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By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By W. L. Connell, O&apos

The properties of some heavy liquids which can be used in sink-float separations are discussed with major emphasis being given to the halogenated hydrocarbons. Data are presented on density, viscosity, thermal characteristics and the effects of moisture and temperature on the corrosiveness of the liquids towards various materials of construction. The toxicity of these materials, the hazards involved in handling them, and the procedures for handling them safely are also discussed. True liquids have certain advantages over colloidal suspensions for sink-float separation of minerals which makes their use especially advantageous when close separations, fine particle sizes or water-soluble minerals are to be treated. For best separating results, the medium should have an easily controlled, uniform, stable density. Here, true liquids have the advantages of allowing closer control of density and of not requiring agitation to maintain a uniform den- sity in the equipment. Low viscosities are desired in a separating liquid so that rapid separations of fine material can be made. Many liquids have lower viscosities than the colloidal suspensions at operating gravities of 1.4 to 5.0. For economic reasons and to prevent contamination of the product, the separating medium must be easily and completely removed from the ore. Normally, true liquids must be more completely removed than the cheaper suspensions and thus cause more problems in this area. The fact that the medium should not react with the minerals, air, water or the common materials of construction limits the choice of liquids which can be used, but many are available which are sufficiently stable. A more serious objection to the use of true liquids is that many of them present a toxic hazard to operating personnel and users of the product. Most true liquids are toxic to some extent, but modem knowledge of toxicity allows us to recognize the hazards inherent in handling them and enables us to design around them. Three types of true liquids are available for this use: 1) Halogenated hydrocarbons cover the gravity range from 1.2 to 3.3. They are generally more volatile and less viscous than the other liquids.

Jan 1, 1963

By J. C. Osmond

One of the least known geologic regions in the U.S. is the area now called the Basin and Range Province. It is paradoxical that so little geologic information has been compiled for a province that has yielded billions of dollars worth of metals and is currently producing a small amount of oil. Regional stratigraphic studies of parts of this large territory have been published only recently, and regional structural interpretations of even parts of the province are rare in the literature. This, of course, does great injustice to the earliest workers: Gilbert,1,2 Russell,9 Le Conte,4 Spurr,5 Louderback,8 and others, who recognized the area as distinctively different from the rest of North America. Their simplified picture of the structure of the ranges and the province as a whole is the groundwork for present understanding and has never been superseded. Since their early works, however, geologic data from the province has consisted largely of detailed reports of widely scattered mining districts. Each district has been described as though it were an island in an unknown sea. More recent syntheses of the geologic history have been prepared by Lindgren,7 Ransome,8 Nolan,9 Bill-ingsley and Locke,30 Longwell,11 and Eardley.12 The tentative nature of the present interpretation, which treats the structural evolution of the Utah and Nevada area, must be considered in light of the scarcity of geologic information from the province as a whole. The methods of interpreting tectonic history from stratigraphy are based largely on the concepts of Marshal Kay.23 Discussions with Hoover Mackin also have aided in organizing the Tertiary history. TECTONIC AND STRATIGRAPHIC SETTING Two approaches to the subject of the tectonic history are possible; they correspond to looking through opposite ends of a pair of binoculars. One involves an expansion and extension of detailed work and the other an interpretation based on regional geological relationships. It is believed that the second approach, used here, is not in disagreement with detailed observations. The area of the Basin and Range Province is shown in Fig. 1. Within this area middle Tertiary to Recent high-angle faulting has controlled development of mountain ranges and valleys. Only the part of the area north of Las Vegas, Nev., and south of the Snake River in Idaho will be considered in this article. Within this part of the province most of the ranges trend north-south. Approximately two thirds of the area is covered by late Tertiary to Recent valley fill and lake deposits.

Jan 1, 1961

By P. G. Hallof

Only recently has the term Induced Polarization found its way into geophysical literature. Schlumberger first mentioned the possible use of the induced polarization effect in one of his early papers. Later, induced polarization was the subject of several university theses, such as Seigel's at the University of Toronto and Bliel's at the Michigan School of Technology. In addition, a group at the New Mexico School of Mining and Technobgy has done work on induced polarization. There is very little to be found in print on the subject of induced polarization. Several papers have been presented at meetings, the 1958 AIME and SEG* conventions, for instance, on laboratory measurements of the effect and theoretical considerations useful in the interpretation of field results. This paper is the first attempt to present actual field results which show the usefulness of induced polarization as a prospecting technique. There are several phenomena that can cause polarization when electrical current is passed through the ground. In a paper presented at the 1958 SEG* meetings Professor T. R. Madden of M. I. T. demonstrated that only two of these gave rise to appreciable effects. The first is a result of the membrane and diffusion effects in a sandstone that contains appre- ciable amounts of clay minerals. The unbonded charges associated with the clay mineral forma material that passes positive and negative ions with different mobilities. When current is passed through such a system for some period of time, polarization results. The second phenomenon, which gives rise to very much larger polarization effects, is the one used in the new prospecting technique. These effects are a result of the blocking action or polarization of metallic or electronic conductors in a medium of ionic solution conduction. This electrochemical polarization, called "the over-voltage effect" by electro-chemists, occurs whenever electrical current is passed through a volume of rock which contains metallic minerals such as base metal sulphides. This polarization at metallic interfaces in ionic solutions depends upon the chemical energies necessary to allow the ions to continue the flow of current by giving up or receiving an electron from the metallic surfaces. The energy stored in this reaction isanalogous to that stored when a condenser is charged. If a d. c. current flowing through such a system is interrupted, the polarization can be detected as a small, decaying current that flows after the applied current is discontinued. The decaying potential measured is a result of the current flow caused by charges returning to their equilibrium positions from the positions they assumed under the applied potential field. Because of the polarization, there is an excess of change at each metallic interface. There is an alternate method of measurement of the induced polarization effect. The electrical

