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By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C' where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.'-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,' and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.' The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6'14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth's crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,' resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By James Boyd

Scientists and engineers must concern themselves not only with technical problems, but with the socio-economic difficulties of our scciety. The author states that raw materials are basic to the economic process and that mineral raw materials occur naturally in nearly limitless quantities. He feels that the economic pocess will provide sufficient raw materials for man's needs, and discusses in some detail the world economic environment. As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experiences to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. RAW MATERIALS BASIC TO THE ECONOMIC PROCESS There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as "All productivity is based on three factors: 1) natural resources, whose form, place, and condition are changed by the expenditure of 2) human energy (both muscular and mental), with the aid of 3) tools.77* It seems strange that such an obvious statement needs to be made. It is forgotten by all of us, however, at one time or another when we get involved in the complicated theories of economics dealing with the financial and fiscal policies of the various governments, in the financing of enterprises, in marketing, and in labor relations. Unless decisions in all of these fields are made with this, and the rest of the "Ten Pillars of Economic Wisdom," consciously in mind, the resultant policies are doomed to eventual failure, whether these are policies of individuals, companies, or governments. The economic process is basic to society. But economics and the social aspects of humanity are inevitably intertwined. If human needs are not provided for within the basic economic structure, conflicts arise to disrupt the most carefully laid social plans. Similarly, it is the failure of society to cope with basic economic prerequisites that leads to discord within the body politic and thus to eventual economic disaster. We who are engaged in the various aspects of the mineral industry, therefore, have a large part to play in society's future development. MINERAL RAW MATERIALS OCCUR NATURALLY IN NEARLY LIMITLESS QUANTITIES Throughout my career in and out of government, I have formed my decisions on two principles: 1) Fundamentally, all mineral raw materials exist within the earth's crust in quantities greatly exceeding man's needs; 2) Any problems of supply of these materials are primarily economic in nature. With respect to my first assumption, analyses by geochemists enable them to estimate the quantities in which each of the known elements exist in the earth's crust. One of the most cautious and famous suggests that the average copper content of the lithosphere to a depth of ten miles is about 55 ppm. If this is valid, then the lithosphere contains about 1.4 quadrillion (1.4 x 10 ") tons of copper metal — an unimaginable quantity. This is 8,500,000-fold that which has been consumed by man in his existence. To illustrate further, consider that the deepest copper mine in history went to about 9000 ft below the surface; the present copper mines of the world now average less than 1500 ft in depth. We can assume that in most continental land areas of the world it is technically feasible to mine to a depth of at least one mile. The land areas of the world to an average depth of one mile, then, contain 343 billion tons (343 x 10') of copper metal, or 2000 times that which has been extracted to date. I don't believe man will ever expend his energies to extract copper from rocks which contain only a few parts per million, but he knows that each element

