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Jan 1, 1896

Lester Guttman (General Electric Research Lab-boratory)—Seybolt has measured the thermodynamic activity of silicon in dilute solution in a iron. The anomaly which appears at 800 °C in the approximate range 1 to 6 wt pct Si is most naturally attributed, as Seybolt has done, to the existence of a region of

Jan 1, 1960

Jan 1, 1923

By J. R. Hunter

Current trends in mining practices within the United Kingdom, with particular reference to longwall retreating systems in thick and steeply pitched coal seams at depth, are explained. Various successful mining layouts are considered with their associated machinery and operation, together with the future trends in mining practices to obtain higher outputs. Environmental difficulties are tabled and discussed, including strata control, methane emmision, and dust prevention, together with some modified systems and techniques to overcome them. The problems associated with developing and maintaining a continuance of longwall panels are outlined. The constraints on technical designs and output achievement imposed by noncommercial factors are also considered.

Jan 1, 1978

PRESIDENT HORACE V. WINCHELL MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y.

Jan 1, 1923

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By Edwin B. Johnson

The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but no appreciable tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962.

Jan 3, 1963

By Harry K. Ihrig

Jan 1, 1947

By Harry K. Ihrig

Jan 1, 1947

Jan 1, 1898

By R. W. Hyde, B. S. Old, S. E. Eaton

INTRODUCTION ONE of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects on both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steelmaking. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2.1 The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2,3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. Still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States, It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaSO4), The sulphur is subsequently found in the coke in combination with carbonaceous material of unknown composition and as calcium and iron sulphides: In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke, Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two major forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high in total sulphur, would yield coke of fairly low sulphur content, Using the new

Jan 1, 1948

By Philip B. Bucky

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Jan 1, 1942

NORTH AMERICA ALASKA Anchorage.-Strandberg, H. Tuck, R. Coal Creek.-Moore, E. G. Spencer, W. W. College.-Hance, J. H. Henricksen, R. Henton, H. M. Comet.-Albertson, F. E. Cordova.-O'Neill, W. A. Douglas.-Cahill, W. E. Fairbanks.-Crawford, J. D. Earling, R., B. Fowler. D. A.

Jan 1, 1937

By Harry E. Cross

Kiln Products commissioned a Waelz kiln 4 metres in diameter by 75 metres long, in South West Africa in March, 1969, to recover nine in a form suitable for the production of electrolytic zinc. The raw material consists of a mixture of zinc silicate concentrates and zinc rich tailings purchased from an adjacent zinc mine - the mixture containing 20% to 25% zinc. The chemical composition of the ore is tabulated and the initial test results are described. Due to the comparatively low temperature at which the ore starts softening the kiln has certain unusual features to enable the temperature to be controlled within the necessary limits. A detailed description of the kiln, the starting-up problems and present operating conditions and results are presented.

Jan 1, 1970

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By P. Pollard

A method has been developed for evaluating acid treatments in fractured limestone fields by breaking down pressure drawdown into three component parts: (I) pressure differcntial across "skin" near the borehole face, (2) pressure differential due to flow resistance in the coarse communicating fissures and (3) pressure differential between the fine voids and the coarse fissures. It is apparent that in most successful acid treatments the first term, skin resistance, has been reduced or eliminated. Further, it is often possible to estimate the volume of coarse fissures associated with the second term, coarse fissure flow resistance. In cases where this volume is comparable with practical acid volumes it seems likely that this resistance also may be attacked with a suitably retarded acid. INTROD UCTION Acid treatment has been successfully applied as a general practice in the limestone wells in the Mara/ Maracaibo districts of Venezuela for some 10 years. At the same time the need has been felt for a more precise method of: (1) evaluating the effect of an acid job and (2) selecting wells which should benefit from an acid treatment. The following method, based on an analysis of build-up curves for wells producing from fractured limestone, provides a means of forecasting the effect acid will have on a well and in many cases the probable order of production rate increase which may be expected. In certain cases it is also possible to calculate the fissure volume through which the acid has to be displaced for best results. Various approximations are introduced in the method, but within the limitations of these the analysis gives an indication of how a well, whether previously acidized or not, may be expected to respond to acid treatment. Suitable build-up curves cannot be obtained on "tight" wells which do not give sustained production and the method is not applicable to such wells. Figs. 1 through 7 illustrate various types of build-up curves obtained from limestone wells in Western Venezuela. Curves are included showing (1) both skin and coarse fissure resistance, (2) skin resistance only, (3 and 4) reduction of skin resistance by acidization, (5) fissure resistance only, (6) reduction of coarse fissure resistance by acidization, and (7) acidization failure. This theory has been successfully applied for over three years during which 22 acid treatments have been carried out specifically to reduce skin resistance and three treatments to reduce coarse fissure resistance. The method has been found to be a useful aid in the selection of wells for acidization.

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960