Jan 1, 1961

By J. M. Weehuizen

Complete details are given of the drilling method by which two shafts were sunk at the new Beatm'x mine of Staatsmijnen in the Netherlands. The nature of the rock strata in the Dutch mining district determined choice of the drilling rather than the freezing method. Data for each step and details of the equipment used are given in the illustrations. Staatsmijnen was founded in 1902 with government financial backing, but it is run as a private enterprise, on a commercial basis, with the normal fiscal obligations. The company now has four mines in operation with annual outputs amounting to 7 1/2 million tons of coal. In 1952 it was determined that a new mine—the Beatrix—would be opened. Details of the shaft-sinking operation are described in this paper. SHAFT LOCATION The coal-bearing carboniferous rock in the Dutch mining district is overlain almost completely by soft water-bearing strata, which at the site of the new shafts are about 1600 ft thick. The sinking of the new shafts through this soft water-bearing overburden (Fig. 1) is a costly and time-consuming affair. From the two availaible sinking methods: 1) Poetsch's well known freezing method or 2) the drilling method of Honigmann-de Vooys, the latter was preferred, not only because of its relative cheapness, under the prevailing conditions, but primarily because by using the drilling process, a special type of shaft lining of steel, concrete, and bitumen could be used. The new shafts, located 330 ft apart, have an inner diameter of 18 ft, 4 1/2 in. The boreholes, which have a diameter of 25 ft and which were drilled through nearly 1600 ft of overburden and some 100 ft of carboniferous, each contain more than 29,000 cu yd—by far the largest in the world. DRILLING METHOD The drilling method is based on the use of mud-flush—a thin mixture of clay and water—to keep the borehole filled during the entire drilling period and during insertion of the lining (Fig. 2). The pressure of the mudflush against the borehole wall is greater than that of the water in the surrounding

Jan 1, 1961

By Roger L. Beals, George A. Tweedy

I. INTRODUCTION. THE results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time, hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data Pan- Amalgamation. Cyanidation. 1905. 1907. 1903. Tons treated, . . 51,387 53,983 69,300 Value per ton (U. S. currency),. $10.75 $8.39 $8.28 Extraction, per cent., 65.00 88.50 S7.45 Extraction, per ton. .- $7.00 $7.4.; $7.24 Total cost, per ton treated, 6.50 4.311 4.01 Profit, per ton treated, . . 0.50 3.07 3.23.;

Feb 1, 1910

By George Bell

THE mine and milling plant of Demonstration Gold Mines, Ltd., is near the city limits of Baguio, Mt. Province, P. I. The mine road connects with the main highway to Manila. The nearest railway point is near sea level, approximately 40 miles distant. The Baguio district is very mountainous and has one of the heaviest rainfalls in the world. It is therefore difficult to maintain roads or to impound tailings and mine dumps. All supplies are trucked into the district direct from Manila or the nearest railway point, which means uncertain deliveries and high freight rates. Installation of equipment is difficult and costly. The average elevation at the mine is 4000 ft. and the climatic condi-tions.are ideal except for a three months rainy season. The company generates its own power for mining and milling opera-tions with three 400-hp. Ruston Diesel engines direct connected to 250-kw. General Electric alternating current generators. Labor conditions have been excellent, although at present social security laws are causing some unrest. Labor receives a higher average wage rate in this district than other labor in the Islands. The com-pany also furnishes free living quarters, hospitalization and work-men's compensation. Taxation has been reasonable up to the present time, but some of the new mining legislation may make it difficult to operate and pay dividends. The future depends largely upon the continuation of $35 gold and the political outcome in the Islands.