Jan 1, 1968

By T. L. Joseph, G. Bitsianes

THE layered structure of partially reduced iron ore was described in a previous paper.' Reduction by hydrogen was found to take place at well-defined interfaces between layers of the solid phases. In the present investigation, a detailed study was made of the wiistite phase that had formed during the partial reduction of a cylindrical compact of chemically pure hematite. An unusually wide band of wiistite permitted a rather detailed study of this phase. The specimen was made from Baker's C.P. hematite in the form of a cylinder 1.5 cm in diameter and 1.8 cm long. A dense ore structure with about 6 pct porosity was attained by heating the specimen in air at 1100°C for 3 hr. To confine reduction to the top surface, a ceramic coating was applied to the bottom and sides of the cylindrical compact. The specimen was then partially reduced in hydrogen at 850°C and subjected to a coordinated sequence of macro-, micro-, and X-ray examinations. A section of the partially reduced cylinder is shown in the macrograph, Fig. 1. Four layers consisting of metallic iron, wustite, magnetite, and unreduced hematite are clearly shown. The effort to force reduction to proceed downward in topochemi-cal fashion was only partly successful, as some reduction occurred along one side and bottom of the cylinder. A rather wide layer of dark wustite phase had formed, however, and permitted sampling for X-ray studies as indicated. To supplement previous work and to study the wustite layer in more detail, ten separate layers were removed for X-ray examination. Broad and diffuse patterns were obtained with the as-filed powders, especially with those of iron and wiistite, and the condition indicated a cold-working and variable composition effect within the respective layers. This condition was corrected by annealing the entire series of powders at an appropriate temperature. For the annealing treatment, the ten powder samples were wrapped in silver foil, sealed under vacuum in small quartz tubes, and heated at 750°C for 16 hr. The specimens were then drastically quenched in cold water to preserve the annealed condition. These annealed specimens were X-rayed in turn and the compiled patterns are shown in Fig. 2. The standard patterns for iron and its oxides have been interjected at appropriate positions for purposes of comparison and phase identification. All of the patterns obtained were clearcut and concise so that positive identifications could be made for all of the phases. The outermost layers A, B, and C were composed almost entirely of iron with a small amount of wiistite being detectable at the X-ray limit of phase detection. Layer D from the iron-wustite interface showed both of these phases. The next four layers E, F, G, and H were all in the dark phase band which had been tentatively identified as wustite by the macroexamination, Fig. 1. The diffraction data with their single-phase patterns of wiistite for these layers checked the visual evidence. Continuing the X-ray analyses after layer H, the macrograph (Fig. 1) shows that layer I came largely from the magnetite zone but included some fringes of the wiistite-magnetite interface. The diffraction pattern for the sample confirmed this observation. Layer J came from the unreduced core of the specimen and its diffraction pattern indicated a preponderance of hematite phase. The reduction behavior of synthetic compacts has thus been found to be similar to natural dense iron ore. The previous results were supplemented with measurements of the diffraction films and calculations of the respective unit parameters. These X-ray data are summarized in Table I and offer some interesting correlations as to the compositions of the various phases undergoing reduction. The iron layers that were analyzed gave lattice parameters close to that of pure iron at 2.8664A. Evidently this iron was present in layers A through D as a pure phase with little or no oxygen dissolved in its lattice. With the wiistite layers an entirely different situation prevailed in that there was a definite and

Jan 1, 1955

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By T. Seldenrath

In the development of a fluid -operated hammer drill' for accelerated penetration of hard rock formations in oil wells, a research investigation was conducted to evaluate the percussion effects obtained with different design characteristics and to determine the possibilities of percussion in the low frequency range. Tests were conducted on granite blocks and comparable impact forces were measured with a load cell under selected test conditions. These full-scale laboratory tests provided an evaluation of the effectiveness of percussion which was further supported by actual downhole field performance. While much pertinent data have been presented by other investigators the method of evaluation described in this article resulted in good correlation between laboratory and field performance and may be applicable in other low frequency percussion developments. EXPERIMENTAL METHOD For these tests the bit was held stationary and the test block was rotated and forced upward against the bit by a hydraulically-lifted rotary table. "Weight on bit" was calculated from pressure readings on the fluid system of the lifting cylinders—corrected for tare and friction. Percussion was obtained with several tubular hammers of different weights up to 320 lb. These were lifted mechanically and allowed to drop by gravity from various heights onto a slidably-mounted bit sub or "floating anvil" for calibration of the load cell response with known kinetic energy of the hammers. During evaluation of percussion effects, the hammers were hydraulically operated to provide a range of percussion frequencies up to 1,020 blows per minute delivered to the anvil. To obtain comparable test readings, the load cell of the strain gauge type, was attached to the bottom of the anvil or bit sub in place of the bit. The load cell rested on a typical granite test block mounted on the drilling table. The latter was hydraulically supported as in the actual drilling operation. The effect of support resistance was the same for all tools when calibrating. Impact forces so determined werethusdirectly comparable with one another for the purposes of this investigation. When a roller bit was substituted for the load cell for actual drilling, the impact force would probably be reduced due to the resiliency of the bit body, legs. cones and teeth and the penetration of the teeth into the rock. However, since the bits and rock specimens were uniform in these tests, an evaluation of actual tool performance, in terms of parameters previously determined with the load cell at the selected standard conditions of calibration, proved satisfactory. Throughout these tests, 8¾-in. standard tricone, hard rock toothed roller bits and carbide-insert roller bits were used. Rotary speeds were 50 and 100 rpm; static weight on bit was applied up to 40,000 Ib, and percussion frequencies up to 1,020 blows per minute were available. During this investigation it was found that toothed bits on which the teeth had developed flat ends about 3/16 in. wide did not change appreciably for the duration of a test. Hence, all toothed bits used in this study were in this condition. Conventional reference curves obtained in these tests show that increasing weight on hit by 2:1 yielded an increased penetration rate of approximately 2.7:1, while an increase in rotary speed of 2:1 netted an increased penetration rate of roughly 1.7:l. Results are thus of the same order as those reported for hard rock drilling by other investigators." CALIBRATION Under the selected standard test conditions previously described, with the lifting table hydraulically supported, and the anvil interposed between hammer and load cell, the hammers were dropped from known heights. Thus, with the kinetic energy of the hammer known, the corresponding maximum impact force shown by the cell was determined. (It may be of passing interest to note here that special drop tests with the hammers showed that no appreciable reduction in impact force resulted from introduction of the anvil or hit sub.) From these calibrations, it was possible to determine the theoretical kinetic energy available in the hammer from the maximum impact force shown by the load cell while operat-

