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By C. C. Wright, R. J. Day

Although data on the exact tonnage of recoverable coal silt are not known, the quantity produced in 1943 was estimated to be over five million tons for the anthracite region of Pennsylvania alone. Since that time the recovery of the No. 5 buckwheat size previously included in silt estimates has increased greatly thus reducing the total silt tonnage. As a compensating factor, however, the methods of recovering silt previously escaping into the rivers and streams have been markedly improved so that the net figure may not have changed materially. Comparable estimates for bituminous coal are lacking, but undoubtedly the silt represents a significant tonnage. With the trend toward increased wet cleaning of the smaller sizes of bituminous coal, it is to be expected that even greater quantities of silt will be available in the future. The raw silt from anthracite collieries usually contains a high mineral matter content, but technological developments in fine coal cleaning have been making rapid advances and it appears probable that more extensive use of these methods will be employed in the near future. Bituminous coal silt in many instances contains a similar high mineral matter content. As with anthracite silt, however, the cleaning of this material, where necessary, appears both technologically and economically feasible. With a view to upgrading the size and value of silt, considerable laboratory and pilot plant work has been conducted by a number of organizations on what is commonly known as pelletization. Actually the process is one of extrusion in which the moist silt is extruded from a die in the form of rods, which usually break into relatively short lengths—a few inches long—as they fall from the die. Fig I is a photograph of some extruded 3/8-in. diam pellets and of the anthracite silt from which they were produced This technique of producing larger sized material from fines is by no means new, having been used extensively by the industrial carbon and clay industries for years.' The application of the process to coal silt appears, however, to be relatively new. The first major program of investigation dates back only to July 1945, when a group of engineers representing the Anthracite Institute, The Pennsylvania State College and the J. F. Pritchard and Co. conducted preliminary tests on the extrusion of anthracite silt at the Floridin Co. plant at Warren, Pa. Since that time these three organiza-tions—individually, together, and in cooperation with other interested groups— have actively pursued work on various phases of the problem. Much of the early history and details of the laboratory and pilot plant work by the Anthracite Institute, has been reported by Mulcey and Eckerd.2 It is the purpose of this paper to report additional information on the process, especially with respect to the factors influencing the quality and use properties of the product, and the current develop-

Jan 1, 1949

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By C. L. Kinney

The rapid increase in the amount of steel produced by the basic open-hearth process is an index of its ability to produce high-grade steel from raw materials of the most, varied physical character and chemical analysis. This inherent adaptability of the process has resulted in a lack of care in the selection of raw materials, so that in far too many cases charges are used of a chemical and physical character not justified by local economic conditions. A practice, or series of practices, should be used that will result in the greatest economy for the plant as a whole; therefore, the operations of blast furnace and open hearth must be considered together. In this paper, an effort has been made to show those variations in both open-hearth practice and cost that follow changes in the analysis of the pig iron arid it may be said that the theoretical costs shown are worthy of careful study and consideration. Carbon, manganese, silicon, phosphorus, and sulfur constitute the principal metalloids in basic pig iron and play the leading role in the production of steel by the basic open-hearth process. The percentages of each of these metalloids, with the exception of carbon, is a variable that has its genesis in the economic relation of the blast-furnace plant to its ore and fuel supplies. As the amount of carbon in the iron is a saturation function of the temperature at which it is produced, the variation in the amount carried is, for any given locality and grade of iron, practically negligible and is so considered in the eight heats discussed in this paper. The melting and refining reactions in an open-hearth furnace, either acid or basic, are essentially oxidizing and vary greatly with the type and age of the furnace, as well as the character of the fuel employed. The outstanding characteristic of the basic process, and the one that explains its predominance over the acid, is its ability to form out of the lime charged and the phosphorus oxidized from the charge a stable

Jan 1, 1924

By J. H. Nead

OBJECT THE experiments herein described were undertaken with a view to investigating thoroughly the influence of carbon on the tensile and impact physical properties of carbon steel. The original comprehensive plan included investigation of a series of steels with varying carbon contents over a wide range of heat treatments. These were to be studied as to their static tensile qualities, and also their resistance to shock as measured by the Charpy impact bending test. A thorough metallographic examination was likewise included in the schedule. The Charpy tests and the metallographic examination have not been completed to date, and are accordingly withheld for another report. All heat treatments, however, have been made, and the static tensile tests have been completed. A description of the procedure of the experiment and the results thus far obtained are therefore reported herein. CONCLUSIONS No attempt is made to draw general conclusions from these experiments, but the curves and the data are submitted as being of general importance and wide applicability.

