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By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By H. W. C. Prommel

While Utah remains an unimportant factor in oil production, exploratory drilling was carried on in six widely separated areas, extending from the southwest to the northeast corner of the state. One new gas field, the Last Chance or Starvation Creek anticline in Emery County, and two new gas horizons in the Clay Basin field of Daggett County, were thereby discovered during 1934. Exploratory Drilling South Central Utah Emery County—Last Chance Anticline.—The test of the Ramsey Petroleum Corporation in sec. 18, T.26S., R.7E., on the apex of this anticline (vert. closure 700 ft.; area within closing contour line, as mapped by U.S. Geological Survey, 26,000 acres) encountered gas in the Moenkopi formation of lower Triassic age at depths ranging from 2530 to 2863 ft. The total thickness of sandstone, sandy shale and -limestone beds in which gas was encountered is approximately 50 ft. The well was tested at a depth of 2755 ft., gaging 21,000,000 cu. ft. of gas, R.P. 410 lb. The well is being plugged back to the lowest gas horizon at 2771 ft. from a total depth of 3168 ft. Gas from this well probably will be used for the drilling of a second well structurally lower, to test the oil possibilities of the Moenkopi formation as well as of the upper and lower Pennsylvania formations, of which the latter so far remains untested in South Central Utah. The well was not drilled deep enough to determine more definitely the western margin of the petroliferous Paradox Basin of lower Pennsyl-vanian age of southeastern Utah. Woodside Anticline.—This field, lying immediately northeast of the San Rafael swell, contains, according to maps of the U.S. Geological Survey, 8380 acres within its lowest closing contour line 700 ft. below the apex. A well was drilled by Utah Oil Refining Co. at the apex in sec. 12, T.l9S., R.l3E., during 1924. Gas was encountered in the Moenkopi and Kaibab formations of Triassic and Carboniferous (Permian) age respectively. The flow is estimated at 21,000,000 cu. ft., R.P. 900 lb.,

Jan 1, 1935

By John Birkinbine

In the spring of 1878 the Pine Grove Furnace, located in Cumberland County, Pa., was blown in after lying idle for several years. The fnrnace was constructed in 1770, and for over a century it has been in almost continual operation. The plant consisted in 1877, when the writer was first called there, of a stone stack 32 feet in height, inclosing a shaft and boshes, the latter being 8 feet in diameter. The blast was supplid by two wooden blowing-tubs discharging into a third, having a floating piston sustaining a box weighted to give the desired pressure, the power being furnished by a waterwheel. A small 18-pipe hot-blast stove heated the blast. The furnace was remodelled during the winter of&apos;77-78, and a Weimer blowing-engine with a blowing-tub 5 feet in diameter and 2 feet stroke, and the necessary boilers, were substituted for the wooden tubs and water-wheel. The stack was raised and enlarged, and provided with a bell and hopper having a central drop. Water dam and tymp were added, and general repairs were made. The hot oven, however, was not increased. The furnace had always been operated with charcoal as fuel, and its reconstruction was made with a view to continue the use of charcoal, but provision was made for ample blowing capacity should other fuels at any time be employed. Although liberal arrangements had been made in cutting wood, the stock of charcoal supplied in 1878 was insufficient for the increased requirements of the remodelled plant, and notwithstanding the purchase of some 80,000 bushels from an adjacent idle furnace, there war: riot enough to keep the furnace in constant blast until a new supply could be obtained, particularly as the season was unusually backward. Instead of following the established precedent of many charcoal furnace managers, i. e., blow out every February, it was detemined to continue in blast, using coke as fuel. Accordingly, when the charcoal stock was exhansted, on March 22d, 1879, Connellsville coke was substituted, the change of fuel being made at once; that is, the coke charges followed immediately upon the last charcoal charges. After working a few days, the strike in the Connellsville coke region cut of the supply, and anthracite coal was obtained, a mixture of the two fuels being employed. The strike continuing,

