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By C. O. Tarr, G. V. Smith, R. F. Miller

Metallurgists have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 205o°F.l This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In I935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0. I5 per cent carbon steel that had been in service for about 26,000 hr. at a temperature of about IIOO° to 12oo°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7oo°C. (I29o°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, observed graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 12oo°F. Unstressed samples of 0.60, 0.86 and I.I4 per cent carbon steels graphitized almost completely in 360 hr. at I200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at I2oo°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from I6oo°F. and by cold-working prior to annealing. In creep tests of normalized 0.15 per cent carbon steel killed with 2.5 Ib. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at Iooo°F. under a stress as low as 1500 lb. per sq. inch. .

Jan 1, 1944

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.'-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.'' This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12'14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77' and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By D. F. Stein

In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Because of this limited success, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. As a result of these calculations, it was concluded that autoradiograPhy is a rather insensitive technique to measure grain boundary segregation. The range (energies) of the emitted particles (ß and a) must be low, and the concentration of the radioactive speczes at the grain boundary must be (in general) two or three orders of magnitude greater than the concentration within the grain. Because of these very restricted conditions , the limited success of the technzque is not surprising. In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Sulfur segregation in iron1 and possibly polonium segregation in Pb-5 pct B1 2 alloys are the only autoradi-ography experiments that have demonstrated segregation to grain boundaries in metals without the formation of a second phase. Segregation to a boundary without the formation of a second phase is often called Gibbs' absorption and is discussed by McLean in Chapter 5 of Ref. 10. There are several394 experiments showing grain boundary diffusion of a radioisotope, but this type experiment is not representative of equilibrium between the concentration of an element at a grain boundary and that in bulk, so it will not be discussed in this paper. In an attempt to determine if temper embrittle ment of low-alloy steels was associated with segregation of antimony to grain boundaries, a program to use auto-radiography (using Sb-125) was initiated. Even though other measurements strongly suggest that segregation is occurring during embrittlement, no evidence of grain boundary segregation was observed in the auto-radiography experiments. An attempt was also made to detect segregation of carbon (using C-14) to grain boundaries in iron during slow cooling. There is again strong indirect evidence7 that segregation occurs during such a treatment, but the autoradiography experiment gave no evidence of such segregation. Because of the failure of these experiments and the general lack of success by our metallographic unit in measuring grain boundary segregation using autoradi-ography, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. MODEL SYSTEM The model system is illustrated in Figs. 1 and 2. It is a semi-infinite bicrystal with a single grain boundary perpendicular to the top face. The width of the grain boundary, W, is defined as the region to which segregation has occurred and it is assumed that this region is of constant composition. The assumption of an infinite dimension is for mathematical reasons but the results of such an analysis (as will be demonstrated later) are valid for even very small specimens. It also is assumed that the measurement is not limited by means of detecting the radiation (photographic emulsions, counters, and so forth) but that the means of detecting radiation is linearly sensitive to the radiation and has infinite resolving power. The distance y is the perpendicular distance from the center of the grain boundary to the point at which the background radiation is measured and x is the integration variable. CALCULATION FOR BETA PARTICLES Two values of the intensity of radiation will be calculated, the intensity at the center of the grain boundary and the intensity far from the grain boundary. The radiation at the center of the grain boundary can be calculated in the following way. Assume a grain boundary of width W having a uniform concentration equal to Cgb + Cb where CGb is the excess concentration of the element under consideration at the grain boundary and Cb is the bulk concentration. The intensity of radiation, IgB, at the center of the grain boundary, is a consequence of the amount of radioactive material, decay rate, absorption, and geometrical factors which can be represented mathematically by the following expression:

