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By R. I. Jaffee, H. P. Nielsen

In recent years much attention has been given to high melting alloy systems. It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. Past Work Miillerl determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from I771 C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Miiller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and Jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at I000 C. Vines and WiseS report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. Materials The platinum powder used in this work was kindly supplied by the Research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio. It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HC1. The resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1949

By J. W. Spretnak, V. Kandarpa, G. W. Powell, R. A. Erickson

Neutron-diffraction pattens were obtained at room temperature from two austenitic manganese steels, oxc wth n carbon content of 1.23 zct PC/ and the olher 0.63 wt pct. Analysis of the data showed that the curOan atols (ions) occupy tile octaheadral site. any of the cavbon is in the tetahedral site, tile concentration is too strzall lo be detecled by tzeulr-on d$facton. AS part of a long-range investigation of eutectoid decomposition, a study of the structure of austenite has been undertaken in order to characterize as best as possible the parent phase in the Fe-C system. Austenite is a solid solution of carbon atoms in fcc iron, the carbon atoms being located in interstitial positions. Of the two kinds of interstitial sites, octahedral (0, +, +) and tetrahedral (4, a, $), in this lattice, the larger octahedral sites are usually considered as the probable position of carbon. The strain energy involved in pytting a neutral carbon atom (covalent di; ameter 1.54)' into a tetrahedral site (diameter 0.56A) is considerably greater than that associated with p2tting carbon into the octahedral site (diameter 1.08A). Dayal and arkeen' observed the migration of carbon in iron under the influence of an electric field indicating tha tye carbon is ionized. pe ionic radius of C'4 is 0.15A and that of C" is 0.29. Consequently, it is conceivable that carbon ions could occupy the tetrahedral sites if one considers only the strain energy. Size considerations alone do not provide a complete explanation for the formation of the interstitial solid solutions, however. because metals such as copper, zinc, and cadmium do not appear to form interstitial solid solutions in spite of their large interstitial sites. Evidence which suggests partial ioni-zation of the carbon in austenite has also been obtained by Speiser, Spretnak, and alor who derived formu- lae relating the observed change in lattice parameter to the effective diameter of the solute atom. Assuming the carbon occupies the octahedral site. they computed the effective diameter of carbon to be 1.33A whereas the covalent diameter is 1.54A. petch5 concluded from powder X-ray diffraction experiments that carbon atoms occupy the octahedral sites. His conclusion was based on the general trend observed in the intensity of the diffraction lines as the carbon content of the austenite was increased. However, the major difficulty associated with application of X-ray diffraction to this particular problem is the relatively poor scattering power of carbon. Williamson and smallman' utilized X-ray diffraction to study the line broadening caused by the strain field about carbon atoms inferrite: these investigators concluded that at least 85 pct of the carbon in ferrite occupies the octahedral (0: 3, B) site rather than the larger

Jan 1, 1967

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By Herluf P. Nielsen, Robert I. Jaffee

IN recent years much attention has been given to high-melting alloy systems, It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. PAST WORK Müller1 determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from 1771°C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Müller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at 1000°C. Vines and Wise3 report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. MATERIALS The platinum powder used in this work was kindly supplied by the research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio, It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HCI. the resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1948

By J. L. Lamont, W. Crafts

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By H. L. Couch, J. D. Lubahn

In decarburized mild steel, the strain hardening arising from 1/2 pct strain can he partly recovered by subsequent heating, even though re crystallization or grain growth does not occur. This recovery varies from 5 pct in an hour at room temperature to 70 pct at 800°C. The variation with temperature was qualitatively similar to that reported for copper, but occurred at lower temperatures. Except for the initial portion (Bazdschinger effect), the stress-strain curve following recovery can be superimposed on the original curve by shifting it to the left. In other words, the tensile behavior is essentially the same after straining and heating as if there had been less strain and no heating. The importance of this observation in understanding simultaneous deformation and recouery is explained. AN earlier investigation1 on copper showed that strengthening due to strain hardening was augmented by heating at moderate temperatures, but was diminished by heating at higher temperatures, Fig. 1. Auxiliary experiments1 indicated that recovery and strain aging are independent processes, which may proceed simultaneously, and whose effects are additive as indicated in Fig. 1. In order to study recovery by itself, similar tests were made on decarburized mild steel, where strain-aging effects are known2 to be absent. MATERIAL, TESTING PROCEDURE The specimens were made from rimmed, hot-rolled SAE 1020 steel 0.040 in. thick, by stamping out rectangular blanks and end holes, Fig. 2, and pack milling the reduced section. These were wet-hydrogen treated2 for 16 hr at 720°C to remove carbon and nitrogen completely and then heated 1 hr at 850°C in vacuum to stabilize the grain size. Auxiliary ex- periments showed that heating up to 800°C will not cause grain growth. They were prestrained 5 to 7.5 mils per in. using the special grips shown in Fig. 2. Such small strains are less than the "critical" strain for recrystallization and, therefore, will not cause recrystallization, even at high temperature. The recovery treatment after prestraining and before the retesting consisted of heating for 1 hr in wet hydrogen at the desired temperature. In one test, Huggenberger gages were used to define more accurately the loading and unloading curves. Fig. 3 illustrates the creep during the early stages of unloading, the hysteresis due to cold stretching, and removal of hysteresis by heating.3 RESULTS The load-deflection curves had ratner widely differing shapes for different specimens, both before and after the recovery treatment. Some specimens showed perfectly smooth curves, Fig. 4, while others exhibited an inflection more or less suggestive of a yield point (Fig. 4 shows all extreme case). Some curves were much steeper than others; Fig. 5 shows two extremes. Some additional ex-