Jan 1, 1880

By Thomas T. Read

REVIEWING the events of the year in mineral industry education, a certain amount of either amusement or irritation, depending upon one&apos;s viewpoint, can be derived front the section dealing with mining engineering in Walter B. Pitkin&apos;s "New Careers for Youth" which appeared during the summer. On p. 102 Prof. Pitkin says "The mining engineer is disappearing .. . because . . . the profits of mining decline rapidly with the age of the mine." In his "Are Too Many Students Taking Mining Courses?" published in the May issue of this journal, W. B. Plank presents statistics showing that there was some decline in student enrollment in mining and metallurgical courses in 1932-3 and 1933-4, compared with 1930-31, but that the decline was proportionate to that in all lines of engineering study combined. Informal reports from Institute officials that have visited tinning schools during the fall indicate that nearly all schools showed an increase in enrollment for the current school year. Pre else statistics will be made available by Prof. Plank at the Annual Meeting. His study last year provided, for the first time, accurate and complete information on the enrollment in mining schools, as well as the number of various courses and the degree granted, and it will be interesting to have comparable figures for this year. Prof. Pitkin&apos;s views on the future opportunities for mining engineers were discussed at some length - on pages 439-4.40 of the November issue of MINING AND METALLURGY.

Jan 1, 1935

By E. S. Machlin

The wzodel of Blandin and Diplunt;, generalized to include a phase factor, is applied to the carbon-carbon interaction in iron. Darken&apos;s "energetic" model is generalized to include not only first neighbor interactions but further neighbor interactions as well. On the bases of these generalized models relations are derived for the activity of carbon in both austenite and ferrite in terms of the carbon-carbon Pair interaction energies. A single function then yields the pair interaction energies consistent with the experimental activities of carbon in both ferrite and austenite. Thus, a simple explanation is given for the observation that the nearest-neighbor interaction between carbon is repulsive in austenite and attractive in ferrite. Certain consequences of this approach are explored. OnE object of the present paper is to attempt to take into account the consequences of electrostatic contributions to the carbon-carbon pair interaction energy for carbon as a solute in iron. Friedel&apos; has shown that oscillations in electrostatic potential are to be expected about a solute atom in a metallic solution. Blandin and 6lant6&apos; have shown that such oscillations yield an interaction energy between pairs of solute atoms that obeys the relation: W{ = A cos(2ftFri + 4>)/(kFri)3 [l] where kF = Fermi wave vector, ri = distance between solute atoms comprising the pair7 <p = phase factor dependent only on electronic nature of solute and solvent, A = coefficient dependent only on electronic nature of solute and solvent. Machlin3 found that Eq. [I] accurately described the pair interaction energy derived from short-range order measurements based on field ion microscope observations of dilute alloys of platinum. He also found that the value of the phase factor $ derived from residual resistivity measurements agreed well with that obtained from the analysis of the short-range order data. Harrison and paskin4 were able to predict the long-range ordering energy of 0 brass using Relation [I] and residual resistivity values to predict the value of the phase factor $. Machlin5 has repeated their analysis and applied it to the prediction of the long-range ordering energy in AgZn and AgCd with excellent agreement between prediction and experiment. Both A and $ are independent of the crystal structure. The Fermi wave vector depends uniquely upon the conduction electron concentration per unit volume in the spherical approximation of the Fermi surface. Thus, Eq. [I] is expected to apply to both fer- rite and austenite with only one set of values of A and $. Mossbauer studies6 yield the result that iron has one 4s electron. We shall make an assumption found to hold previously for platinum3&apos;7 and nikel, which is that only the s electrons are involved in shielding the perturbing potential of carbon. With this assumption, kF = 1.35 A-l. Although A and $ may be obtained from certain mdels&apos;&apos;&apos; we shall take A and $ to be empirical constants in the spirit of Kohn and osko.&apos; Thus, Eq. [I] involves two adjustible parameters. Consequently, two independent relations in A and $I are required in order to evaluate them for carbon as a solute in iron. We may use a recent analysis of Aaronson, Domain, and poundg who showed that Darken&apos;s energetic model,1° as well as others, can be used to describe the activity-temperature data for carbon in iron in both the aus-tenitic and ferritic phases. Darken&apos;s model takes into account only first neighbor pair interactions. For our needs, all neighbor pairs need to be taken into account. It is convenient to generalize Darken&apos;s model. The result for the partition function for austenite is: over the temperature range 800" to 1200°C and where the uncertainty corresponds to one standard deviation. Eq. [4] effectively yields only one relation. Another relation is required to obtain unique values for A and $. One property of Eq. [4] is that it is independent of crystal structure. Hence, data for a iron can be used to obtain another relation. To arrive at this relation we must generalize Eqs. [2] and [3] so that they may be applied to the bcc a iron. The result is that:

Jan 1, 1969

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.&apos;, &apos; They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast&apos; postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,&apos;&apos; a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world&apos;s mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep¬resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geological Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is, one of the most important minerals, was omitted because not more than one or two per cent of the world&apos;s production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By O. W. Ellis

CERTAIN alloys1 that, as a result of quenching, are retained in the form of homogeneous solid solution are known to increase in hardness and strength on standing at room temperature or on heating at slightly elevated temperatures. Other alloys" that, on rapid cooling, are held in the form of homogeneous solid solution (as, for example, certain steels) behave in like manner on heating to somewhat higher temperatures. The observed increase in the hardness and strength of these alloys, referred to as "aging" or as "secondary hardness," is widely accepted as being occasioned, either in whole or in part, by the precipitation in submicroscopic form of such constituents as were held in supersaturated solid solution as a result of cooling in excess of a certain critical rate. In earlier discussions of the cause of age hardening or secondary hardness, the question of the hardness of the precipitated particles does not appear to have been raised. At present, however, the general opinion appears to be that age hardening and secondary hardness are occasioned by the precipitation of hard particles within the supersaturated solid substance.3 The authors may be wrong in their belief that the last is a prevailing opinion. Nevertheless, it is thought that the following experiments,

Jan 7, 1924

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.&apos; In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.&apos; The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.&apos; Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By J. C. Uy, A. A. Burr

IN the primary solid solutions of zirconium-base alloys, there is a striking regularity of the effect of solute valence on the stabilization of the allotropic phases.1 The valences derived by pauling2 are for elements as they are bonded in the solid metallic state. Effects of variations in isotopes, alloying elements, and allotropes on their valences are difficult to determine and such data are presently unavailable. Pauling&apos;s values are somewhat empirical and approximate, but if some definite correlations can be found between those values and experimental observations, this will lend support to the tacit assumption that the possible variations in valence mentioned above are small. Pauling has amassed a large amount of evidence of such correlations. It is the purpose of this technical note to show another application of the Pauling valences and to offer a possible explanation for this observation. The relationship between the Pauling metallic valence of the solute and the stabilization of allotropic phases in zirconium is shown in Table I, which has been compiled from available data in the literature3 plus the results of work done at Rens-selaer Polvtechnic Institute.&apos; The chemical valences are included for comparison. It can be seen that a solute whose metallic valence is lower than that of the solvent tends to stabilize the a phase while one whose metallic valence is higher than that of the solvent tends to stabilize the 0 phase. It should be noted that, inasmuch as the Pauling valences are periodic with atomic number, this is tantamount to saying that the elements in groups I-A, 11-A, III-A, III-B, IV-B, V-B, and VI-B are a stabilizers while those in groups IV-A, V-A, VI-A, VII-A, VIII-A, I-B, and 11-B are ß stabilizers. The chemical valences do not show such consistency. Although the zirconium-rich end of the Zr-Au diagram is not available, it call be expected that gold, having a metallic valence of 5.56, would stabilize the ß phase. At absolute zero, the Fermi energy level is the criterion of equilibrium, i.e., the structure having the lower Fermi level will be more stable. Conse- quently, allotropic transformation occurs in a metal when thermal excitation raises the Fermi level to a point at which the atoms can be better accomodated by a different structure which yields a lower Fermi level.4-6 Thus in allotropic transformation, a change in structure occurs as a result of the change in the energies of the bonding electrons. Since the Pauling valence is the number of bonding electrons per atom, and these are the only electrons whose energies are affected by thermal excitation,* it can be inferred that the introduction of a solute which has a higher Pauling valence than that of the solvent raises the initial Fermi level; consequently, the transformation temperature is lowered. The converse is also true. The fact that at the transformation temperatures this statement is still fairly valid implies that the contribution due to the difference in specific heat terms of the two allotropes is comparatively small.