Jan 1, 1939

By Wendell S. Williams

Single crystals of TIC doped with boron at high temperat~ires develop second-phase inclusions. The inclusions are in the form of lamellae lying parallel to {l 11 } planes of the Tic matrix and can be vevealed by etching [100] cleavage faces of the boron-doped Tic crystals. measurements of the critical resolved shear stress. t, of TIC crystals containing such inclusions showed that the ropid drop in t wilh increasing temperatu.ve found for pure Tic was greatly reduced. At 1600°C, the inclusion containing crystals had a value of t five limes that of pure Tic. The hardening effect also was found to inhibit hot pressing of TiC powders containing boron impurity. Thermochemical and crys-tallographic arguments suggest that the inclusions are TiB2. The boron content of the hardened carbide is a few tenths of 1 pct. TITANIUM carbide is noted for its high room-temperature hardness. However, measurements of the critical resolved shear stress, T, of single crystals of Tic at high temperatures have shown that t decreases exponentially with increasing temperature.' This temperature dependence of t is attributed to thermally activated dislocation mobility limited by a large Peierls stress.' In turn, this large Peierls stress is believed to be a consequence of strong co-valent and ionic binding in Tic. The rapid drop in 7 with increasing temperature, characteristic of pure Tic, is lessened by the introduction of second-phase inclusions. Exposure of Tic to boron at high temperatures produces such inclusions. A report of the influence of boron on t in Tic is presented, followed by a discussion of the nature and formation of boron-containing inclusions in Tic which are believed to be responsible for the hardening effect. I) CRITICAL RESOLVED SHEAR STRESS OF BORON-DOPED Tic CRYSTALS Tic single crystal boules grown by Union Carbide Corp., Linde Division, were doped with boron by placing them in a carbon crucible packed with boron powder and heating in a vacuum furnace to 2000°C for 1 hr. Samples 1 by 1 by 3 mm were cleaved from these doped boules. High-temperature compression tests' were made on these samples to determine the critical resolved shear stress as a function of temperature . The rapid drop in critical resolved shear stress found for pure Tic crystals' did not occur: tests indicated that the boron-doped crystals at 1600°C had values of T equal to those of pure Tic crystals heated to only 1100°C, Fig. 1. No difference in the shape of the individual stress-strain curves was produced by the boron doping, but the stress scale was multiplied by a large factor. The hardening effect of boron in Tic probably extends to temperatures lower than those used in the present work (1100°C minimum). At room temperature, however, the influence of boron is difficult to determine because the stress required for gross plastic flow in pure Tic is SO high that in practice fracture cccurs first. Microhardness is the only test that can give an indication of the yield stress in Tic at room temperature. such measurements were made5 on boron-doped Tic; the matrix had a hardness value

Jan 1, 1967

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By Fred D. Wright, Philip B. Bucky

FOREWORD By E. D. Gardner[$] THE present known petroleum reserves are limited, and unless important new fields are discovered the Nation will be dependent, in the not too distant future, upon imports or upon synthetic liquid fuels to supplement domestic petroleum supplies. As a national defense measure, it would appear desirable to develop a substitute source of liquid fuels within the borders of the country if new discoveries of petroleum should prove disappointing. Congress undoubtedly had this in mind when it passed the Synthetic Liquid Fuels Act (78th Congress, approved April 5, 1944). The act directed the Bureau of Mines to construct and operate demonstration plants for producing synthetic liquid fuels from coal and oil shale, and from forestry and agricultural products. As a part of this program, the Bureau of Mines has built a demonstration plant at Anvil Points, near Rifle, Colo., for retorting the oil shale, and has developed a mine to supply the plant with oil shale. At the beginning of mining operations, the physical qualities of the oil shale, which would have a bearing upon the selection of mining methods and practices for exploiting the deposits, were largely unknown. A comprehensive mining-research program has been set up to determine the best methods and practices to follow to obtain the lowest overall practicable mining cost for producing the oil shale on a large scale. Unusually low mining costs will be necessary for shale oil to be produced commercially. Consideration now is being given to exploiting a series of flat-lying beds 70 ft thick by a room-and-pillar method of three benches with the advance heading at the top. This report is one of a series giving the results obtained in research on mining problems. INTRODUCTION The structure and physical qualities of the oil shale indicate that the 70-ft interval of the oil-shale measure can be safely mined in open stopes; studies indicate that this method would be the most economical one to use.1 As labor will be a major item of expense, the largest equipment that could be operated efficiently in the workings would be required to obtain the lowest practicable mining cost. It was therefore desirable to know the maximum safe span of unsupported rooms and the size of pillars necessary to support the overburden. This paper describes the work done at the Columbia School of Mines Barodynamic Laboratory in determining the maximum safe unsupported roof spans and the minimum safe pillar dimensions for the oil-shale mine at Rifle, Colo.