Jan 1, 1960

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By W. E. Horst

Flotation feed was hell constant for batch laboratory tests and continuous pilot and commercial plant tests on a spodumene ore to determine the relation.ship between flotation behavior and the size and type of flotation machine. Results. showed that additional retention time would be needed in the plant flotation circuit to duplicate laboratory or pilot plant performance when operating Dariables of the. plant flotation machines remained unchanged. During the past few years of operation at Kings Mountain, N. C., full-scale flotation has generally yielded poorer metallurgical results than those obtained in the laboratory or pilot plant. After 2 min in each size of Denver flotation machine in the spodumene rougher circuit, pilot recovery (41.7 pct) was almost three times that of the plant (13.6 pct) and about twice that of the laboratory (21.0 pct). Pilot and commercial plant data are based on continuous operation, and laboratory results on batch testing of rougher performance. The ore is a pegmatite containing spodumene, feldspar, quartz, mica, and amphibolite. Data were accumulated to evaluate the scale-up relationships between laboratory, pilot plant, and plant flotation cells. Flotation rate constants and dimensional analysis were used to define the relationship existing between flotation behavior and scale of operation. Measuring Flotation Rates: Efficiency of the rougher stage was measured by flotation rate, defined as the recovery that can be attained within a given time." • The problem of measuring flotation rates has been studied by many investigators, whose methods have varied. Published studies an flotation kinetics have been summarized recently by Gaudin.l When comparing flotation rates, it is more satisfactory to compare straight line relationships between recovery and flotation time than exponential curves resulting from plotting cumulative recovery vs cumulative flotation time. To convert the exponential curves into straight line relationships, rate equations were applied similar to those used in chemical kinetics to study the velocity of chemical reactions. Two rate equations have been used in this investigation to measure efficiency of the various cells: 1.5 order Rate Equation dR/dt=k (A-R)1.0 [Eq.1] Second Order Rate Equation dR ---- - K(A - R)2 [Eq. 2] dt Upon integration Eq. 1 becomes 1/(A-R)1/2=k/2 t+1/A1/2 [Eq. 3] and Eq 2 becomes: or fEq. 4] t/R=1/A2K+t/A [Eq. 4] where R = cumulative recovery [percent recovery of total value (spodumene) in flotation feed]. A = initial concentration, pct (100 pct of mineral to be separated). t = flotation time (minutes). k = flotation rate constant for 1.5 order rate equation [units: 1/(percent) 0.5 (min)1. K = flotation rate constant for second order rate equation [units: 1/(percent) (min) 1.

Jan 1, 1959

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By D. O. Hobson, J. O. Stiegler, C. J. McHargue