By J. J. Gilman

Examination showed that characteristic cleavage step patterns are observed on the cleavage surfaces of undeformed, slipped, bent, twinned, compressed, and indented zinc crystals; and the effect of temperature is discussed. Dimples were seen to produce cleavage steps in a treelike pattern in otherwise undeformed crystals. The steps seem to originate when cracks intersect screw dislocations. IT has been known for a long time that the path of fracture in polycrystals may be discontinuous (see Jaffe, Reed, and Mannl for review). Recently, Kies, Sullivan, and Irwin2 have proposed, and given evidence, that crack propagation is discontinuous within individual crystals as well. Other evidence has been given by Low.' When discontinuous cracks within a crystal join together to make a macrocrack, the lamellae between each set of two cracks are torn somewhere, forming small cliffs. These cliffs appear as lines when the cleavage surface is observed microscopically.4,5 The lines have been called vein, tree, and riverlike markings by various authors, and they have sometimes been mistaken for fissures. The descriptive term cleavage steps is used in this paper. Cleavage steps vary in height over a wide range of values, from molecular dimensionsG to lor. and larger. Kies, Sullivan, and Irwin,2 as well as George,' have shown that the gross cleavage step patterns for plastics, polycrystalline metals, and for mono-crystals are sometimes similar. Thus, they depend mostly on the mechanical variables that prevail during cleavage and are relatively insensitive to the structure of the material. For example, parabolic markings2,7,8 sometimes result when cracks open up ahead of, and not coplanar with, the main crack front. If the advance crack has the same velocity as the main crack, their intersection line is a parabola, otherwise it is a hyperbola or an ellipse. The patterns are strongly affected by differences in crack velocities. This results in chevron patterns which point to the place of origin of the main crack. It is the purpose of this paper to demonstrate the existence of a mechanism of cleavage step formation which is a continuous rather than a discontinuous process. Also, certain characteristic step patterns are described, and the strong effect of temperature is shown. The specimens were zinc monocrystals (grown from 99.999+ pct pure metal). These were cleaved at room temperature and at — 196°C. Results and Discussion Cleavage step patterns are highly variable from point to point on a given specimen, as well as from one specimen to another. Although the patterns shown in the photographs are typical, they have been selected for graphic illustration. Figs. la and lb compare undeformed crystals that were cleaved at —196 °C and room temperature, respectively. Cleavage at room temperature (Fig. lb) resulted in a higher density of high steps (dark black lines) and enhanced the visibility of the fine background markings. Deformation by simple slip caused no marked change in the step patterns until the glide strain reached about 1.0. But, as Fig. lc shows, the density of high cleavage steps was greatly increased by large glide strains. Corrugations lying perpendicular to the slip direction may also be seen in Fig. lc. These are caused by deformation bands. The cleavage resistance of the crystal of Fig. lc was very high compared to undeformed crystals (estimated by the force on a needle required for cleavage). Striking and varied cleavage step patterns were observed on bent crystals. Two characteristic patterns that were observed on crystals bent at 25°C, and cleaved by reverse bending at —196°C, are shown in Figs. 2a and 2b. The first, Fig. 2a, consists of V-shaped lines similar to the parabolas of other materials2,7 Fig. 2b shows a pattern that is the equivalent of Fig. la, consisting of faint background lines with a few higher step markings. Cleavage of bent crystals at room temperature resulted in Figs. 2c and 2d. Now, the cleavage step lines show a strong tendency to follow one of two perpendicular paths. In Fig. 2c (bent once), many of the cleavage step components that lie parallel to the bend axis are assembled into irregular lines. In Fig. 2d (bent twice), the cleavage steps again tend to consist of two perpendicular components, but neither of the components is assembled into lines. Also, the step density is higher.

