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By Richard L. Ashbrook, John F. Wallace

Several high-temperature eutectics of cobalt and nickel alloys were modified by small additions of selected elements. Thes-e alloys were compared to unmodified melts for microstructural variations. A few modified compositions were selected on the basis of structure and their tensile and stress-rupture behavior determined. The results of stress-rupture tests in air at 1800 F and room-temperature tensile tests of four high-temperature eutectics showed modification capable of producing substantial improvements in properties. The microstructures were altered and mechanical properties improved by: a.) dispersing a subordinate phase more uniformly throughout the matrix; b) replacing large continuous -network or platelike constituents with small equiaxed discontinuous phases; and c) by forming new, finely divided phases. tHE term "modification" is most commonly used to describe the refinement in microstructure of the Al-Si eutectic that occurs as a result of rapid cooling from the melt or on slow cooling after treatment with small amounts of sodium.1 "Modification" has also been used to describe the change from flake to spheroidal graphite in the austenite-graphite eutectic of cast iron.2 This change of graphite shape is accomplished by small additions of cerium or magnesium.3 Other systems have also been shown to be capable of modification, for example: Pb-Sn by copper;4 Al-Cu by sodium;5 Al-Mn by sodium;5 and Pb-Sb by aluminum.5 Although modification of Al-Si alloys and cast irons is usually accompanied by improved mechanical properties, a general definition of modification has been suggested to include the effect of small quantities of impurity elements on the microstructures of all eutectic alloys, regardless of the effect on the mechanical properties.6 In this paper, the term "modification" is employed in a broad sense to include the formation of third phases or even the supplanting of one of the binary eutectic phases by a third phase. The mechanism of modification, as for any solidification phenomenon, must be considered primarily in terms of nucleation and growth. Although both nuclea-tion and growth mechanisms are required to explain all the phenomena observed in connection with the solidification of modified eutectics, various investigators have usually favored one or the other.7"16 It has been shown that modification of a binary eutectic can be effected by addition of a solute element that has greatly different distribution coefficients or k values in the two phases of the eutectic. Under these conditions, differences in the temperatures at the solid-liquid interfaces of the two phases retard the growth of one phase with respect to the other.4 It has also been shown that increased undercooling favors a transition from a rodlike eutectic to a globular eutectic.17 A mechanism proposed for the transition from lamellar to rodlike eutectics depends on the concept of constitutional super cooling.18 The modification of eutectic alloys may be of interest for high-temperature service as well as at room temperature. Although "high-temperature eutectic alloys" may appear to be a contradiction in terms, many eutectic systems, including those studied in this work, have melting points in excess of 2400°F. One of the mechanisms by which high-temperature alloys are strengthened is dispersion of a relatively brittle phase such as an oxide, carbide, or an inter-metallic compound throughout a ductile matrix. For a given volume fraction of dispersed phase, strength is increased by decreasing the size and spacing of the dispersed particles.19'20 Furthermore, room-temperature ductility may also be increased by changing the shape of a brittle dispersed phase from platelike to equiaxed or spheroidal.8 Overaging and redissolving of the secondary phase limit the maximum temperature to which precipitation-hardened alloys can be used. However, in a binary eutectic system, both phases coexist up to the melting point. Although all eutectic structures are not completely stable,21 a dispersion-hardened cast high-temperature alloy might result if a fine distribution of one of the eutectic phases could be obtained during solidification. An additional reason for interest in eutectic alloys is their excellent castability.22 Since eutectic alloys, like pure metals, freeze at a single temperature rather than over a range of temperatures, their castability is superior to solid-solution alloys with long liquidus to solidus ranges. The purpose of this research was to study the effects of small solute additions on the microstructure and mechanical properties of a number of high-melting-point eutectic compositions.