Jan 1, 1947

By W. T. Hicks

The oxidation of CbO was studied by a gravimetric technique from 400° to 1200°C in oxygen. In this temperature range the oxidatiotz is characterized by an irlductive period of low oxidation rate, which becomes shorter as the temperature increases, followed by a rapid parabolic oxidation. The oxidation of CbO cannot be rate controlling in the oxidation of Cb metal in the temperature range, 800° to 1200°C. A thin optically inactive layer has been observed between the metal and Cb2O5 layer of Cb oxidized at 700°C or higher temperatures. Figs. 1(a) and 1(b) show the edge of a sample of Cb reacted to 50 pct of complete oxidation at 800°C. Fig. l(a) taken under bright field illumination shows a layer of oxide adhering to the unoxidized metal core. Fig l(b) taken under polarized light shows that this oxide layer is

Jan 1, 1962

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch' observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-' sec-'. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

The Report on the Manufacture of Coke for the year 1880 by J. D. Weeks1 includes an historical account of the early days of coke-making that is very complete and accurate, and but little can be added to it to fully cover the period prior to 1885. The few additional references that have been found follow. The earliest suggestion found about making coke in this country is in a letter from D. M. Randolph to Harry Heth, dated August 22, 1808. Heth was then operating the mines in the Richmond, Virginia coal field and had sent Randolph to England to investigate steam engines for hoisting and pumping and other conditions in the coal industry there. The letter was written in London and said: "I shall explain to you, how, by turning Deep Run fine coal in Coak, to make great profit from what has heretofore been useless. You will do well to ascertain the price and amount of demand for this article throughout the U. States among brewers and manufacturers. I know how also to make every bushel of such fine slaty coal, fetch as much as any of the best grate coal, by turning it into Coak: and that too, after paying all expenses of the process."2 His interest was to use the slack more for domestic purposes than otherwise, probably, although what the interest of brewers would be in coke as fuel does not appear. Nothing ever came of this suggestion, and so far as known, no coal from this field was coked excepting in gas-making. The Plumpsock Iron Works, mentioned by Weeks as having used coke, was advertised for sale in June 1818.3 It was stated that stone coal was the only fuel used at the works, the pit being within 100 yards of the forge. "Three men with a horse and cart are sufficient to raise coke, and haul to the forge all the coal necessary for keeping the works in full operation." The coke, of course, was made in ricks, or heaps, and not in ovens. The first real coke oven in this country was probably built in Connellsville, the coal coming from a mine nearby on Mounts Creek. L. L. Norton operated an iron foundry and was persuaded by his foreman, one Nichols, who came from Durham, England to build a coke oven. The oven was 12 feet square, and the first coke was produced in 1833. Later

Jan 1, 1942

By P. D. White, J. T. Moss, J. S. McNiel

Results of experimental work on the in situ combustion process were first published in this country in 1953' when Kuhn and Koch described results of a three-well test in Jefferson County, Okla. Shortly there-after Grant and Szasz2 described field studies in Nowata County, Okla., in which several modifications of the basic combustion process were investigated by injection of various oxidizing gas mixtures other than air. In the past five years speculation concerning this method of oil recovery has continued, with a number of interesting papers on various aspects of in situ combustion appearing in the literature3,4,5,6,7. However, only one of these' provided actual engineering information on pattern-type field experiments. The primary objectives of the Oklahoma three-well test were to check operation of specially designed electrical ignition equipment and evaluate problems associated with initiation of combustion in a natural oil sand reservoir. Immediately following successful completion of this test in the Pontotoc sand, plans were activated for a second field experiment to be conducted in the same sand a short distance away. The objective of this second field test1 as to establish a relationship between field observations and information derived from laboratory experimentation and computations. Secondary objectives of the test were to develop operating tech- niques and define operating problems, and to obtain information that would assist in the economic and engineering appraisals of the process. Careful planning was required since this test was designed with the hope of providing basic information on the characteristics and operation of a combustion drive. It was necessary to include test facilities which would not only permit precise control and measurement of the process variables but would also provide sufficient flexibility of control to insure that variables in the combustion process could be studied during the course of the test under a wide range of conditions. In order to accomplish these objectives elaborate instrumentation and several control wells were included in the design of the test installation. This type installation was felt to be well suited for an experimental study, but was in no respect intended as a counterpart of a commercial-scale operation. PRELIMINARY LABORATORY WORK An important objective of the field experiment, as stated previously, has been to obtain reliable data on operating variables which might be compared with similar data obtained in laboratory combustion tests. The value of successful correlations between quantities that can be measured in the laboratory and those obtained in a full-scale commercial venture has been well established for other industrial processes. The difficulty of following a process underground should make such correlations even more essential here. Also. approaching the field test phase of development of in situ combustion, it was considered desirable to precede design of test equipment with laboratory combustion studies under a variety of conditions to establish likely ranges of variables. These included temperature, air injection rate, frontal advance rate and produced gas composition.

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By M. B. Bever, A. K. Jena

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2'3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969