Jan 1, 1956

By R. V. Higgins, A. J. Leighton

Interest by petroleum engineers in the flow of three phases—oil, gas and water—in irregularly bounded porous media lies mostly in the performance calculation of water floods of reservoirs that have been partially depleted as the result of expansion of much of the originally dissolved gas. The authors present a method to forecast three-phase flow in complex geometry and explain the details by the use of a specific example of a five-spot water flood of a partially depleted stratified reservoir. In this example, the fluid and rock properties of a field given by Prats, et al,' were used. The computed results fit the field performance more accurately than Prats, et al, and Slider.' The time required for the high-speed digital computer to make the calculations, including the contributions from the different layered zones, is about one minute. INTRODUCTION The declining rate of discoveries of new oil fields in the United States makes the recovery of more oil from known reservoirs more attractive than previously. Water flooding has an excellent proved background for recovering additional oil economically. Accordingly, the main interest of this paper is in this type of recovery. In petroleum engineering studies, commercial interest in three-phase flow is mostly in the water flooding of reservoirs in which the oil has been partially produced by the expansion of dissolved gas. When water is pumped into these reservoirs, three-phase flow takes place. Although this paper is concerned with these conditions, the principles involved could be used for other conditions when and where they come to the fore. Many investigators have made contributions to non-empirical forecast methods using basic scientific engineering principles. Several of these used the oil in place at the start of the water flood and the oil remaining after a large quantity of water has passed through a core for key values in their calculations. Recently, Prats, et al,' and Slider have reduced assumptions by adding the third phase—gas—in their forecasting methods. Slider uses the mobilities in the immediate vicinity of inlet and outlet wells as an aid to simulate the resistance effect in the five-spat pattern of the flow of oil, gas and water. Prats, et al. minimize assumptions by using previously determined laboratory data for determining sweep efficiency in the five-spot pattern. In neither of these papers is the saturation profile continuously affected by permeability-saturation curves. Sheldon and Dougherty- recently described a method that employs continuously changing saturation profiles using permeability curves, has a minimum of assumptions and needs no prior sweep efficiency. The Higgins-Leighton method, described in this paper, has all of these features; however, many of the techniques are different from those of Sheldon and Dougherty. The Higgins-Leighton method, tested in May, 1961, is direct and easy to apply and requires very little computer time to calculate a forecast. The short computer time is especially helpful in the study of a reservoir containing many layers of different relative permeabilities. In the Higgins-Leighton method, the individual pressures do not have to be calculated, as the resistance to flow in each cell in the flow pattern is readily determined without the use of any iterative techniques. The saturation and permeability distributions are readily determined. These data and the shape factor, which is measured only once from the potentiometric model when mobility ratio is one, determine the resistance to flow in each cell. THEORY The authors showed in a previous paper4 that, as an aid to calculating performance, the reservoir can be divided into channels using the streamlines of a potentiometric model as a guide. See Fig. 1. This procedure also was used in this paper. The authors also showed that, by treating conduits as approximately one-dimensional and neglecting pressure gradients transverse to the main flow, the Buckley-Leverett equation may be expressed as The principles expressed by this equation are employed extensively in the three-phase flow, as they were in two-phase flow. In the three-phase flow, the channels (the size and shape of which are taken from a potentiometric model)

