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By W. P. Sykes

In connection with a study of tungsten steels, Honda and Murakamil reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. Materials The iron powder used in preparing the alloys was obtained as follows : Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000" C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 per cent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon. The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly for several days at temperatures up to 1500' C. and for shorter periods

Jan 1, 1926

By Robert S. Williams

NO new ferrous alloys have been produced in the last five or six years that are as outstanding contributions to civilization as were the high-speed steels of the early part of the century or the stainless steels announced at the close of the World War. There have been, however, many developments of major importance having to do either with modifications of existing alloys or with new methods of treatment of older iron or steel alloys. Only a limited number of these new developments can be discussed and their selection does not necessarily imply that these are the most important but merely that they are of general interest rather than perhaps of greater importance in highly specialized fields.

Jan 1, 1939

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.&apos;, &apos; Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,&apos; are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By Terkel Rosenqvist

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann&apos;s finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author&apos;s reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp p/RT, where p is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf&apos;s can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,&apos; the revised activity coefficient of silicon

Jan 1, 1965

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.&apos; Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,&apos; over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann&apos; calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7&apos;8 on the oxygen activities in these melts.

Jan 1, 1962

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By John Chipman

HE lecture on &apos;Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.&apos;,B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By J. S. Marsh

OPPORTUNITY to pay tribute to the memory of Professor Henry Marion Howe is a strenuous assignment as well as an honor. Upon recalling Howe lecturers and lectures of the past 25 years, glancing over the list of those earlier, and rereading Howe&apos;s books, I arrive at several conclusions: 1—Many lecturers either worked under or knew Professor Howe. 2—It is virtually impossible to pick a subject on which Professor Howe did not touch. 3—There is precedent for a technical paper based upon pursuit of a single subject. 4—There have been listening lectures and reading lectures. There is solid comfort only in 2: the subject field is wide open. I did not know, nor even ever saw, Professor Howe, so can supply no fitting reminiscence. As a college student I was dimly aware that he counted among the giants. Fuller appreciation of his stature came with reading his books and papers, growing acquaintance with some of his associates, and the intrinsic dignity of the climax of the Annual Meeting, beginning at four o&apos;clock of a Thursday afternoon in the auditorium of the Engineering Societies Building in New York. As for producing the technical paper sort of thing, it is my lot to have reached an age and assignment such that to do so would be to filch information from those who did the work and whose story is theirs to tell; for this I have no enthusiasm. As for the final conclusion, Professor Howe was one of the chosen few so highly expert at expository writing that he could produce a lecture or paper that reads as though it would also have listened well. One of his tricks was the free use of words not ordinarily part of the technical vocabulary, provided that such words were likely to communicate most precisely what he had in mind. How wonderful it would be for all who must read reports by the ton if ability at exposition could be taught with the effectiveness open, say to, differential calculus! Perhaps Professor Howe should be required college reading even if for no other reason than to prove that technical writing need be neither dull nor diffuse. My assignment is clearly still strenuous. Another point to consider is the fact that metallurgy is now so tremendously diversified that hope of finding a topic of universal appeal is negligible, even if one were competent enough to be permitted free choice. That which follows is, therefore, a compromise composed of necessity and of the obligation to attempt to avoid boring to slumber those of you who are not especially interested in the general subject chosen. The Iron and Steel Div. is now essentially a process metallurgy division, heavily concerned with the smelting of iron and the making of steel. The American Iron and Steel Inst. figure for present steel capacity of this country is 125,828,310 net tons; how this is divided among processes is indicated by the production totals for 1953, shown in Table I. The glamor girls and boys make the front page and so it is with steelmaking processes. If there is an Antarctic Daily Bugle, it undoubtedly has carried stories of revolutionary development, such as oxygen processes and vacuum melting, and stories of the incomparably rosy destiny of electric arc melting. All such certainly have their place and their future; meanwhile, it is the sturdy and old reliable open hearth that accounts for the bulk of production reported back on the financial page, and it is the old reliable that is most likely to continue to account for the bulk for some perfectly sound raw material, technologic, and economic reasons. This, plus the fact that next year marks a centennial (for it was in 1856 that Frederick and William Siemens conceived the regenerative open hearth), is reason enough to talk about open hearth furnaces, but is not the real one. The real reason is that in some years of association with open hearths, I have accumulated—in addition to a genuine liking and respect for them—certain odds and ends of fact and fancy that this lecture provides a unique chance

Jan 1, 1956

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73&apos;22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526&apos; to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,&apos; Herasymenko,&apos; and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen&apos; concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work&apos; on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm&apos; sec-&apos;. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3&apos; has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By A. U. Seybolt

A. U. Seybolt (General Electric Research Laboratory)— As pointed out in an earlier paper,41 it appears to be very difficult to nucleate Si3N4 in Si-Fe of silicon content up to around 5 pet. Therefore, one observes, as did Pearce, that equilibrations with nitrogen gas yield only nitrogen in solid solution at temperatures above about 700°C, or, as Pearce found, 770°C. Evidently, the free energy of formation of Si3N4 only becomes high enough at -770°C to overcome the reluctance of Si3N4 to nucleate. However, as mentioned in Ref. 41, if some Si3N4 is first formed by a mixture of ammonia and hydrogen, one can then replace this gas mixture by nitrogen gas, and either increase or decrease the amount of Si3N4 present at any temperature by suitable adjustment of nitrogen pressure: that is, to equilibrate with Si3N4. In the equilibration experiments cited in Ref. 41, equilibrium was approached from both sides, and it was found that samples up to 944oC, at least, were in equilibrium with Si3N4. Higher temperatures were not employed, as this would have necessitated a redesign of the apparatus for using nitrogen pressures in excess of 1 atm. To summarize, the results of Pearce&apos;s experiments and those of Ref. 41 cannot be directly compared because two quite different equilibria were studied. Therefore, the statement by Pearce on p. 1398 indicating apparent error in Ref. 41 is unjustified. M. L. Pearce (author&apos;s reply)— There was limited evidence obtained in the current investigation which would indicate that excessive "supercooling" did not occur. A small piece of the same resulting from heat treatment No. 5 in Table III was subsequently held at 800°C for 16 hr in 95 pet N-5 pet H. Isotope-

Jan 1, 1964