Jan 1, 1968

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By J. C. Wright

A practical program of education for workers of the mining industries is being formulated by the Federal Board for Vocational Education in cooperation with the states in which this industry is a dominant one. The Federal Government last year passed a law, known as the Federal Vocational Education Act, that provides for the promotion of vocational education and for cooperation with the states in the promotion of such education in agriculture and trades and industries and in the preparation of teachers of vocational subjects. More than 1,000,000 men in the continental United States are employed in mines and quarries. The following table, from the 1910 Census Report, shows the relative importance of mining and manufacturing pursuits: Manfactures Mines and quaRRies Employees.......... 7,405,313 1,109,410 Capital............. $18,428,269,706 53,380,525,841 Value of product..... $20,672,051,870 $1,238,410,322 Of the more than 1,000,000 men employed in mining, almost three-fourths are engaged in the production of bituminous and anthracite coal; one-fifth, in the production of copper, iron, lead, zinc, and other metals; and the remainder in getting out structural and miscellaneous materials from quarries. The meeting of the needs of the coal-mining industry, therefore, is the problem of greatest importance in the point of numbers to be served. Moreover, the dangers in coal mining are greater than in metal mining. Practically all states have set up educational and technical standards for the position of foreman, boss, superintendent, etc., and every applicant for these positions must have a certificate of competency. The qualifications, too, are becoming increasingly difficult in the field of technical information. In some states, every miner must have a certificate, which is issued by the mine examining board only after an oral examination. Did these state laws not call for definite and comprehensive plans for the vocational education of men in the mining regions, the conditions

Jan 1, 1919

By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970

By C. G. Dunn

MANY investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal orientation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the, complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.1-3 Furthermore, it is believe that high-stress regions exist in the vicinity of these bands4a and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallization.5,6 Similar evidence has been published for nonferrous metals.5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins existed prior to recrystallization.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary orientation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha irons Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing. three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involve more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By H. M. Howe

Page 1. Introduction............................514 2. Definitions.............................517 3. Brevity of the Heating........................517 I. THE HARDENING OF THE BORE..............517 4. The Hardening of the Bore.....................517 5. The Thickness of the Hardened Layer.................517 6. Martensitization..........................518 7. The Hardening Repetitive ......................519 8. The Temperature Cycle.......................519 9. The Hardened Layer is the Merged Layer............... 521 10. The Progressiveness of Merging....................521 11. The Progressive Thickening of the Hardened Layer from Round to Round. 523 12. Merging and Hardening are Cumulative................523 13. Three Additional Causes of the Progressive Thickening of the Hardened Layer 525 14. Progressive Roughening of the Bore..................525 15. Avoidance of an Endothermic Transformation.............525 16. Asymptotic Retardation of the Thickening of the Hardened Layer.....527 17. The Troostitic Layer........................ 529 18. The Usual Lack of Martensitic Markings................529 19. The Thickness of the Hardened Layer Should Increase with the Quantity of Heat Taken up by the Walls of the Bore.................530 20. The Decrease of the Thickness of the Hardened Layer from Breech to Muzsle 531 21. Phstic Deformation as a Contributory aCause of Hardening........531 22. In What Way May Plastic Deformation Hasten Hardening?....... 535 23. Possible Need of Coarsening.....................535 24. Carburization as a Cause of Hardening..........:.....536 25. Does Hardening Increase Erosion?..................-538 11. THE CRACKING OF THE BORE ...............539 26. Appearance of the Bore and Cracks in Elevation............539 27. The Cracks in Elevation in the Rear Ring...............539 28. The Cracks in Elevation in the Forward Ring.............540 29. The Copper Network in the Grooves.................540 30. The Cracking of the Lands......................541

Jan 1, 1918

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday's constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By George D. Graffin.

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3550°C at a triple point under 1250 psi. It sublimes between 3300-3500°C at 14.7 psi. At 3726°C a second triple point occurs at approximately 100,000 atmospheres. Thermal oxidation in the presence of oxygen begins at 300°C and the rate increases with temperature. The three forms of carbon (charcoal, graphite, and diamond) are distinguished by chemical and physical tests. The specific gravity of charcoal is 1.3 to 1.9, of graphite 2.266 g/ cm3 (crystal density), and of diamond 3.5. Graphite has a hardness of 1 to 2 (Mohs' scale). Natural graphite can be divided into three classes: disseminated flake, crystalline vein (fibrous or columnar), and amorphous. Flake graphite is a lamellar form found in metamorphic rocks, such as marble, gneiss, and schist. Each flake is separate, having crystallized as such in the rock. Crystalline vein graphite is found in the form of well defined veins or as pocket accumulations along the intrusive contacts of pegmatites with limestones. The graphite of such deposits is of two types, foliated and columnar. The important Sri Lanka (Ceylon) deposits are vein type. Amorphous graphite is commonly found as minute microcrystalline particles more or less uniformly distributed in feebly metamorphic rocks, such as slates and shales, or in beds consisting practically entirely of graphite. The latter usually are metamorphosed coal seams and carry as much as 80-85% graphitic carbon, while the former, being altered carbonaceous sediments, commonly range from 25 to 60%

