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By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By Eugene P. Pfleider

RECENT interest in germanium centers around its use as a semi-conductor of electricity in electronic devices. It is generally believed that germanium transistors, diodes, triodes, photocells, and rectifiers will largely replace the present-day vacuum tubes. The germanium electronic devices are much smaller, lighter, and more resistant to shock, and they require only a small fraction of current required for conventional devices. Hence only a small amount of heat is given off by the equipment. This development will require many times the quantity of germanium now being produced, which in 1948 was approximately 1000 lb&apos; and was obtained almost entirely from zinc ores in Missouri, Kansas, and Oklahoma. No one knows with certainty what the demand will be for ger-manium by 1956. It may be 40,000 lb.1 Known concentrations in zinc ores are not sufficient to

Jan 1, 1954

By H. S. Choi, I. Iwasaki

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer&apos; stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,2 Mitchell et aL.,3 and particularly Hamilton et al.&apos; have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski&apos;s French Patent No. 847,-215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores. The present article describes comparative results obtained at room temperature and at elevated temperatures by otherwise conventional flotation of iron ores, by single-mineral flotation in the Hallimond tube, and by contact-angle measurements. It is not the purpose of this article to evaluate the commercial feasibility of high-temperature flotation of iron ores, although preliminary calculations show that the cost should not be excessive and that the gains to be realized may well outweigh the extra cost of heating the pulp. LABORATORY FLOTATION TESTS Experimental: All flotation tests reported in this article that use a laboratory Fagergren cell were made on ore A (either containing the primary slimes or deslimed at 20µ as specified) following the preparatory procedures described elsewhere- or this particular ore. Ore A contained hematite, goethite (limonite), quartz, chert, and minor quantities of magnetite. Confirmatory tests made on other ores show that the same general principles apply to ores of similar mineralogy and structure. Conditioning was performed by adding the collector, as a soap, to the vigorously stirred and heated pulp. Conditioning time was 5 min, the pulp contained 60 pct solids, and the equivalent of 0.5 Ib of fatty acid was added per ton of original (unde-slimed) ore. The pH of the pulps ranged from 6.8 to 7.1 (25°C measurement) during conditioning. The pH was adjusted in the flotation cell by addition of either NaOH or H2SO4, the values reported being those of the pulp cooled to 25°C. During conditioning and flotation the pulp temperatures were controlled within l° to 2° by immersion of Variac-controlled Calrod elements in the conditioning beaker and in the cell, and by the use of water, heated to the appropriate temperature, for transferring pulp, adjusting pulp volume, and washing. Selectivity indexes have been calculated on the same basis as those reported in the article by Cooke, Iwasaki, and Choi." Results: Table I gives the results obtained by floating deslimed ore A with pure oleic acid at 25" and 50°C, and Fig. 1 shows the selectivity indexes plotted against pH of flotation. Inspection of Table I

Jan 1, 1961

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By C. S. Smith, L. W. Kempf, C. S. Taylor

The thermal conductivity of aluminum alloys is of considerable industrial importance. This is particularly true in such applications as internal-combustion engines where one of the principal reasons for the use of these alloys is their relatively higher thermal conductivity. In spite of this, relatively few data are available on this property of aluminum alloys. The reason is quite apparent to anyone concerned with the experimental determination of coefficients of thermal conductivity. This determination, in theory so simple, is extraordinarily difficult if any high degree of precision is desired. Fortunately, some .knowledge of the relationship between thermal and electrical conductivity has permitted the use of the latter physical property in deducing the relative approximate values of the thermal conductivities of metals. This fundamental relationship, first enunciated by Wiedemann and Franz&apos; as applying to metallic elements and later shown by Lorenz2 to be applicable to alloys within a single metallic system, has been of service in the industrial application of metals. The electrical conductivity of metals is easily determined with a high degree of precision. It is, therefore, quite desirable that the relationship between electrical and thermal characteristics be determined with the greatest possible precision. This paper presents data on the electrical and thermal conductivities of a number of aluminum alloys of industrial importance. Literature on Thermal Conductivity of Aluminum Alloys Masumoto3 determined the electrical and thermal conductivities of 18 aluminum alloys. His results indicated a relatively constant relationship between thermal and electrical conductivity.