Jan 1, 1962

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,&apos; size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By T. L. Joseph

BLAST furnaces are most efficient thermally when the C02 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyères, is converted later to C02 depends upon the ratio of ore to coke in the charge and the degree to which C02, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + C02 = 2C0. About 300 to 400 lb. of carbon1 per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower C02 in the top gas. Riche has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher C02 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen enter-

Jan 1, 1936

By J. R. Campbell

A DOZEN years or so ago, the general superintendent of our company, now the president, Mr. W. H. Clingerman, detailed me to make a study of the coal-washing problem and collect data, which threw me into contact with the best washery men of the country. and took me to those districts where the washing of coal for metallurgical purposes is carried out. I investigated many kinds of coal-cleaning schemes, made numerous tests on them, and collected voluminous data, yet I confess frankly that I have had but little practical washery experience and that little has been at the Middlefork washery of the United States Fuel Co. at Benton, Franklin Co., Ill., which was put in operation last fall. While this wash-cry installation may not be the "last word," I am quite sure it embodies some long steps in advance over older designs and constructions. From the washery man&apos;s standpoint, the removal of pyrites, or marcasite, a disulfide of iron, is the one vital problem, and the one productive of the most beneficial results, so far as elimination of sulfur is concerned. Sulfates and so-called organic sulfur occupy quite a secondary -position and are generally lost sight of in coal washing: The elimination of sulfur in coal in the past has usually been accomplished by jigging in water, but lately the use of concentrating tables has been employed with good success, and some mention may be made of the flotation process on fine coal, though hardly considered practicable. Coal washing, is rapidly coming into its own, due to the depletion of low-sulfur coals for coking purposes, and before many years we predict as careful attention being given to the design and construction of coal washeries, ,as is now being given to byproduct plants and other allied industries. Heretofore, coal washing has been considered only as an incidental and a necessary evil-instead of the big problem it is one worthy of the most careful study by men well trained along technical lines and capable of delving into the fundamental principles.

Jan 9, 1919

By Granville S. Borden

MANY complaints have been filed by mine prospectors, explorers and producers about inequities in mining taxation. They have insisted upon improvement, and in the past 35 years there has been some progress. Many of the best taxation provisions made to date are those contained in the Revenue Act of 1951. Mining economics presents special problems, a fact even recognized by many textbooks. Certain provisions have been made to take care of mining taxation rights, but these have been made by Congressional act and do not represent basic, constitutional, guarantees. Despite special provision, in the form of depletion allowances, there remain injustices. The industry faces the problem of gaining adequate income tax allowances for exploration and development expenditures, operating losses, and bonus and subsidy payments. Problems in mine taxation arose soon after the adoption of the 16th Amendment. This amendment gave Congress the power to impose income taxes. Supreme Court decisions against a number of mining companies held that Congress, under its power to tax income, could tax net operating revenue before depletion allowance was deducted. The court also ruled that the right to deduct depletion is a matter of Congressional permission. There is no statute provision permitting mining stockholders to recover their investment out of dividends while the mine is being operated. The Supreme Court did not recognize that part of mining proceeds are actually amortization of the cost of mineral rights. Both these omissions stem from failure to recognize that by its very nature mining consumes its mineral rights and therefore that a part of gross proceeds are not income but recovery of capital. Suppose a Congress unfriendly to mining interests repeals the provisions that allow deductions for depletion. Under such a situation assume that a corporation buys a mineral deposit for $300,000. They mine the deposit and earn an operating profit of $500,000. At the current rates they would pay a Federal Income tax of in excess of $250,000. This venture results in a loss of $50,000 as shown in the table below. For the example given the absence of depletion provisions in income tax law would turn ore into waste rock, because the word "ore" connotes commercially mineable rock. [ ] In retrospect the conclusion is clear: If the Supreme Court had recognized that a part of mining proceeds represent in reality sales proceeds of mineral rights, then profits derived from such sales would have been taxed at the favorable long-term capital rates, instead of being taxed at the high normal, surtax and excess profits rates. It is a question whether percentage depletion allowances offset this tax situation. History The history of depletion allowances has been one of general improvement. The original act did not include depletion, but an allowance at the rate of 5 pct of gross proceeds was provided in 1913. The Acts of 1916 and 1917 allowed depletion upon cost of property, and in 1918 the law was further changed to permit depletion upon cost, or market value as of date of discovery. In 1932 metal, coal and sulphur properties were permitted to elect depletion in percentages of gross income, limited to 50 pct of net income, in lieu of cost depletion. Shortly thereafter the rule was changed and percentage depletion is now allowable in any case where it is higher than cost depletion. Since 1942 percentage depletion allowances have been extended to cover many nonmetals, and in 1951 the rate for coal mines was increased from 5 to 10 pct of gross income. It is interesting to note that these allowances have been retained, and even