Jan 1, 1983

By M. B. Bever, A. B. Michael

The solidification of aluminum-rich aluminum-copper alloys was investigated for different solidification rates. The measured amounts of nonequilibrium eutectic were compared with the amounts calculated on the assumption of no diffusion in the solid. The morphology of the eutectic was studied and dendritic spacings were measured. Compositions of the cored primary solid solutions were determined by quantitative autoradiography after activation of the solute copper by neutron irradiation. CONSIDERABLE progress has been made in recent years toward an understanding of the solidification of metals. This is especially true for the factors involved in nucleation, the controlled growth of metal crystals from melts, and various aspects of the freezing of ingots and castings. Many features of the solidification process, however, are not understood adequately and much further work is required. In the research reported here the solidification of a series of aluminum-rich aluminum-copper alloys was investigated. Different degrees of deviation from the idealized case of equilibrium solidification were attained by varying the rate of solidification. Thermal analysis and microscopic examination were supplemented by lineal analysis and autoradiography. The latter required the use of radioactive tracers and was adapted to the quantitative determination on a microscale of concentrations of copper dissolved in aluminum. The tracers were produced in situ by activating the copper with neutrons. These techniques permitted a correlated interpretation of the temperature-time history, the amounts of nonequilibrium eutectic and the general morphology of the alloys, and yielded quantitative data on microsegregation. Nonequilibrium Solidification In the general case of the solidification of a solid solution in accordance with the phase diagram, the composition of the coexisting liquid and solid must change continuously. This change requires diffusion, which at best remains incomplete in the solid during solidification. The resulting inhomogeneity of the solid solution crystals is well-known as coring, dendritic segregation, or microsegregation. The generally accepted analysis of coring assumes that, 1—no diffusion occurs in the solid, 2—diffusion is complete in the liquid, and 3—the composition of the solid formed on cooling through any infinitesimal temperature interval is given by the solidus of the phase diagram. On this basis, In this equation m designates mass, x designates the concentration of solute and the subscripts L and S refer to the liquid and solid phases, respectively; the subscript o indicates the initial state, in which the liquid is identical with the entire system. Eq. 1 or its equivalent has been derived repeatedly'-7 and an analogous equation, known as Rayleigh's equation, has been used for distillation. The assumptions on which Eq. 1 is based do not include an infinitely fast cooling rate as sometimes stated. In fact, Olsen and Hultgren %ave shown by experiment that very high solidification rates suppress coring, presumably by preventing diffusion in the liquid and by the effect undercooling has on the composition of the nucleus. Coring thus occurs at rates of cooling which are too fast for a close approach to equilibrium in the solid and too slow to suppress diffusion in the liquid and to cause marked undercooling. If the liquidus and solidus approximate straight lines, Eq. 1 simplifies to The fraction of liquid present at any temperature during nonequilibrium solidification can be calculated from Eqs. 1 or 2. By the lever relation it is

Jan 1, 1955

By Elliot P. Rexford

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

THE John Fritz Medal Board of Award, at its regu¬lar annual meeting Oct. 19, awarded its gold medal to Herbert Clark Hoover. Thus ended a process of selection begun a few years ago. The award was tentatively made a year ago by the Board, which is composed of sixteen recent past-presidents of the four national societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers, having together a membership of nearly 60,000. The sixteen members of the Board are: American Society of Civil Engineers : C. E. Grunsky, Robert Ridgway, George S. Davison and John F. Stevens ; American Institute of Mining and Metallurgical Engineers: William Kelly, J. V. W. Reynders, Samuel A. Taylor and E. DeGolyer; American Society of Mechanical Engineers: Fred R. Low, D. S. Jacobus, Dexter S. Kimball and Charles M. Schwab; American Institute of Electrical Engineers: Farley Osgood, M. I. Pupin, C. C. Chesney and Bancroft Gherardi.

