Search Documents

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

Jan 1, 1883

By Marvin J. Udy

THREE GENERAL REASONS exist for applying metallic coatings to steel: to improve its appearance, to resist corrosion, and to resist wear and abrasion. Coating steel with other metals to improve the appearance and to resist corrosion is an old practice; coating for resistance to wear is one of the newer development's' that has become of importance with the development of chromium plating. Coating for improvement in appearance is practically confined to electroplating. Metals like copper, nickel, silver, chromium, cadmium, zinc and tin, because of their pleasing color, are used for this purpose. But these metals are never quite corrosion-proof, except cadmium and zinc, when applied directly to steel. Improvement in color or appearance must be permanent and therefore corrosion-resistant and tarnish-proof. For this reason, with the exception of cadmium, zinc and tin, the above metals are used in combination to obtain appearance and resistance to corrosion. Resistance to tarnish is dependent on the property of the particular metal. Chromium, being nontarnishable, has made it possible to obtain combination coatings of copper, nickel and chromium, copper and chromium, or nickel and chromium, which improve the appearance and also resist corrosion and tarnish. Such coatings find a wide field in decorative work particularly the copper-nickel-chromium combinations, and when properly applied are very satisfactory.

Jan 1, 1932

By F. R. Archibald, F. C. Jackson

The. prospect of winning aluvinum from clay was recorded almost a century ago at a time when the metal was no more than a curiosity.$ As the industry developed, and it has probably developed faster than that of any other metal, the expanding need for raw materials was adequately met by the ample supplies of bauxite ore. As with the other metals older in industry, however, lower grade ores have gradually entered the raw-material field through improvements in ore dressing, insufficienoy of high-grade ore supplies, favorable geographic location, or national necessity for domestic supply. So with aluminum, or alumina, which has been established as the requisite intermediate, the time may have come when a satisfactory process, with favorable location and suitable raw materials, can hold a sound place both in metallurgy and economics. It is the purpose of this paper to describe the Ancor process and its proposed application in treatment of clay in a plant now under construction at Harleyville, South Carolina, by the Defense Plant Corporation. Development of the AncoR Process The Ancor process has developed through successive stages of laboratory investigation, pilot-plant demonstration using neph-eline syenite and pilot-plant demonstration using kaolin-type clay from South Carolina, and is now in preparation for unit trial on an operating plant basis using the latter material. The laboratory studies were carried out over a number of years in the laboratory of the American Nepheline Corporation in Rochester, N. Y., and for the same company in the ore-dressing laboratory of Beattie Gold Mines, Que. Ltd. at Dupar-quet, Quebec. Both companies are associated with Ventures Ltd., Toronto, and its associated American companies. The work was originally undertaken with a view to recovery of alumina and alkalies from nepheline syenite as an adjunct to the American Nepheline Company's established business in the glass and ceramic trades, but as a process developed the possibility of application to clay and other aluminous raw materials became apparent and the laboratory studies were broadened to include these as well. Under the more pressing impetus of wartime needs and possibilities, pilot-plant operations were undertaken at the Canadian Bureau of Mines Ore Dressing Laboratories in Ottawa, and for purposes of demonstration under joint sponsorship of the Canadian Bureau of Mines, The American Nepheline Corporation, and The Aluminium company of canada Ltd. Upon completion of this program, of

Jan 1, 1944

By Charles H. Moore

When lime and magnesia are used as fluxes in the smelting of titaniferous ores fluid, digestible slags low in iron oxide and high in titanium dioxide are produced. The mineral phases present in such slags are (Fe,Mg)O.2TiO2, CaTiO3, and minor amounts of silicate glass (or its devitrification products). The flux additions are added to the ore in relative amounts to crystallize a ratio of (Fe,Mg)O.2TiO2 to CaTiO2, of near the eutectic proportions of 60 pct (Fe,Mg)0.2TiO2 and 40 pct CaTiO3. FeO-Ti02 (ilmenite) remains present in the slag until the FeO content is reduced to approximately 8 pct. Op- timum slag composition is obtained by reducing the FeO content to between 2 and 6 pct. Continued reduction shifts he (Fe,Mg) 0.2Ti02 to oxygen deficient structures classified as MgTi30e and MgTi204. Further reduction yields titanium oxycarbides and freezes the melts.