Jan 1, 1967

By W. McA. Johnson

THE work of J. E. Johnson, Jr., on the effect of small amounts of oxygen in cast iron in increasing its strength and resistance to shock, is of interest from the technical and scientific standpoints. The following exposition of the theory carries Mr. Johnson's explanation further and, in my opinion, will disclose certain related phenomena and perhaps shed further light on the subject. Some facts, so novel in character as to excite incredulity, have been accepted finally by many metallurgical authorities. One of these is that oxygen to the amount of 0.060 per cent. in cast iron gives it a breaking strength of 3,500 lb. per square inch, compared with a breaking strength 2,500 lb. per square inch in cast iron of the same composition with re-ect to elements other than oxygen, but having only 0.010 per cent. oxygen. The "oxygenated" cast iron, even if made in a coke furnace, has properties equivalent to the best charcoal pig iron. Mr. Johnson has also established the fact that the variations in combined carbon cannot account for the results. By microphotographic evidence he has shown that in oxygenated cast iron the graphite particles are dense and spherical, while in well-deoxidized cast iron the graphite particles are flaky and leaf-like. It is just a matter of common sense that iron of the latter structure is much weaker than the former. The analytical and microscopical work has been done with care and there is no doubt in my mind about the accuracy of the, experimental results. In this paper then, we shall consider it as accepted that small amounts (0.060 per cent.) of oxygen increase the strength of cast iron by producing a structure in which the round and solid particles of graphite are surrounded firmly by a principal matrix of ferrite. The purpose of this paper is to show that the reason why the graphite particles are round is founded on the fact that the particles of any precipitate are made denser and harder by the presence of a reagent having a solvent action on the precipitate. This can be stated as a law, although I have never seen it so given in any textbook.

Jan 2, 1916

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.' Recent work' indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken's 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. 'V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By L. A. Wilson, N. H. Harrison, R. R. Clay, R. L. Reed. D. W. Reed

Experiments have been performed in a linear near-adiabatic system for the purpose of extending data on reverse and forward combustion from atmospheric pressure to 1,000 psig. Results obtained from reverse combustion appear to conform qualitatively with the existing description of the process when reaction kinetics are suitably modified to account for the increase in pressure, i.e., increasing tbe pressure decreases the peak temperature and increases the combustion zone velocity. Forward combustion appears to be a fuel dominated process wherein peak temperature and combustion zone velocity are not very sensitive to changes in pressure. The moderate effects of pressure that do exist at low flux virtually disappear at high flux providing all oxygen is consumed. With this provision. increasing the pressure decreases the frontal velocity and increases the peak temperature. Results me shown graphicaIIy which demonstrate the effects of presswe on peak temperature, rate of advance, oil recovery, air/oil ratio, carbon oxides produced and temperature distributions. INTRODUCTION Numerous field tests of oil recovery using the technique of underground combustion are now in progress. Operating pressures used are always substantially in excess of atmospheric pressure. Nevertheless, the literature contains no laboratory data pertaining to the effects of pressure except for those of Martin, Alexander and Dew.1 Unfortunately, these data appear to reflect heat losses which may have obscured some of the effects of increased pressure. The underground combustion processes are exceedingly complex, and general concepts relating to them have necessarily been described in relatively simple terms. Particularly with regard to forward combustion, the interaction between multiphase fluid flow, heat transport and various rate mechanisms is so involved that to date a rigorous treatment is not available. In this paper a linear near-adiabatic system is described which was found capable of operating at pressures up to 1,000 psig and temperatures of at least 1,100 F. Using this equipment, experiments on both forward and reverse combustion were accomplished at elevated pressures and the data presented as a function of air flux or temperature. It will be assumed that the reader is familiar with the papers of Wilson, Wygal, Reed, Gergins and Henderson on forward combustion and that of Reed, Reed and Tracht3 on reverse combustion, so that it is not necessary to repeat the details of the two processes. EQUIPMENT AND PROCEDURE It was decided to study the effects of pressure over the interval 0-1,000 psig using a near-adiabatic system. Since satisfactory operation of such a system requires very thin tubing walls, it proved necessary to insert the entire combustion tube and heater assembly into a high pressure jacket in such a way that the internal tube pressure could be counterbalanced by pressurizing the annulus. This meant that the numerous heater and thermocouple wires had to pass through gas-tight seals that required considerable effort to maintain effective. An unexpected difficulty arose in connection with the nature of the annulus pressuring gas. It turned out that the composition of this gas critically affected the functioning of the adiabatic control system. Operation of the equipment at elevated pressures was not particularly difficult. The problems that did arise were a direct consequence of the large numbers of connections and seals involved. EQUIPMENT The equipment consisted of the combustion tube which fitted within the pressure jacket. This jacket was in turn mounted on a wheeled carriage which facilitated movement and provided for rotation of the

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By Paul Tyler

STRATEGICALLY situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cial operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennesse's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1, 1938, was approximately 19,000,000 tons. Official estimates of reserves are overly conservative and evidence submitted before a joint Con-gressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1939