The effects of alloy composition, deformation temperature, heal treatment, ad inlerstilial contamination on the occurrence of deformation twins were studied. The twinning transition temperature varied with composition and was a maximuni of 140°C for the 40 pcl V composition. Tire remperature range of the transition was very narrow. Alloys of 20 to 70 pet V could he cold-rolled and exhibited profuse twinning. The alloys which did not twin at room temperature (10, 80, and 90 pel V) could plot be cold-rolled. Oxygen additions systematically lowered the transition temperatures for all vanadium contents. The transition temperature for a 30 pet V alloy increased with annealing temperature, apparently due to changes in dislocation density and configuration. Twinning did not nucleate fracture in any specimen in the 20 to 60 pet V composition range. THERE is great current interest in the refractory metals and alloys as structural materials. An important factor in considering the ductile-brittle behavior of such materials is the role of mechanical twinning as a deformation mechanism. Mechanical twins have been observed after deformation at low temperatures or at high loading rates in the pure metals iron,1 vanadium,2,3 columbium,4,5 tantalum,6 Chromium,7 molybdenum,8 and tungsten.9 Binary alloys in which mechanical twins have been observed include: iron with silicon,10 phosphorous," or aluminum;12 and chromium, molybdenum, or tungsten with rhenium.13-17 The increase in low-temperature ductility obtained by alloying the Group VI-A elements with rhenium is very important with regard to fabricability, and there has been considerable effort to understand the so-called '(rhenium effect". Factors suggested to explain this effect include:'' 1) increase in solubility of interstitial impurities with alloying (electronic effect): 2) changes in the nature of grain boundary phases; 3) changes in interfacial energies of grain boundaries and stacking faults: and 4) promotion of twinning. Although an outstanding characteristic of these alloys is the profuse twinning that accompanies low-temperature deformation, most studies of the rhenium effect have been concerned with the other factors. During recent studies of refractory-metal alloys, it was noted that solid solutions of columbium and vanadium exhibited high hardness and strength at room temperature and elevated temperature and, surprisingly, also showed considerable ductility at room temperature and below. These alloys deformed by twinning at room temperature when subjected to slow loading rates. It appeared that the low-temperature ductility resulted at least in part from the relaxation of stresses by twinning in a system where slip is difficult. The reason for enhanced twinning behavior in some bee solid-solution alloys is unknown. There have been suggestions18,19 that, as in fee alloys, the

Jan 1, 1965

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By H. Kreye, E. Hornbogen

An increase in electrical resistivity during aging or after quenching from high temperatures is known in a large number of alloys. Plastic deformation of alloys in this condition leads to a decrease in resistivity. This anomaly has been called the K effect. This effect has been reported in Ni-A1 alloys by several authors.'-4 The nickel-rich solid solution y is in equilibrium with Ni,A1 (y') with CkAu structure. With this alloy it is therefore possible to produce a homogeneous solid solution as well as a coherent mixture of y and y. The changes in resistivity should be determined for these two conditions. In the present literature on the K effect no distinction is made between them, because of experimental difficulties to determine small coherent particles. In the present work transmission electron microscopy and image formation by (100) and (110) superlattice reflection of the y' phase was employed for a detailed determination of the temperature dependence of solubility of aluminum in nickel and the resulting microstructures with alloys up to 15 at. pct Al. The solubility line follows the equation indicating a smaller solubility than given in the literature at temperatures below 700°C. X-ray scattering was used to get evidence for short-range ordering in the homogeneous solid solutions.5 Parallel to the determination of the microstructure electrical resistivity was measured as a function of aging tempera- ture, time, and aluminum content, which led to the following results: 1) Resistivity increases slightly during aging of a homogeneous solid solution which was quenched from a high temperature as a consequence of short-range order, Fig. 1, curve c,. 2) Resistivity shows a maximum during aging of all alloys which are heterogeneous according to the phase diagram, but which were obtained as a supersaturated solid solution by quenching, Fig. 1, curve c,. The increase in resistivity is mainly due to coherent precipitation of y'. In Fig. 2 the effects due to short-range order pN and due to precipitation of particles APT are shown for an aging temperature of 450°C and different aluminum contents. 3) The increase in resistivity depends on the size !f the coherent particles. A critical diameter of 15 5A for the maximum was found for all alloys and aging treatments by extrapolating particle sizes determined by electron microscopy. 4) The maximum of resistivity of the heterogeneous conditions does not occur if particles, larger than the critical size, have formed already during quenching. 5) Plastic deformation destroys short-range order as well as small coherent particles. Therefore a decrease in resistivity is observed if the increase in resistivity caused originally by these phenomena is

Jan 1, 1967

By W. L. Fink, L. A. Willey

DURING the war there was introduced a new higher strength aircraft alloy designated 75S.1,2.3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75S alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75S alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. PROCEDURE Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75S "as rolled" sheet (0.064 in. thick). The composition° was as follows: Weight Percentage Cu Mn Mg Zn Cr Al with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16 in. i.d. by ¼ -in. o.d. by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064 in. thickness over the junction and adjacent lead wires for a distance of 1 ½ in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3 in. by 9 in. by 0.064 in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75S extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of ¾ in., 2 in., 3 in. and 4 in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 ½ in. Thermocouples were peened into the bottoms of 1/8 in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1947

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943