Jan 1, 1937

By John A. Mathews

During the prosecution of the aircraft-production program in 1917 and 1918, the writer visited many plants engaged in the manufacture of motors, planes and parts, in carrying out his duties as chairman of the Committee on Aircraft-engine Forgings. On several occasions, when the question of expansion was discussed, it was noted that there was confusion in the use of the terms: the true coefficient of expansion, a physical constant, and distortion in hardening. One engineer, referring to a steel shown in the accompanying table, stated that he could not consider it for crankshafts because of its excessive coefficient of expansion, while another steel, also Iisted in the table, was said to be especially good because it had no coefficient of expansion, since it came out of the oil bath perfectly straight. Many years ago one of our employees designed a new oil furnace; when asked what became of the products of combustion, he replied: "There ain&apos;t any, we burn them all up." While the coefficient of expansion is not without its effect in volume changes in hardened steel, it is not a determining factor in the matter of distortion and going out of shape. Irregular heating, uneven furnace bottoms, and carelessness in withdrawing the part from the furnace, as well as the manner in which the part enters the quenching bath are of greater moment. Generally speaking, also, steels of relatively low hardening temperature will distort less than those requiring higher hardening heats. The coefficient of expansion must be considered in engineering design most frequently when different metals or alloys are used in the same construction. For example, the difference of expansion between a steel crankshaft and an aluminum crank case might be of real importance and a steel with no coefficient of expansion would be much less desirable than one with the normal coefficient. About 15 years ago, the writer made many determinations of the coefficient of expansion at low temperature ranges, usually between 20&apos; and 100" C. Among the materials tested were: Pure forged electrolytic iron, 11.73 parts per million for l° C.; cast aluminum (99.93 per cent. AI.),

Jan 1, 1922

By John A. Mathews

During the prosecution of the aircraft-production program in 1917 and 1918, the writer visited many plants engaged in the manufacture of motors, planes and parts, in carrying out his duties as chairman of the Committee on Aircraft-engine Forgings. On several occasions, when the question of expansion was discussed, it was noted that there was confusion in the use of the terms: the true coefficient of expansion, a physical constant, and distortion in hardening. One engineer, referring to a steel shown in the accompanying table, stated that he could not consider it for crankshafts because of its excessive coefficient of expansion, while another steel, also Iisted in the table, was said to be especially good because it had no coefficient of expansion, since it came out of the oil bath perfectly straight. Many years ago one of our employees designed a new oil furnace; when asked what became of the products of combustion, he replied: "There ain&apos;t any, we burn them all up." While the coefficient of expansion is not without its effect in volume changes in hardened steel, it is not a determining factor in the matter of distortion and going out of shape. Irregular heating, uneven furnace bottoms, and carelessness in withdrawing the part from the furnace, as well as the manner in which the part enters the quenching bath are of greater moment. Generally speaking, also, steels of relatively low hardening temperature will distort less than those requiring higher hardening heats. The coefficient of expansion must be considered in engineering design most frequently when different metals or alloys are used in the same construction. For example, the difference of expansion between a steel crankshaft and an aluminum crank case might be of real importance and a steel with no coefficient of expansion would be much less desirable than one with the normal coefficient. About 15 years ago, the writer made many determinations of the coefficient of expansion at low temperature ranges, usually between 20&apos; and 100" C. Among the materials tested were: Pure forged electrolytic iron, 11.73 parts per million for l° C.; cast aluminum (99.93 per cent. AI.),

Jan 1, 1922

By R. L. Rickett, N. C. Fick

Despite the large volume of literature on alloys of iron and silicon,&apos; there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By N. C. Fick, R. L. Rickett

Despite the large volume of literature on alloys of iron and silicon,&apos; there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-&apos; mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz&apos; for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.&apos; These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By E. W. Davis

IF the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indica-tions that this new process may make commercially possible the manu-facture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to mag-netite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe304) is easily accomplished by heating the ore to a dull red tempera-ture in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900° F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1936

By Eugene McAuliffe

The term "mechanical mining" carries an ambiguity which justifies a preliminary word of explanation. . All mining activity conducted in this day is more or less mechanical; that is to say, power expressed in the form of electricity, steam or compressed air is used in some portion of practically every mining activity of consequence. "Mechanical loading" is more nearly correct than "mechanical mining" in reference to present practice. The first substantial effort made in the direction of mechanical mining, subsequent to the application of steam for hoisting and underground pumping purposes, was that of substituting for hand labor undercutting and shearing by power-driven machines. The undercutting of coal by hand represented at one time the most arduous task confronting the miner. Occupying a kneeling position in the thicker beds, or lying on his side in the thinner coal, the task was tedious and exhausting. The first attempt to substitute crude air-driven, and later electrically driven, "punchers," as the percussion type of machine was called, met with much the same opposition on the part of the workers as was expressed by workers in the other industries when any innovation, whether labor-saving or otherwise, was introduced. We should not be too critical of this attitude of mind shown by the mine workers. The peculiarly isolated character of the work carried on in semidarkness by a class of men who to a large extent lived and held themselves aloof from the other branches of society led long ago to the development of a craft consciousness which they have found difficult to surrender. It was not until 1891 that a definite record of the results obtained by the use of undercutting machines of all types was made available, the quantity undercut in that year totaling 6,211,732 tons of bituminous coal from all American mines. The volume of bituminous coal undercut by machines in 1928 totaled 369,687,007 tons, or 73.8 per cent. of the nation&apos;s production. In the light of this experience, we can properly feel that the work of introducing the coal-loading machine as a substitute for hand shoveling is making substantial progress.