By R. Q. Shotts

This paper is a review of recoverable reserves of bituminous coal in the Southern Appalachian area, according to the latest published estimates. A few comparisons are made, some apparent trends are discussed, and some comments are made regarding the limitations of present estimates. The definition of Southern Appalachian area used in this report is somewhat arbitrary. It includes all the bituminous coal deposits of Alabama, Georgia, and Tennessee. All of West Virginia has been excluded. The East Kentucky and Virginia counties included were selected in connection with a literature study the writer made in 1959 of possible coal supply areas for the Tennessee Valley Authority. The selected counties were considered to be the only ones from which TVA might expect to obtain coal. The availability of coal from some of these counties is doubtful, but no other East Kentucky counties were considered more than remote possibilities. With these limitations, the Appalachian area covered is that from which producers of electric power and steel and commercial coal users, located in the Southeastern U. S., may expect to obtain their supplies of coal. Of course, it is recognized that coal from the eastern interior fields is also available to many of these same organizations. RANK AND QUALITY OF THE COALS Practically all the coals in the Southern Appalachian region are of high volatile A bituminous rank. An occasional sample indicates a slightly lower rank, but such samples may be oxidized or otherwise not representative. Some thin beds in Lookout Mountain and Sand Mountain in Alabama and Georgia, are low volatile bituminous coals, but they have not been mined extensively in modern times. There is a possibility that some of the deeper beds along the southeastern edge of the Warrior field of Alabama are near the Low-medium volatile bituminous dividing line. The Sewanee bed and some other minor ones of the Southern Tennessee field, some of the lower beds in Virginia, many beds in Sand and Lookout Mountains in Georgia and Alabama, one or more beds in the Coosa field, possibly some lower beds in the Cahaba field, and most of the beds along the southeastern edge of the Warrior field and the southern end of the Sequatchie anticline of Alabama, are of medium volatile bituminous rank. The quality of the Southern Appalachian coals is highly variable. Some of them, particularly such prevailingly thin ones as the Black Creek bed of Alabama and the Straight Creek bed of Kentucky, are unusually low in mineral matter— probably the lowest in the U. S. With the exception of certain beds and local areas, Alabama and East Kentucky coals probably have as low average ash and sulfur content as can be found in any sizeable coal area in the country. The sulfur content of Southern Appalachian coals is also variable, but few beds are consistently high in sulfur. In Alabama, sulfur generally increases from southeast to northwest across the Warrior field, but this trend is not quite as clear in the other states. A few beds in Northern Tennessee are prevailingly high in sulfur. All Southern Appalachian coals are potential coking coals if they can be prepared to meet chemical requirements. Only a comparatively small part of the medium volatile A bituminous coal, but most of the medium volatile bituminous coal mined is actually used for coking purposes. An estimate of reserves of coking coal under the requirements of present practice, could be compiled comparatively easily, but this probably has never been done. The reserve of coal that can be coked as an ingredient of a suitable blend is probably many times the size of the reserves of coal that will yield suitable blast furnace and foundary coke without blending. WHAT CONSTITUTES ECONOMICALLY RECOVERABLE COAL RESERVES? When one first realizes the vast extent of the coal-bearing rocks in the Southern Appalachian area, (see Fig. 1) the thought is likely to occur that the supply of coal is inexhaustible. This is particularly true on realizing that in some of the basins of thicker coal-