Jan 1, 1949

By L. E. PORTNER

INCREASING military demands on the petroleum industry have brought into bold relief the crude-oil reserves now available to meet combined military and civilian demands, emphasizing the necessity for a greater efficiency in recovery from what has been discovered than ever before, particularly in light of the absence of new discoveries. This situation-and the fact that the industry, as well as members of the Government charged with governing oil production, desire to meet all crude-oil demands made of the industry with the least loss in tangible reserves through production practices-paves the way for increasing application of sound principles of production engineering and conservation.

Jan 1, 1944

By R. L. Bowron

GROWING use of basic slag in the agricultural industry is of special interest and importance to the iron and steel industry of the Birmingham district, providing an increasing outlet for this by- product. Such use of basic slag was first developed in England about fifty years ago where it soon became wide- spread. About twenty years ago the Tennessee Coal, Iron & R. R. Co. began its production in the United States after exhaustive tests had demonstrated its high value here as in Eng- land. It is particularly valuable on heavy clay and acid soils, improving their physical condition, increasing their alkalinity where that is desirable, and providing soluble phosphate and small amounts of manganese to soils deficient in these respects. Its use in agriculture is growing as its advantages are becoming more widely known.

Jan 1, 1937

By Harry M. Mikami, Harold A. Heiligman

The term chromite is often used to cover all chrome ores and concentrates which are the designations actually employed by most industrial users and producers. Chromite is, of course, the predominant mineral in chrome ores which are aggregates of chromite and gangue minerals, most commonly magnesian silicates. Most chrome ores now used are petrographically chromitites which is a rock, rather than an individual mineral term. The title of this chapter, following past usage, is meant in the broad sense. Chromite is the only primary commercial source of chromium. This book is intended to deal only with nonmetallic minerals and rocks. Chromite uses are both metallic (ferroalloys) and nonmetallic (refractories and chemicals), but any discussion of mineralogy, geology, and mining is common for all types. A number of the major commercial ores are interchangeable, and their uses are determined by economic considerations. Mineralogy COMPOSITION [Chromite is a term embracing a wide range of chromium-bearing spinel*-group minerals the compositions of which can be expressed as (Mg,Fe2+)0.(Cr,AI,Fe3+ )203.t This can be further generalized to R2+O.R23+03 and the molecular RO: R,03 ratio is generally close to one. The exact composition may be arbitrarily expressed as a solid solution of six end-members, MgAI2O4, MgCr2O4, MgFe2O4 FeCr2O4, FeA12O4, and Fe2+.Fe23+04 with the proportions of each stated or plotted in the six-cornered prism of Johnston and Stevens61 or this scheme may be simplified to comprise only three endmembers making up a composition triangle, Fig 1. [ ] FIG 1-Triaxial composition diagram showing molecular compositions of chromites listed in Table 1. The RO.Fe2O3 corner includes Ti02 norms listed in the table. Note that the high-alumina chromites (1, 2, 3, 9), form a cluster well apart from the high-Cr2O3 chromites. There is a tendency for high-iron chromites to be higher in Fe2O3 + TiO2 but it is not a consistent or systematic relationship. The MgO/RO ratio must also be known to characterize the chromite chemically. Simplest and most convenient method is Thayer's' in which a chromite such as (Mg.65Fe.352+)O.(Cr.40Al.50Fe.103+)203 would be written as (Mge,) Cr eAlo. The molecular pro- portions of ferrous and ferric oxides can be seen at a glance as the divalent and trivalent oxides]