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

By M. A. Hunter

THIS paper gives the results of an investigation of the specific resistance and temperature coefficient of the electrical resistance of nickel and its important alloy, monel metal. For most of the pure metals, the temperature coefficient of resistance is approximately 0.0004 per degree centigrade at 2.0° C. Nickel and iron, however, are exceptions. This property is important as it gives us good material for the construction of thermometers and other instruments involving electrical control. A summary of information on this subject has been published by the Bureau of Standards.1 The present experiments antedate this publication by several years and as the information obtained is not contained in it, the results of the experiments are published as additional information. ELECTRICAL PROPERTIES OF PURE NICKEL It is generally conceded that the lowest values for electrical resistance are obtained in the purest metal. In the case of nickel, the best material obtainable is electrolytic nickel, which contains approximately. 99.80 per cent. nickel, 0.15 per cent. iron, and 0.05 per cent. copper. Any cobalt that may be present is included in the nickel figure. If the electrolytic sheet has been deposited without intermission, it is possible to cut a section from the sheet and roll it into wire without melting. By this means a nickel wire may be obtained that is uncontaminated by any of the impurities always taken up by nickel during melting.

Jan 5, 1922

Later this month (June 24-27) in San Francisco, the Society of Mining Engineers of AIME, together with the American Society of Civil Engineers, the Canadian Institute of Mining & Metallurgy and the Engineering Institute of Canada, is sponsoring the second biannual Rapid Excavation and Tunneling Conference. The dominant theme of the Conference is the practical application of techniques and research relating to underground rapid excavation and tunneling. In the following pages, ME gives highlights of many of the 24 technical sessions and some of the papers being presented. The full proceedings of the Conference will be published by SME-AIME later this year.

Jan 6, 1974

By Halbert Powers Gillette

In every chemical reaction heat is either developed or absorbed, and this plus or minus heat of formation is as definite in quantity as the weights of the reacting elements. In this paper I shall show that each chemical element and each chemical radical has its own definite heat-valency,—a fact which, so far as I know, has hitherto escaped the attention of investigators, but, I feel sure, will be admitted after the demonstration here given, and may lead to some practical conclusions of value. When Berthelotys " law of maximum work " was found to have so many inexplicable exceptions, the pendulum of a scientific theory swung away from a recognition of the truth underlying that proposition; and this reaction went so far that not only has thermal chemistry been relatively neglected by recent investigators, but it is not uncommon now to find textbooks on physical chemistry which practically ignore all that Thomsen, Berthelot and others have done. To this temporary tendency of thought I attribute the failure to recognize the principles herein announced and explained. Not long ago, while studying tables of the formation-heat of various salts, I noticed that in this respect all potassium salts in solution differ from the corresponding sodium salts by 9.3 cal.1 I found also that similar differences exist between other salts, not only when the basic radical is varied, while the acid radical remains constant, but also when the acid radical is the variable. Thus chlorine salts in solution differ from bromine salts in this respect by 10.9 cal. Upon further study, I found that Thomsen had noted similar constant differences, but, so far as I can ascertain, he appears to have attached no great significance thereto.

Jan 1, 1904

By H. J. Gluiskoter

The chlorine content of the coals in the Illinois Basin ranges from 0.00% to more than 0.60%. The chlorine content of the Herrin (No. 6) Coal has been mapped on a regional scale and, in general, increases with the depth of the coal. The depth-chlorine correlation exists because the coal is in apparent equilibrium with the composition of the ground water associated with it, and the salinity of the ground water generally increases with depth. At least part of the chlorine can be easily removed from the coal in the laboratory. In a natural weathering experiment, chlorine values decreased markedly during an 8-week period. Results to date indicate that none of the coals studied has a sufficiently high chlorine content to make it unusable in high-temperature steam boilers, although special steps may be necessary in the preparation or utilization of some of the highest chlorine coals. Investigations into the occurrence and distribution of chlorine in Illinois coals have been in progress at the Illinois State Geological Survey for over 35 years. Since 1948, chlorine analyses of face channel samples and of drill core samples of coal have been made routinely. The increased interest in chlorine and alkalies in coal in the U.S. followed that in Europe, where power plants during World War II were called upon to produce at higher levels than previously and with less down time for maintenance. Higher steam temperatures were reached, resulting in increases in the amount of fouling of external heating surfaces and in corrosion of boiler tubes when high chlorine coals were used. Early studies of the problem showed that coals with high chlorine content were more likely than those low in chlorine to cause difficulties in installations fired with powdered fuel. Crossleyl reported that the first rule of thumb developed for British coals was that coals considered to be high in chlorine (more than 0.30%) caused the most trouble, those intermediate in chlorine content (0.15% to 0.30%) were less likely to cause difficulties and those low in chlorine (less than 0.15%) generally were not associated with alkali bonded deposits and corrosion. However, this relatively simple picture was not adequate to characterize the difficulties that could be expected during the utilization of a large number of coals and Crossley1 developed another scheme for assessing the chances of superheater corrosion. This scheme took into consideration the observation that coals high in sulfur as well as chlorine are more likely to cause corrosion and fouling than coals low in sulfur and high in chlorine. Crossley also considered the ash content. When two coals had the same chlorine and sulfur contents, the one with the greater amount of ash would be the less likely to cause difficulties. Knowing only the amount of chlorine in a coal obviously will not give all the answers. Indeed, the significance of the chlorine content has been much discussed and it has been suggested that perhaps the total alkalies are a better indicator of possible troubles. The observation that the deposits that form