Jan 1, 1962

By K. E. Beu

IN the measurement of retained austenite concentrations in steels using the integrated intensity method,1 Averbach has pointed out" that the absorption factor A(0) for a flat sample making a glancing angle 4 with the incident X-ray beam can be combined with his constant factor R to obtain our constant factor" G provided that "1—There is no preferred orientation in the sample, and 2—The geometric requirements [for the sample, film, and X-ray beam] have been met precisely."' If A(0) can be combined with R to give G according to the equation G = R . A(0) [14] then the possibility for making non-compensating errors in the austenite determination has been eliminated. This has been described previously in a technical note." Because of the brevity of the previous note,3 it was impossible to emphasize the fact that the two conditions on preferred orientation and geometry can be easily met experimentally, contrary to Aver-bach's statement that: ". . . the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2 [the theoretical equation for A(0)]."" he way in which these two conditions can be met experimentally will be discussed briefly to help clear up this point. In addition to these two conditions, other factors such as sample shape, homogeneity, and grain size which also affect A will be included in this discussion. A (0) depends on sample shape. The theoretical function for A was derived originally for a flat surface.' In general we have found that a flat sample surface is readily obtainable." If such a surface can * The effect of surfaces which are not flat on the measurement of retained austenite will be discussed later. be obtained, it has the following advantages: 1—it is easily reproducible from sample to sample, 2—it is the form required for metallurgical examination —this type of examination being frequently desirable for this work, and 3—it is an efficient shape for diffraction purposes. Perhaps the most important of these features is that a flat sample surface is easily reproducible; hence, this requirement on the repro-ducibility of A from sample to sample is met for all such samples. Fig. 1—Schematic diagram of the quartz crystal monochromator diffraction unit. The centerline of the main beam is at 6' to the target face. The tangent to the crystal face is at 16.8' to the moin beam. The centerline of the monochromatic beam is at 33.6 to the main beam. The sample surface can be rotated in its own plane. The angle of the sample surface and the monochromatic beam can be adjusted by rotating about the vertical axis, The film holder can also be rotated about B so that the film can be exposed over the desired angular range. For Fe K, X = 1.932A. 1011 planes of quartz have d = 3.35A. A(0) depends on homogeneity and grain size. If the sample is badly segregated or the grain size is large, the effect of micro-absorption and primary extinction1. ' must be considered. It has been shown, however, that for most plain carbon or low alloy hardened steels, neither micro-absorption nor primary extinction effects are present.' A (0) depends on camera geometry. For a given angle 0, A remains theoretically constant from a geometrical viewpoint only if the following factors are kept constant: 1—the angle of inclination .+ of the sample to the X-ray beam, and 2—the centering of the sample with respect to the film cylinder. These are mechanical problems which can be solved readily if the facilities of a good machine shop are available. The arrangement used to insure that the angle 4 remains constant and the centering of the sample is reproducible is indicated schematically in Fig. 1. The sample is clamped against a thin plate with a hole in it by means of a spring-loaded pres-

Jan 1, 1954

By H. R. Crawford, P. B. Crawford, A. F. Tragesser

A method has been developed to calculate wellbore temperatures during mud circulation and the actual cementing operation to aid in the design of cement slurries. The method agrees within 10F with previously measured values. The calculation technique provides temperatures, as functions of time, at varying depths in both the casing and annulus. The technique also provides this information if a relatively cool cement slurry is pumped into the well immediately following circulation of hot mud. Circulating bottom hole temperatures of brine and a bentonite mud were measured. INTRODUCTION As wells are drilled deeper, greater demands are being made on all phases of the industry, and new technology has been developed to provide satisfactory well completions. However, little or no work has been conducted on accurately determining bottom-hole, static and circulating temperatures.. In designing a cement slurry, such factors as density, fluid loss control, viscosity, deterioration from ternperature, compressive strength and pumping time must be considered. Individual well conditions often make it necessary to include still other factors. Pumping time is a primary consideration and, as wells are drilled deeper, encountering higher bottom-hole temperatures, this property becomes even more important. Cement slurries must be designed with sufficient pumping time to provide safe placement in the well; however, the slurry cannot be overly retarded as this will prevent the development of satisfactory compressive strength. The pumping time of a specific cement is currently obtained by subjecting the cement to simulated conditions of temperature and pressure. A reasonably accurate bottom-hole pressure may be obtained by considering hydrostatic heads of fluids, friction pressure and wellhead pressures. However, accurately determining bottom-hole temperatures is much more difficult. Bottom-hole static temperatures are estimated by considering several sources of information, including logging temperatures, published temperature gradient maps and field experience. This information is usually questionable due to disagreement of data from the various sources. Temperature gradient maps were constructed based on temperatures recorded many years ago while running bottom-hole pressure tests. These thermal gradients then represent an average of well conditions and cannot always apply to a specific well. Also, logging temperatures may be affected by the time since fluid was last circulated, rate of penetration, circulating rate and many other factors. Therefore, even though logging temperatures are available, the question still exists as to the correction factor that should be applied to obtain an accurate static temperature. After obtaining static bottom-hole temperature, it is then necessary to relate this to circulating temperatures actually encountered by the cement slurry. This is accomplished by selecting a test schedule from the API RP-10B corresponding to the estimated well conditions.' The API-recommended practice for testing oilwell cement provides testing schedules for various well depths and conditions. These schedules are intended to simulate down-hole conditions during cementing. They provide a rate at which both temperature and pressure are increased until the estimated circulating conditions are reached. These testing schedules represent circulating temperatures for an average well and, although there is flexibility in choosing the test schedule that most accurately simulates the temperature of an individual well, it still is not possible to consider all the well conditions that will affect the bottom-hole temperature. Many factors affect cement temperatures; for example, the length of time a well has remained static prior to running casing and cementing, the circulation time, the temperature of fluids used in cementing, fluid density and flow properties of fluids. The pumping time for a typical retarded cement could vary from 2 to 4 hours with a 10F change in testing temperature. Variations in pumping time are the most critical in highly retarded cements used in deep, hot wells; yet, predicting bottom-hole circulating temperatures is more difficult in these wells. This work was conducted to develop a means of calculating circulating temperatures as a function of well depth, casing and hole size, pumping rate and time, fluid and reservoir physical properties and thermal status of the well. PREVIOUS WORK In 1941 Farris reported on a study to develop information leading to a more practical laboratory evaluation of oilfield cementing mixtures and performance.' It was then recognized that the pressure factor was being neglected,