Jan 1, 1960

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By AIME AIME

ON MAY 22 the American Institute of Mining and Metallurgical Engineers will commemorate the sixtieth anniversary of its founding at Wilkes- Barre, Pa., in May, 1871. The Directors have transferred the May meeting of the Board to Wilkes-Barre, and the Pennsylvania Anthracite Section has invited as many members of the Institute as can to be present at this time and to join with their fellow-engineers at Wilkes-Barre in the inspection trip through a portion of the anthracite district that has been planned. Ac- cess to Wilkes-Barre is easy, from nearby points, over excellent automobile roads, or by train. The distance from New York is only about 140 miles. , It is hoped to engage a special car for those travelling by train from New York, which will leave the Pennsylvania Station over the Lehigh Valley Railroad at 11:50 p.m., arriving in Wilkes-Barre the next morning. Return can be made from Wilkes-Barre by sleeper the same evening, arriving in New York Saturday morning. Other trains are available for those who prefer a daylight journey.

Jan 1, 1931

By H. C. Rickaby

BY August 1944 Canada expects to be shipping 56 percent hematite ore from its new Steep Rock iron mine, via Port Arthur on Lake Superior, to the steelmaking centers in Canada and the United States. This is indeed welcome news to steel men, especially if they operate open hearth furnaces, as the Steep Rock ore is a high-grade lump and will be valuable as charge and feed ore. But better news is the fact that this first big producer of high-grade hematite ore in Canada, since the exhaustion of the Helen mine in the Michipicoten area north of Lake Superior in 1918, has a proved ore body of 16,757,000 long tons and a probable ore body of 14,000,000 long tons, thus giving an over-all total of 30,757,000 long tons and assuring production for a number of years to come.

Jan 1, 1943

By E. W. Engelmann

RAPID progress has been made during the past year in the copper mills throughout the country. Particular efforts have been made to increase the fine-grinding efficiency by the installation of larger classifying units operating in closed circuit with ball mills, such as the 78-in. high-weir Akins installation at the Phelps Dodge plant at Ajo, Ariz.; also the Type "FX" Dorr classifiers of Nevada Consolidated at McGill. Nev. and the "FX" Dorr bowl classifier of the Braden Copper Co. in Chile. Some of the copper milling plants in the Southwest, such as Chino in New Mexico and Ray Con. in Arizona, have replaced rolls operating wet in their fine-grinding circuit by rod mills. At Hollinger primary rod mills were formerly used in open circuit followed by pebble mills in closed circuit with classifiers. They now have primary ball mills in closed circuit with large extra heavy classifiers and no secondary mills. This new installation is producing the same grinding on 5000 tons per day with a reduction in cost of nearly 4c. per ton. At the Braden plant, in Chile, short-head Symons crushers have replaced 54-in. rolls, thereby in- creasing crushing capacity with some saving in maintenance cost.

Jan 1, 1939

By Walter C. Holmes

IN the recently published book entitled "Man in a Chemical World," by A. Cressy Morrison, the several pages discussing explosives were included in the chapter on "Serving Industry." Such a classification is entirely correct, as blasting explosives function only as a tool for accomplishing certain useful work, a tool which is completely destroyed in one use. Explosives are so important to industry and to modern society, in fact, that it seems impossible to imagine the existence of civilized nations without access to commercial explosives as ready servants. Two main types of explosives are now in use, the low-velocity or deflagrating type, such as black powder, which is adapted for use in coal mining and other applications where a slow, heaving effect is desired, and high explosives of the dynamite type,

Jan 1, 1938

By D. I. Cameron

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at 1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystal- line thoria.

Jan 1, 1962

By T. S. Lundy, J. I. Federer

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystalline thoria.