Jan 1, 1928

By Elliot P. Rexford

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By SAM A. LEWISOHN

IT is popular today to dramatize in a journalistic spirit, some particular factor among the causes of unemployment. Naturally the time chosen for such emphasis is usually when the factor in question is temporarily a particularly active one. A few months ago, in the unemployment then current, we saw largely the results of a healthy acceleration in changes in processes, greater efficiency, a more intensified use of labor-saving devices, perhaps also a change in products. So we have been hearing a great deal about the influence of mechanization on unemployment, the so-called technological unemployment. Many talk as if this kind of unemployment were a wholly new phenomenon, for- getting that it is a constant process in a growing industrialism, though it sometimes becomes more pronounced. At other times one would think that seasonal unemployment is the only type of unemployment, and then again the fashion changes and we hear .about nothing except cyclical unemployment. Every few years there seems to be a different fashion in labelling the germ supposed to be the cause of unemployment.

Jan 1, 1929

By D. R. Mitchell

FOR the second consecutive year, attendance at the Coal Division sessions far exceeded exoectations. Those in charge were continually faced with problems of finding seats and space for attending members. 115 seats were set - II~ for the annual luncheon meeting of the Division and approximately 175 members showed un. Since the hotel management would not serve more than the 115 it meant that 60 members were forced to eat elsewhere. This created hard feelings with some members. How- ever, officials of the Division were not able to obtain in advance any indication of this overflow crowd, but are suggesting to the New York Office that some means other than ticket sales be adopted to obtain an estimate of Division luncheon and dinner attendance. Members could be circularized prior to he meeting or they could be checked when registering as to the events they expect to attend. Under the inspiring leadership of Cadwallader Evans, Jr., Chairman, the Coal Division had a phenomenal growth during the year. Reporting at the luncheon meeting, Newel1 Alford stated that approximately 190 new members had been obtained. A few more years of continuing increase at this rate will make the Coal Division one of the largest Divisions in the Institute.

Jan 1, 1944

By Carle R. Hayward

GENERAL conditions in the lead industry have registered a distinct improvement. The first signs of a strengthening market were found in an increasing demand for scrap. There is keen competition for old battery plates both by large and small dealers. The large operator smelts them either alone or in combination with ores or other lead-bearing material, giving an antimonial lead for which there is brisk demand. The small operator usually has three alternatives. He may simply melt out the metallics in a kettle at low temperature, giving an antimonial lead and a pulverulent lead oxide; he may fuse under oxidizing conditions, giving a soft lead and lead-antimony slag; or he may fuse under reducing conditions, giving a relatively low-grade antimonial lead and a low-antimony slag. In each case the metal product is used or sold, and the dross or slag sold to a large smelter. It will be interesting to see what the final outcome will be of this situation which is generally conceded to be unsatisfactory.

Jan 1, 1937

By Scott Turner

IT has been considered that the training of an engineer is too often vocational training; that it is a pity all engineers cannot have had a period of liberal training before taking up' pure engineering. Offhand, the so-called liberal courses should bring more ready adaptability to deal with the unexpected, to face with assurance situations which have had no parallel in one's experience, and to move without hesitation under conditions which were heretofore unknown to one, than the specialized course in mining engineering. We hear increasing talk as to the necessity of making the engineer articulate and bringing him into public life. The social implications, and responsibilities of engineering are pointed out, as of equal importance with the prodigious marvels of engineering ingenuity. You often read of this as the logical result of the in¬creasing consciousness of the engineer as to his rela¬tive position in our modern industrial civilization. , Some wag has noted that man is the noblest work of God, but that man is the only one who has said so. Perhaps engineers are the only claimants as to the necessity of their going in for public life and service; at any rate, some liberal educators' still maintain that a well-rounded general education is the better training.

Jan 1, 1930