By Josiah Royce

To evaluate chemically the sample of rock obtained by diamond drilling, it has long been recognized that the analyses of the two components of the sample, core and sludge, must be given appropriate influence in computing the average analysis of any unit of depth. The purpose of this investigation is to set forth what means are available for apportioning the effect of core and sludge on the final analysis, what variables affect the problem, and what combination of applied mathematics will closest approximate the truth under each condition as these variables proceed within their limitations. A drill hole is bored in iron ore exploration principally to test variations in rock composition with depth and is usually directed as nearly normal to the bedding of a horizon to be tested as possible. This practice has a tendency to minimize variation in composition laterally which in any event is not likely to be great. It is obvious that the opportunity for change in analysis of a particular rock is not statistically as great radially in a diamond drill hole where the distance in which such a change may occur is from 0.719 in. (EX bit) to 1.469 in. (NX bit) as there would be longitudinally even in a' run as short as 5 ft. Variations in composition of bedded or layered rocks are usually greater normal to the bedding than parallel thereto. Even in massive rocks, like porphyries, variations are functions of distance. Hence. in either case, variations along the hole are of greater effect than across it. Let us examine Fig 1 briefly to observe a cross section of a unit of depth of a typical diamond drill hole. If we neglect radial change in chemical composition, which we have seen is small compared to lengthwise variation, we can see that if core recovery was 100 pct, the core and its surrounding area, which would be recovered as cuttings (assuming 100 pct sludge recovery), must analyze the same if the sampling is perfect. This is the foundation of this paper, namely, that if core recovery is complete we may assume that the core constitutes as nearly as possible a perfect sample of the ground drilled. Now let us pass to the methods of weighting core and sludge in the final analysis and then develop each in turn. One might employ core analyses only, sludge analyses only, or apportion the influence of each by one of several methods. The most common apportionment is by direct proportion to relative theoretical vol- ' ume occupied by each component in the cylinder hollowed out by the drill, known as the Longyear formula. Another logical treatment would be to consider core and sludge in the final analysis according to the weight of each recovered. This procedure was elaborately set forth and refined by R. S. Moeh1man.l Then to be sure that we have embraced all the possibilities, we must admit that some other method or methods may be devised empirically or by mathematical maneuvers. Should a drill machine be capable of recovering 100 pct of the core in all types of rock, certainly core alone need be analyzed and no complicated mathematics are required; but although some companies have had fair success in obtaining high percentages of core in certain homogeneous ores on the Mar-quette Range, their same methods have proved disappointing on the Menominee, Cuyuna, and Gogebic Ranges where the iron formation often varies widely from flinty chert beds interstratified with soft hematite to wholly leached ore material composed of an unpredictable mixture of hematite and limonite with occasional zones of sugary, recrystallized chert. In spite of numerous mechanical improvements in core barrels, few drilling programs can count on complete core recovery. The sludge alone might be analyzed but for practical reasons this is inadvisable when core is obtained due to the numerous opportunities for contaminating or losing portions of the cuttings. The Longyear formula involves a weighting of the core and sludge in proportion to the theoretical volume of each, that is, where the volume of the core recovered is one-third of the total cubic volume of the cylindrical hole made by the drill, the analysis of the core is given one-third of the weight in the final analysis. This approach to