Jan 12, 1915

ALABAMA Aldrich.-Lloyd, T. W. Anniston.-Carrington, F. G. Klugh, B. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson V. Salmon, h. S. Stuart, Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong. W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Carter, E. Crawford, G. G. Davis, C. B. Dryer. T. B.

Jan 1, 1923

The following list comprises the names of those persons who became members during the period May 10, 1919, to June 10, 1919. ALAYZA, CARLOS Box 850, Lima, Peru, S. A. BALLARD, P. A Surveyor, Midwest Refin. Co., Custer, So. Dakota. BARNEBL, A. J., JR.... Mech. Eng., The Dorr Co., 101 Park Ave., New York, N. Y. BILLINGS, GOODSELL Platteville, Wis. BRONSON, C. B., Mech. & Met. Engr., New York Central Lines, Room 1520, Grand Central Terminal, New York, N. Y. BUNCE, E. H Met., The New. Jersey Zinc Co., Palmerton, Pa. CHARLTON, D. E. A., Editorial Staff, Engrg. & Mm. Journals 10th Ave. & 36th St., New York, N. Y. DAVIS, JOHN N., Supt. of Mills, Engels Copper Min. Co., Engelmine, Plumas Co., Cal. DUKES, GLENN H., Chief Engr., The Sunday Creek Coal Co.,1001 Outlook Bldg., Columbus, Ohio. ERICKSON, ARTHUR .... Engr., United Smelt., Refin. & Min. Co., Mldvale, Utah. FLYNN, A. E Supt., Rand Consolidated Mines, Ltd., Goudreau, Ont., Canada. HIBBARD, WALTER R 63 Ashley St., Bridgeport, Conn. HOBSBAWN, I. BERKWOOD, Cons. Tech. Chem., Messrs. Gibbs. & Co., Valparaiso, Chile, S. A.

Jan 7, 1919

By A. W. Fahrenwald

PRACTICALLY all fine grinding is done in a ball mill or some modification of a ball mill. Millions of tons of material are ground each year. The cost varies from, say, a minimum of 10 c. to a maximum of 35 c. per ton. It is thus obvious that even small improvements, which may result in increased grinding efficiency, would be welcomed by mill operators. A review of literature shows that various phases of the subject have been studied independently by many investigators. Also, it is now a subject of investigation at various laboratories in the United States and in foreign countries. Notwithstanding this extensive investigation, ball milling still remains a subject of some speculation. This paper presents the results of an experimental study of some of the factors entering into ball mill grinding.

Jan 1, 1931

By Charles W. Carter, Alfred H. Bell

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By Alfred H. Bell, Charles W. Carter

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By G. C. Hancock

The operating plant of The Broken Hill Associated Smelters Pty. Ltd. is situated at Port Pirie in South Australia and it treats to finality the whole output of lead concentrates from the mines of The Zinc Corporation Ltd., North Broken Hill Ltd., and aroken Hill South Ltd. at Broken Hill, New South Wales. Lead bearing ores from other sources are also purchased for treatment and lead scrap and residues are treated on a toll charge basis. The present output of the plant is approximately 200000 tonnes of refined lead per annum and there is a substantial production of by-products including refined silver, gold, cadmium, antimonial lead alloys, copper matte and sulphuric acid. Recently the Company commenced the production of zinc by slag fuming and electrolysis from a six million ton dump of lead blast furnace slag, which has been accumulating at Port Pirie for over fifty years. The slag fuming plant contains two furnaces of conventional design, but features a high degree of pre-heat for the blast air and this is obtained by the use of all-metal recuperators. The raw zinc oxide fume produced by the plant is roasted in a rotary kiln prior to treatment in the leaching and electrolysis sections, which follow conventional practice for nigh current density plants. Present output is approximately 36000 tonnes of electrolytic zinc per annum.