Jan 1, 1968

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965

By Y. C. Liu, G. A. Alers

The anisotropy of Young's modules has been measured in a series of Cu-Zn alloys containing from 1 to 28 wt pct Zn and cold-rolled to 97.5 pct reduction in thickness. These modulus data show a transition in texture as a function of zinc content. In alloys containing 3 pct Zn or less, the texture is essentially that of copper. A transition is clearly seen to develop in 5 and 8 pct Zn alloys, and to have been completed in a 12 pct Zn alloy. Increasing the proportion of zinc to 28 pct does not produce any further changes in texture. The ease and clarity with which this texture transition can be seen in the modulus data is in great contrast with the inccertainty in the visual detertiination of the range of texture transition from a series of pole figures. It is also shown that the rolling texture of the high zinc content alloys cannot be a one-COIIIponenl texture, characterized by the (110)(112) ideal orientations, as usually assumed. A second, quite important component must also be present. Furthermore, the present data are inconsistent with matrix orientations on which the "oriented growth" hypothesis of the Formation of recrystallization textures is based. THE rolling textures of binary fcc alloy systems have generally been considered to lie between two terminal textures. One of these terminal textures is the copper type and the other is the 70:30 brass type. Alloys of intermediate solute content exhibit a texture which is said to be a transition between the two terminal textures. On the basis of efforts to correlate rolling and recrystallization textures, two concepts have been advanced in the literature on the nature of these transition textures. One school1 suggests that the addition of alloying elements, e.g., zinc, causes a gradual rotation about one of the (111) poles from the (358)( 523) ideal orientation of the copper-type rolling texture to the terminal {1 10)( 112) ideal orientation used to describe the rolling texture of 70:30 brass. This concept is depicted in Fig. 1 with the angle of rotation corresponding approximately to the zinc content and is designated here as the "rotational concept", since the ideal orientation of the transition textures varies continuously with alloy content. The other concept,' the "mixture concept", suggests that the copper-type rolling texture is a two-component texture. {358) (523) and {110)(112). The addition of alloying elements affects only quantitatively the relative amounts of these two components—a decrease in the amount of material in the {385}(523) orientation and an increase of that in the {110)(112) orientation with increasing solute content. An experimental distinction between these two concepts is essential to a better understanding of both the mechanism of formation of rolling textures and the subsequent formation of recrystailization textures in fcc metals. Because of the lack of resolution inherent in pole figures, it has not been possible to differentiate between the two concepts on the basis of this data. Both concepts, in fact, make use of the same set of pole figures but interpret them in a manner acco-rding to the view held.'" Experimental results obtained from inverse pole figures or selected-area electron diffraction3j4 simply -yield more refined pole figures but do not eliminate the ambiguity of interpretation. Quantitative measurement of an entirely different, orientation-dependent property must thus be considered

Jan 1, 1967

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University's Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By W. L. Honnold

(San Francisco Meeting, September, 1915) OWING to a unique labor situation and other unusual circumstances, the mining methods of the Rand are hardly comparable with practice elsewhere. They are' of considerable interest, however, and their impor-tance is increased by the magnitude of the industry with which they are identified, gold of $166,186,000 value, say 40 per cent. of the world's production, having been recovered from 25,701,954 tons of ore milled in 1914. In the sketchy remarks to follow, attention will first be drawn to some influential factors of general bearing, after which certain features at two mines of the writer's group will be referred to. It is hoped that engineers associated with similar or different conditions and practice will contribute to broaden the discussion. Before proceeding, recognition is due the generous assistance of C. E. Knecht and F. A. Unger. GENERAL OBSERVATIONS The principal mines are situated along the northern limit of an irregularly shaped geological basin, and extend in almost unbroken continuity over a distance of about 60 miles. As the boundaries are defined by vertical planes there are both "outcrop" and "deep-level" properties, all differing in size and in technical features. So much has been written in regard to the geology of the Rand that only a few pertinent features need here be recalled. Briefly, the ore deposits are profitably enriched portions of certain conglomerate beds or "reefs," rarely more than three, which are interposed between quartzite, or quartzite and slate, and lie so closely together that where more than one are mined they are dealt with as a work-ing unit, although they may lie stoped separately. Their collective extension is locally referred to as "the Reef."