Jan 1, 1931

THE Geophysics Education Committee has devoted several years to a consideration of the problem of training geophysicists. Past reports have dealt largely with fact finding and with the discussion of particular aspects of geophysical education. In the present report it is proposed to review the subject more comprehensively. This involves the question of what educational qualifications the geophysicist of the highest professional standards should possess, and the related question of what changes must be effected in existing educational institutions in order that prospective professional geophysicists may obtain instruction of the desired quality. The type of geophysicist here contemplated is one familiar with what is known already in the several branches of earth physics, and capable not only of following contemporary progress in any of these branches, but of contributing to that progress in a research capacity. Geophysics in its broadest sense, as has been emphasized repeatedly by this Committee, is the study of the physics of the earth and of terrestrial processes. This includes both the static and the dynamic characteristics of the gaseous, the liquid, and the solid portions of the earth, as well as its gravitational, thermal, and magnetic and electrical manifestations. Some branches of earth physics have been cultivated but slightly; others have reached an advanced state of development. Those branches whose development is sufficient to warrant explicit recognition in the form of organized Sections of the American Geophysical Union are: geodesy, seismology, tectonophysics, and volcanology, dealing with the rock constituents of the earth; oceanography and hydrology with the aqueous constituents; meteorology with the atmospheric constituents; and terrestrial electricity and magnetism with the electromagnetic manifestations. At present, instruction on the professional level in any of these branches of earth physics can be obtained in but few universities in North America. In most institutions where such instruction is undertaken different subjects are given in different and independent departments. Geodesy and hydrology are taught, if at all, as a part of civil engineering. The nearest approach to volcanology and tectonophysics ordinarily is represented by petrology and structural geology given

Jan 1, 1944

By D. G. Westlake, E. S. Fisher

The habit planes for zirconium hydride precipitation in crystals of a zirconium have been determined at various hydrogen concentrations. The (10 • 0)planes are the predominant habit planes; some (10 • 5) and (10 -1) planes were observed after charging conditions which pevmitted formation of a surface layer of hydride. No platelets zrlere observed parallel to any of the twinning planes. Mechanisms for em-brittlement due to hydride precipitation are discussed. LANGERON and Lehr1 found, in 1956, that zirconium hydride precipitates in zirconium in platelets lying parallel to (10.0) slip planes. In 1960, Kunz and Bibbz reported observing the platelets in three different families of twinning planes, (10.2) {11.1), and {11.2), but never in the slip planes. The present study was undertaken to ascertain the cause of these seemingly contradictory results. EXPERIMENTAL Two specimens of iodide zirconium were used in the experiments. Specimen I was a single crystal, while specimen II contained three grains. Grain growth was accomplished by the technique of Lange-ron and Lehr. Three faces were ground on specimen I; the first was 2 deg from the (00.1) basal plane, a second was 2 deg from the (10.0) prism plane, and a third was 4 deg from the (12.0) plane. One face was ground on specimen II such that the poles of the surfaces of crystals A, B, and C were as shown in Fig. 1. After the faces were ground on 600 grit silicon carbide paper, they were chemically polished by dipping in a solution of 8 parts hydrofluoric acid, 50 parts nitric acid, and 50 parts water. This removed all cold worked metal from the surface. The samples were charged to various levels of hydrogen content by heating in hydrogen gas which had been purified by reaction with uranium powder. The various charging conditions are shown in Table I. Specimen I was heated to the reaction temperature at the indicated hydrogen pressure and allowed to react until essentially all the hydrogen was used up. Then the temperature was raised for homogenization. Specimen II was charged by making periodic addi-

Jan 1, 1962

By John Hall

SOME months ago one of the authors was asked to write a paper on the heat treatment of steel castings that would be more comprehensive than other matter lie had published; this is an attempt to present in condensed form the results of experimental work and actual practice carried out for the most part in 1907, 1908; and 1909. It is not a laboratory research and the work done was carried out for the express purpose of putting in practice the processes discovered as fast as possible. Most of the tests are the result of commercial practice and not of bars annealed in our laboratory; most of the micrographs were made for our own records and not for publication. Certain of the micrographs, therefore, are not as clear as we may wish but they were good enough for our purpose at the time they were made. The tests and micrographs are selected from several thousands in our files. All of these micrographs are magnified 60 diameters. These experiments were conducted almost entirely on steel made in a 3-ton bottom-blown converter, and most of the steel illustrated analyzes about 0.05 in phosphorus and sulfur. Unfortunately, a certain number of specimens are shown of which we do not have the complete analysis, but in most cases in which the phosphorus and sulfur vary much from the figure just given that fact is noted. For purposes of comparison, we have included a certain number of micrographs and tests of steel made in the electric furnace, some of which were from specimens made in other shops and some in our own shop, and some tests of acid open-hearth and tropenas steel.

Jan 9, 1919

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951