Jan 1, 1950

By F. W. Archibald

The American Smelting and Refining Co. has standardized its copper converting practice to attain a maximum unit blister production with a minimum of refractory consumption by careful location of the tuyeres and by applying magnetite coatings on the hard-burned magnesite brick linings. THE American Smelting and Refining Co. operates four primary copper smelters in the United States with a total of 17 Peirce-Smith type converters; 15 of them are 13 ft in diameter by 30 ft long, and two are smaller. Some details of operations vary with locale; however, fundamentals of design, operation, and maintenance are common to all plants. All converter shells are l-in. thick except for one new converter with riding rings on the ends which has a shell thickness of 1 1/2 in. More tuyeres can be installed with rings on the ends and hence more air can be used. Welded construction is replacing riveted. Minor shell repairs are made after each campaign. Principal causes of complete shell replacement are warpage and cracking resulting from localized over-heating. A 13x30 ft shell is being replaced after 34 years of operation and a total production of approximately 750,000 tons of blister. Converters are driven by 80 hp DC motors through company-designed worm gear reducers. Rotation is 0.38 rpm which permits the skimmer to spot the converter quite accurately for skimming slag. At three of the plants, protection against unscheduled air or power failures is afforded by the installation of emergency drives, consisting of auxiliary air motors or storage batteries. In order to avoid excessive splash out of the converters, the converter mouths are located as far back on the shells as existing flue facilities will permit. At one plant, the back of the mouth is only 13" to the rear of the vertical center line of the converter,. whereas it is 28" at another plant. Newly-lined mouth areas vary from 36 to 44 sq ft with effective operating areas about 25 pct less. It is important to keep the converter mouths as clean as possible. Dirty mouths create back pressures in the converters and as a consequence the tuyere air volumes are reduced. Mouths are generally cleaned by bumping with an empty ladle. Small mouth-cleaning rams have been used but unless extreme care is exercised the brickwork may be damaged. After considerable experimentation, the plants standardized tuyere elevations at 4 to 4% in. below horizontal center line at the shell with a downward pitch of about 13/16 in. per ft of length. Tuyeres are spaced at 6 in. centers except at the riding rings where there are no tuyeres. With this tuyere location, several of the plants now freeze magnetite slag in the bottoms, fronts, and backs up to the bottom of the tuyeres to control the internal shape of the converter. This has the effect of improving the agitation and mixing so that there is a marked increase in converting speed besides affording protection to the brick lining. Currently, the trend is to increase tuyere diameters from 1% to 2 in. to increase the air flow. At present, all converters are hand-punched but one converter is being equipped with a set of mechanical tuyere punchers. Rods for punching are % in. hexagonal smelter bar upset to ll/s in. and rods for cleaning tuyeres are upset to about 1% in., or larger, depending upon the tuyere diameter. Two of the plants use pneumatic reamers for cleaning the tuyeres between charges to minimize disturbing the coating on the inside of the refractory lining. Most of the puncher's platforms are pneumatically or hydraulically mounted so that a convenient punching position can be maintained regardless of tuyere position. For normal operations, tuyere air pressures vary from 15 to 13.5 psi, although some cycles such as magnetiting require pressures down to 8 psi. Air requirements vary from an average of 25,000 cfm on the newer installations down to 12,000 cfm on the older ones. Converter hoods are designed to protect the punchers from sparks, splash or hood accretions as well as to prevent the escape of objectionable

Jan 1, 1955

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953