Jan 1, 1970

By AIME AIME

AN IMPORTANT innovation in Alabama in the semi-longwall type of coal mining as applied to low-dipping thin seams has been introduced by the Galloway Coal Co., mining the Mary Lee high-ash seam which averages only 26 in. thick. The property is their Mill Creek mine, near Carbon Hill, Ala., in the Warrior coal field. The results, although not final, indicate that roof conditions can be successfully handled by this method without loss of walls, with a rate of recovery much above that possible with the room-and-pillar method, and at the low production cost necessary for this grade of coal. Double cross-headings are turned off a main haulageway on 60-ft. centers and driven 40 ft. wide with thin chain pillars between. These double entries are turned at 525-ft. intervals, leaving a solid block of coal 440 ft. across; that is, from the outside of one pair of headings to the inside of the next pair is 440 ft. The bottom, which consists of hard fireclay, is taken in these entries 8 ft. wide and 4 ft. deep for head room.

Jan 1, 1934

By V. R. Garfias

Although the work on which this paper is based was carried on by the writer as Special Commissioner of the Petroleum Department of the Mexican Government, the opinions expressed are only his personal views for which the Mexican Government can in no way be held responsible. Notwithstanding that the appointment covers all phases of the so-called petroleum question, as the one question of immediate importance was that relating to taxation, it was decided to devote all the time to this phase of the work. The present report has been divided into two closely related parts, the first dealing with the production and marine transportation of Mcxican petroleum, and the second, with the Mexican taxation on petroleum and its products. The writer wishes to acknowledge the loyal cooperation rendered by Mr. M. C. Ehlen, who had charge of the statistical work, and by Miss S. Stern and Messrs. E. P. Heiles and J. E. Morrissey. The aim throughout the work has been to pave the way for a thorough understanding between the Mexican Government and the oil operators and to present a true and clear statement of facts relating to the questions at issue. Mexican Oil Fields Development The salient features in the development of the Mexican oil fields may be summarized as follows: 1901. First commercially productive well in Ebano field. 1902. Tehuantepee field came in; Diaz Government granted concession to Pearson & Son on practically all Federal lands along the Gulf of Mexico. 1907. First producing well in the Furbero field. 1908. Dos Bocas well caught fire, advertising tremendous productivity of Southern oil fields of Mexico.

Jan 1, 1921

By E. C. Harder

IN view of the gradually decreasing known reserves of high-grade manganese ore and the rapidly increasing consumption of iron-manganese alloys in the steel industry, it is well to turn our attention to the development of low-grade manganiferous ore deposits and to the utilization of these ores in steel manufacture. The dependence of this country on imported manganese ore and ferromanganese has been forcibly brought to the attention of steel makers during the last few years by the cessation of manganese-ore imports from Russia, the restriction of manganese-ore imports from India and of ferromanganese imports from Europe. Should the importation of manganese ore from Brazil cease, the steel industry of this country would face a serious situation. The present practice of steel making requires ferromanganese in large quantities and ferro-manganese of the grade used at present can be produced only from high-grade manganese ores such as the United States appears to possess only in insignificant amounts. There are in the United States, however, large reserves of manganiferous iron ore which could probably be used extensively in the steel industry if certain changes in the practice of steel manufacture were made. Thus high-grade manganese ore could be conserved. Among the most important deposits of manganiferous iron ore in this country are those of the Cuyuna iron-ore district of Minnesota. It is probable that in case of restriction of foreign supplies, the users of manganese in the United States would have to rely to a large extent on the Cuyuna district to make up the shortage.

Jan 9, 1917

By H. [Eyring], B. J. Zwolinski

[ ] The authors are to be commended for their excellent work on the activities of components in the solid state. It is, however, felt that certain points require clarification with reference to diffusion in the solid state. It is a well established point that any rate process in a non-ideal system can be expressed by the general equation [ ] where ko is the specific rate in an ideal system, and ?A, ?B ... , the activity coefficients of the reactants and ?± and ?M,?N the activity coefficient of the activated complex and the intermediates, respectively. With reference to diffusion, the following simplified treatment in correcting for non-ideality is proposed. The same free energy change is involved in moving a particle from a solution of one activity to a solution of another activity,