Jan 1, 1952

By John Howe Hall

The recently announced run of three years, nine months and eleven days made by a crucible steel melting furnace of the Columbia Tool Steel Co., which is claimed as a world&apos;s record, brings forcibly to our attention the great improvements that have been made in the design, construction and operation of the Siemens regenerative crucible melting furnace since its introduction in this country. Credit for this advance should be given to the furnace designer, the manufacturer of refractories, and the operators, of the furnaces, whose persistent efforts and intelligent co-operation in attacking the problem have resulted so satisfactorily. There are three factors that determine the life of a crucible furnace, or any other furnace for that matter: Design, nature of refractories, and conditions of operation (including the nature of steel melted); and to some extent these factors are interdependent. Thus, for instance, if a crucible furnace is to be operated single turn and allowed to cool off considerably at night, in order to save fuel, the use of clay-brick melting holes may be advisable, since silica brick is not well adapted to endure repeated heating and cooling. But the total life of a clay-brick melting hole is necessarily short. Again, if local conditions such as danger of flood make necessary the building of the furnace largely above ground, so that the radiation of heat is promoted, the cooling down of the furnace over the week ends, when no steel is melted, will be considerable—and the contraction of the furnace that results tends to wrack it to pieces. The character of the metal being melted affects the life of the furnace to a great extent. Low-carbon steels and steels made from iron and charcoal require higher temperatures and much longer melting time than high-carbon steel or steel made largely from scrap; the life of the furnace will be shorter, and the number of heats melted will be much less, when such materials are melted. The figures available, showing the life of furnaces, are for this reason especially not strictly comparative, since the variations in the steel melted undoubtedly affect the life to a greater or less extent. Probably, however, the method of handling is as important a factor

Jan 1, 1914

By W. H. Nielson, L. S. Diaz

Several techniques are presented to adjust small errors inherent in data collected from material balance measurements on the flotation process. The basic technique used is a Lagrange multiplier adjustment of the filtered data taken from the equipment measurements. The raw data are adjusted such that material balances are closed. The adjustments to each data point is inversely proportional to the square of the standard error of measurement. Problem areas in equipment utilization are discussed. Typical results from on-line measurements are presented. This technique can be applied to either on-line process measurements or metallurgical test data.

Jan 1, 1973

William Metcalf, Pittsburg, Pa. (communication to the Secretary*): I am greatly pleased that some one has at last reached what I have long regarded as the only rational explanation yet given of the reasons why steel hardens. Mr. Field claims originality; and doubtless he is entitled to it, but not to priority, mhich must be granted to Prof. John W. Langley.&apos; The difference between them is that Langley says " Tension, probably molecular," and Field says " Tension, probably atomic "; in either case the vital thing after solution is tension. Mr. Field&apos;s argument carries with it the idea of increase of density with hardness; if he mill study the facts farther he will observe that the case is just the reverse; that is, the greater the hardness the less the specific gravity; it was just this fact that led Langley to his conclusion, in mhich I have always concurred. Field agrees with Langley that the first requisite for perfect hardening is complete solution of the carbon, not combination; and all of the facts agree with this conclusion. The fact that increase of hardness causes reduction of density was first brought to my notice some 40 years ago, when Major William Wade was testing Jones & Laughlin&apos;s cold-rolled iron, and I mas his assistant. We found the well-known increase of tenacity, compressive strength, torsional resistance, and hardness. Specific-gravity tests showed that the cold-rolled iron was less dense than the hot-rolled bars. Major Wade was so surprised at this result that he gave me a lot of samples to weigh, saying that he was not satisfied with

Jan 1, 1904

By Frank Feuille, Edward Schuster

As the time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W. Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.&apos; Colombia requires foreigners to agree to be bound by its alien law. In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. alongitsland

Jan 1, 1923

By Edward Schuster, Frank Feuille

As the time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W. Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.&apos; Colombia requires foreigners to agree to be bound by its alien law. In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. alongitsland

Jan 1, 1923