strength anisotropies due to faults, cleavage, or bedding. He was concerned primari ly with determining the shear stress on such planes and did not mention the effect of friction. Jaeger6 later generalized Bott's work by taking friction into account and presented a limited theory for the failure of rocks having a "single plane of weakness", and also for rocks having a constant coefficient of friction, and a shear strength which varies with bedding plane orientation. Donath and Cohen,7 and Donathg have evaluated rock strengths from shale and slate specimens cut normal and parallel to bedding. A dependence of cohesive strength (7,) on the specimen orientation was also shown. Adler9 has also studied this problem and lists similar results. He assumes that all bedded rocks behave according to Jaeger's single-plane-of-weakness theory. Kalinin and Belorussov10 list results for strength tests parallel and perpendicular to bedding and use this information as a basis for hole deviation analysis. From the literature it is apparent that sedimentary rocks have been tested under widely varying conditions of stress; however, the assumption of isotropy is generally, but not always, made. Since geologic sedimentation often deposits sediments in very definite lavers.,. it seems that more svstema tic attention should be given to the possible effects of this natural bedding. Bedding, as used here, refers to visible regularities of grain size or orientation resulting from depositional processes. The mechanical strength anisotropies, which bedding may present, is not the only anisotronic property to be considered, since the elastic

Jan 1, 1966

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck's work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck's outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."' We were not however very successful in getting values for Schenck's "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck's work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

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 R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By F. Keller, A. H. Geisler

ALTHOUGH the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstätten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged alloys.1 The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will suffice to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. PREPARATION OF SPECIMENS The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously.1,2 Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen. The specimen is polished according to the usual procedure for microscopic examination.3 The specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended. Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens. The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet polishing operation are generally used, but frequently the as-rolled surface is suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1946

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968

By H. B. Smith, B. Egererg

In a previous paper1 the authors dealt with the physical properties of cold-rolled and heat-treated Britannia metal of the approximate composition Sn, 91 per cent., Sb, 7 per cent. and Cu, 2 per cent. It was found that cold rolling to more than 50 per cent. reduction produced a continuous softening of the metal when measured by the Brinell machine, whereas the Shore instrument indicated increased hardness; that the strength of the material followed the Brinell hardness and that the metal therefore became weaker the more it was cold-rolled; and further, it was found that hardness and strength could be largely restored to the cold-rolled metal by "baking" for about one hour at any temperature between 200" and 450" F., the melting point. The higher the baking temperature, the more effective was the heat treatment as far as increased hardness was concerned. It seemed to be of little importance whether the metal was soaked or not at the baking temperature for a great length of time and the rate of cooling seemed to be immaterial. The present paper deals with the same alloy and more particularly with the resistance towards various forms of stress — tensile, bend and deep drawing. The metallography of Britannia metal has in part also been covered and an explanation attempted for the abnormal behavior of this alloy. Tensile and Bend Tests Two ingots 73/4 in. wide, 11 in. long and ¾ in. thick were cast from the same pot. One ingot was cold-rolled in one direction to a strip 0.241 in. thick, which furnished the tensile test specimens; the other ingot was rolled in the same way to 0.253 in. and furnished the specimens for the bend tests. The ingots were cast as described in the previous paper and cold-rolled in six passes.

Jan 1, 1930

By D. T. Peters, C. R. Cupp

Aging of commercial 18 pct Ni maraging steel and of related binary, ternary, and quaternary alloys has been studied by electrical resistivity, X-ray diffrac-tion, and hardness measurements. The aging process is in three stages: 1) recovery of martensite; 2) two precipitation reactions; 3) formation of nickel- rich austenite. The main objective of this work was to discover the nature of the Co-Mu interaction. Addition of cobalt to the Fe-18 pct Ni-5pct Mo alloy results in acceleration of the pvecipitation reaction by increasing the super-sat~lration 0f molybdenum. The cobalt-containing al- loys show no incubation period for the precipitation reaction, but the alloy without cobalt shows an initial slow reaction. These results are interpreted in terms of precipitation on dislocations. At low aging temperatures, the presence of cobalt leads to the appearance of a second type of precipitate which is a particularly effective hardener. Cobalt was found to retard the formation of austenite. Overaging is a combination of classical overaging and the formation of austenite in the structure. he- activation energy for the precipitation reaction determined from resistivity ,measurements is 42.8 kcal per mole and the growth of the precipitate is found to obey at law at high tenzperatures and a tU3 law at low temperatures. HE mechanism of strengthening of the 18 pct Ni maraging steels has been studied extensively since 1962.'-? The strengthening is due to precipitation hardening of the martensitic matrix. The main precipitate is an inter metallic compound involving molybdenum, but there is disagreement about its identity.