Jan 1, 1962

By L. J. Buck

Lead smelting in the ore hearth, first practiced in Europe, whence the traditional name "Scotch hearth, and later developed in America to its present efficiency, is based upon the roast reduction process and is applicable to relatively high-grade galena concentrates. The roast reduction process embraces not only the roast reactions: 2PbS + 70 = PbO + PbSO4, + SO2 PbS + 2PbO = 3Pb + SO2 PbS + 2PbSO4 = Pb + 2PbO + 3SO2 but also, by reason of the addition of extraneous fuel, the reduction reaction: 2PbO + C = 2Pb + CO2 Thus in the ore hearth the roasting of lead sulphide, forming lead oxide and lead sulphate, the reaction of lead oxide and lead sulphate with lead sulphide producing lead, and the reduction of lead oxide by carbon producing lead, go on simultaneously. The Ore Hearth Function of the Ore Hearth.—The ore hearth, through the roast reduction process, provides for the extraction of lead and the immediate disposal of the smelting products—fume, hearth slag and lead, all of which are subsequently treated as follows: the fume is recovered in the flue system and baghouses, mixed with concentrates, and returned to the ore hearth in the form of ore mix; the hearth slag is smelted in a blast furnacc for the further recovery of lead; and the lead is refined and cast into a marketable product. Concentrates Amenable to Ore-hearth Smelting.—Only concentrates that are high in lead content, 70 per cent or more, are ordinarily considered amenable to ore-hearth smelting. Silica should not exceed 2 per cent and iron is allowable only to 4 per cent. These slag-forming constituents occlude both sulphide and mctallic lead, prevent the elimination of sulphur and decrease the lead extraction. Lime and magnesia are beneficial in that both favor a dry slag, promote elimination of sulphur, and prevent occlusions of metallic lead.

Jan 1, 1937

By Charles Will Wright

ALTHOUGH the United States has long led all other countries in both the production and consumption of mineral products, the trend seems definitely toward an increasing dependence upon foreign sources of supply. This is not to take the position that we are either a have or a have-not nation. For years we shall continue to secure a large proportion of our needed minerals: from our own mines, but we must face the fact that this century has seen "a more thorough and intense development of the mineral resources of the United States and a greater depletion of its irreplaceable mineral reserves than has occurred in most other countries. An audit of our mineral production given in the attached charts discloses the extent of our deficiencies. Because of these facts, low-cost foreign sources offer a promising field for the investment of a portion of our mining capital and an opportunity to obtain for the United States a greater supply of strategic metals and minerals. How. ever, to reach this end, the industrialist investing in the foreign field must have the full co-operation and strong backing of the Federal Government and the involved Federal agencies.

Jan 1, 1947

By Paul E. Blackburn, Joan B. Berkowitz-Mattuck, Edward J. Felten

The oxidation behavior of MOSi2 has been studied between 450° and 650°C, the temperature region where "pesling" occurs. Disintegration ("pest-ing") of MoSi2 is shown to occur in the presence of oxygen, but not nitrogen, carbon dioxide, carbon monoxide. or argon. The rate of disintegration is extremely sensitive to oxygen pressure. The crack density of polycrystalline MoSi2 increases ivith lime at temperature. All kinds of cracks are observed: THE excellent oxidation resistance of MoSi, at temperatures of 1000 to 1700°C promises to have important technological benefits. However. the ap- Ihose which are confined within a single grain, those that ci'oss grain boundaries transversely, and those that follow grain boundaries. Laue photographs verify the existence of Iranscryslalline cleavage. Single crystals of MOSi2 do not "pest". Tlrcd solrlbility of oxygen in MoSi2 is extremely low, no lattice changes being observed as a result of exposure of MoSi2 to oxygen in the "pest" temperature range. plicability of MoSi2 is somewhat restricted by the occurrence of a completely destructive oxidation of the intermetallic phase at intermediate temperatures (300" to 6003C). This phenomena was ternled to be the "MoSi2 pest" by Fitzer who first observed it.' Molybdenum disilicide is a metallic material in both physical appearance and electrical properties.

Jan 1, 1965

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,''' who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968