Jan 8, 1915

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metallurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each temperature from room temperature to fusion temperature, and cooled at a rate that is not generally controllable but is predetermined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each temperature zone. The nature of the zones produced by other types of welding is the sane. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and disadvantages of the extent of the zone are of prime moment, and are discussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known. GENERAL METHOD The scheme of procedure in the work herein reported involved the testing of the metal of each temperature zone adjacent to the weld in so

Jan 1, 1935

By C. R. Breck

THERE has been a running discussion over the past several years with respect to the life and adequacy of our natural gas reserves. Some of the experts agree on one phase of the subject at least-that eventually it will be necessary to augment deliveries of natural gas in the northern markets by the development of a more or less comparable synthetic gas made from coal. The purpose of this paper is to point out: 1. It may be later than a good many people think-the demand for addi¬tional domestic and commercial pipeline gas in at least one section of the North will probably be felt rather keenly before an adequate synthetic pipe¬line-gas project, developed on economic lines, could be completed, even if initiated in the near future. 2. The evidence is considerable that such a project would be technically sound and economically self-supporting, although the margin of profit at first might be so small and the magnitude of an economic enterprise so great -that financing would be impossible without Government aid in some form or other. The part of the country referred to is the heavily populated section in the northeast of the United States. To simplify an examination of the situa¬tion, let us take the potential marketing areas within range to the north and east of the three pipelines: 1. Tennessee Gas Transmission Co. as it enters Erie County, New York state. 2. Texas Eastern Transmission Corporation just before the tap that sup¬plies the general Philadelphia area. 3. Transcontinental Gas Pipe Line Corporation as it enters the state of New Jersey. The sources of gas for these three pipelines are in Texas and Louisiana. The ultimate maximum combined capacity of the three lines at the points stated is approximately 1,200,000,000 cu ft per 24 hr at the maximum load factor probable of attainment in normal operation. The areas supplied by the three lines north and east of the points stated, or assumed as eventual markets, are: 1. Central New York state, from Buffalo to Albany (both inclusive).

Jan 1, 1953

By W. J. Taylor

SOME eight years ago I became interested to a considerable extent in one of the well-known deposits of sulphury iron ore in New Jersey, and, as a consequence, soon became interested in the subject of the elimination of the sulphur. On investigation I found that no department of pig-iron manufacture had received less attention than that of roasting or calcining ores for the elimination of sulphur, carbonic acid, water, etc. My first devices to eliminate sulphur were naturally in the lime-kiln line, with solid fuel mixed with the ore, in the same way as common lime is burnt with small coal. While this process will succeed tolerably well for carbonates or calcareous ores, even though they contain sulphur as sulphates, I soon found it would not answer for our magnetites, which are very hard and dense, carrying from 2 to 5 per cent. of sulphur as pyrites, and become very sticky as soon as any attempt is made to roast them at a high heat. Some laboratory experiments developed the fact that the nearer the gaseous current surrounding the hot ore approached in composition pure atmospheric air the more rapidly the sulphur was oxidized, while in an atmosphere composed largely of carbonic oxide, carbonic acid, and nitrogen, it seemed almost impossible to reduce the sulphur more than one-half, which was a confirmation of the well-known fact that just one-half of the sulphur in pyrites volatilizes very easily, and that the trouble is mainly to remove the remainder. It was thus apparent that the atmosphere surrounding the ore was of as much importance as the temperature. This led to the trial of a kiln to heat the ore by conduction through the brick. It was divided into ore-chambers, which were surrounded with flues, through which the products of combustion of gaseous fuel passed without coming in contact with the ore. We did not, however, succeed by this arrangement in getting more than a cherry-red heat, which, of course, was too low to accomplish anything. I had at this point become convinced – 1st. That gaseous fuel only would accomplish the work successfully. 2d. That since a high temperature was required to insure a rapid oxidation of the sulphur, and also to make the ore open and porous,

Jan 1, 1881