Jan 1, 1967

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By W. Crafts, J. L. Lamont

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. L. Lamont, W. Crafts

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By J. J. Jakosky

All electrical geophysical methods depend for their operation upon the effects produced by the flow of an electric current. By studying these effects it is possible to predict the general axis of current flow. The greater flow of current is in the path of greatest effective conductivity; and since the effective conductivity of a mineralized zone is different from that of its surrounding envelope (usually much greater), it is possible to locate such a mineralized zone by the distribution of current. Due consideration must be given, of course, to geological structure, to type of mineralization, and to other factors. A number of methods are used to cause this flow of current, and various methods arc available for detecting the presence of such current flow and for studying its effects. In a rather detailed way, this paper will discuss the theoretical and practical phases of the inductive methods of geophysical prospecting. Electromagnetic Generation of an Electeomotive Force The inductive method is so named because the current flowing in the conductor is obtained by electromagnetic induction, instead of by the use of ground electrodes through which a current is passed as in the applied potential systems, or by direct contact with the orebody. An alternating current flowing in a coil will create an electromagnetic field around the coil. This field will have the same frequency as the current and will radiate or travel outward from the coil in closed magnetic or flux circuits. These flux circuits (in air or a homogeneous medium) will be perpendicular to the plane of the coil and will extend or travel outward with uniform velocity in every direction. Maximum feld exists in the plane of the coil. Such a coil used for transmitting or as the "energizer" will exhibit similar figure-eight characteristics to those exhibited by the direction-finding coil which will be described in detail later.

Jan 1, 1929

By Larry Kaufman, Morris Cohen

THE solid phase equilibria' and the martensitic transformation in the iron-nickel system have been the subject of considerable study. In addition, there have been numerous investigations on the calorimetric and thermodynamic properties of iron-nickel alloys. The purpose of the present work is to extend the existing information concerning the martensitic reaction in the iron-nickel system, and to develop a general thermodynamic treatment which will encompass the equilibrium and non-equilibrium phase

Jan 1, 1957

By D. J. Jr. McAdam

RESULTS of a general survey of corrosion-fatigue phenomena at the Naval Engineering Experiment Station were presented in five previous papers.1-5 In these papers references were given to the work of Haigh in 1917.6 The five papers mentioned gave a general survey of the behavior of metals when tested to failure under simultaneous corrosion and cyclic stress. As a result of this survey the fourth paper gave a tentative analysis of the corrosion-fatigue process. According to this analysis, if the initial stress is below the endurance limit but above the corrosion-fatigue limit, the corrosion-fatigue process is divided into two periods. The first period is the formation of pits. As the initial stress is below the endurance limit, the pitting is assumed to be due to corrosion, not to fatigue. The corrosion pitting, however, is not the ordinary pitting of stressless corrosion, but is an accelerated pitting due to the effect of the cyclic stress on the corrosion. As the pit progresses, both the actual stress and the effective solution pressure increase. The increase of actual stress is due to increasing stress concentration at the bottoms of the pits. The increase of effective solution pressure is due to the increase of actual stress. The mutual intensification of stress and solution pressure continues until the actual stress at the bottoms of the pits surpasses the endurance limit. The second period of corrosion-fatigue then begins. In this period the process is merely fatigue accelerated by the corrosion. The cracks advance at a continually accelerated rate until the specimen breaks.

Jan 1, 1930

By Harrison Souder

UNDER the stimulus of steadily in- creasing 'demands of the steel industry at home, and with the supply of available ores from abroad appreciably diminished owing to vigorous rearmament campaigns in Europe, production of Eastern magnetite ores reached an all- time peak in 1937. Although the figures given in the accompanying table are partly estimated (actual figures were available for eleven months only), it appears that 1937 production was nearly 47 per cent higher than that of 1936.

Jan 1, 1938

By William E. Ford, Edward Salisbury Dana

A. Anhydrous Carbonates The Anhydrous Carbonates include two distinct isomorphous groups, the CALCITE GROUP and the ARAGONITE GROUP. The metallic elements

Jan 1, 1922