Jan 1, 1947

By Arthur Winslow

Location.—The Liberty Bell gold-mine is in the San Juan region, in the southwestern corner of Colorado. It is situated about 2 miles from the town of Telluride, near the summit of the Uncompahgre range, at the head of Cornett basin, at an altitude of 11,000 feet, and in a district of excellent record in the past and of great promise for the future. In the immediate vicinity are such well-known and important mines as the Smuggler Union, with a total production of over $12,000,000; the Virginius and Revenue Tunnel group, with a production of probably $5,000,000; the Tom-Boy, with a production of probably at least $3,000,000; the Japan, the Cimarron, and a number of others. History.—The first prospecting in this district is reported to

Jan 1, 1900

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By Richard D. Harvey, Arthur M. Squires, Robert A. Graff, George Kan

Particles of half-calcined dolomite (CaC03 + MgO) that had undergone cyclic absorption of H2S and regeneration with C02 in laboratory tests reveal enlargement of the crystallite grain structure, reduction in the number of pores but enlargement in their size, and partial development of a relatively dense mosaic microstructure on outer surfaces of cyclically reacted particles. Scanning electron microscopy, X-ray microanalysis, microprobe analysis, and X-ray diffraction techniques were used to evaluate microstructural properties of particles after tests conducted at pressures of 1 and 21 atm and temperatures of 7000 to 9000 C. The tests conducted at 7500 C and 21 atm showed the most favorable absorption and regeneration capacities of the dolomite tested. The changes in structure and pores play a major role in reducing the sulfur reactivity of half-calcined dolomite particles. The mosaic microstructure forms more rapidly at 1 atm than at 21 atm pressure. Once it occurs it seals the surface of the natural pore channels that existed in the half-calcined dolomite and restricts further conversion of crystallites of CaCO3 within the particles. Although a relatively coarse, granular mosaic of crystallites is present on some particles cycled at 21 atm pressure after only three absorption-regeneration cycles, it does not completely cover the particles, and that is true even after 30 cycles. Individual crystallites of MgO were not resolved by the X-ray microanalysis, but we believe that during the tests the MgO occurs as crystallites no more than 0.1 um in diameter that are homogeneously distributed through the particles, and it remains essentially inert during the reactions. The MgO contributes to the maintenance of the original fine-grained and microporous structure of the particles, an effect that is most advantageous to absorption and regeneration.

Jan 1, 1976

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By J. D. Mote, A. Rosen, J. E. Dorn

The effect of strain rate and temperature on the critical resolved shear stress for (1100) [1120] prismatic slip was determined for the intermediate hexagonal phase containing about 67 at. pct Ag and 33 at. pct Al. Whereas the flow stress increased only slightly as the test temperature was first decreased below room temperature, a rapid increase inflow stress was obtained with yet greater decreases in temperature from about 240" to 4°K. The effect of both temperature and strain rate on the flow stress over the low-temperature range could be completely rationalized in terms of the Peierls mechanism when the deformation is controlled by the rate of nucleation of pairs of kinks. A few years ago Mote, Tanaka, and Dorn1 observed that the critical resolved shear stress for prismatic slip of a 67 at. pct Ag plus 33 at. pct A1 hexagonal intermediate phase by the (1100)[1120] mode decreased precipitously as the test temperature was increased from 4" to about 160°K. Their results for both basal and prismatic slip are given in Fig. 1. It is obvious that only the flow stress for prismatic slip is strongly temperature-dependent, whereas the flow stress for basal slip is independent of temperature. If the temperature dependence of the flow stress were primarily due to interstitial impurities, it might be expected that they would influence the flow stress for basal slip as well. Since the activation volume at 115°K for prismatic slip was determined to be about 15b3, where b is the Burgers' vector, this thermally activated deformation process was tentatively ascribed as being due to the Peierls mechanism. But the various analyses of the Peierls mechanism then available as formulated by Seeger2 and also by Lothe and Hirth3 did not agree well with the experimental data. Since that time a more realistic theory for the operation of the Peierls mechanism under conditions where the strain rate is determined by the rate of nucleation of pairs of kinks has been presented by Dorn and Rajnak.4 The present investigation was, therefore, undertaken in order to provide the essential data for a careful check on the agreement between this theory and the low-temperature deformation by prismatid slip of the above-mentioned Ag2A1 intermediate phase. EXPERIMENTAL TECHNIQUE Single-crystal specimens so oriented that the [1120] direction and the normal to the (1100) plane were at 45 * 2 deg to the tensile axis were grown from the congruent melting composition of about Ag2Al for the intermediate hexagonal phase by the

Jan 1, 1964

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967