Search Documents

By J. D. Vincent, Paul A. Weyler

Climax Molybdenum's plan for the Henderson 30,000 tpd molybdenite plant didn't just happen. It slowly evolved over a period of 3% years. Many plants cannot afford similar delays, but the Henderson project will take about 10 years to complete from the time the orebody was first discovered until production begins. Pilot plant testing results with both the single stage and two-stage semi-autogenous grinding circuits were highly favorable in terms of operating costs reduction-so much so, that the Amax subsidiary made the decision to go with semi-autogenous grinding for the Henderson mill.

Jan 5, 1972

By John F. Abel

Personal gain seems to be the most powerful incentive to economic progress. One of my first exposures to this phenomenon was the comparison between company stopes and leaser's stopes in a vein gold mine. The company stopes were 4 to 6 ft wide, whereas the leaser's stopes were so narrow that in some places one could not turn around. The company leased only that ground it felt was marginal to mine with day's- pay miners, but by skillful, careful and energetic mining, the leasers managed in most cases to make money for themselves and the company. The Hurting Truth This capitalist system, which puts a premium on successful risk taking, is under attack. Not that it hasn't been under attack all along. What hurts and angers us at this time is that the attack comes from the children of the system-its youth. Such blasphemy should, of course, be eradicated, root and branch. Or should it? Are we hurt in part because some of the things they say are true?

Jan 1, 1970

By J. C. Reed

CINNABAR was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigel1 by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County-across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done con-siderable exploration work and has retorted the high-grade ore so .obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district.

Jan 1, 1935

By Steven Mitchell

BACKGROUND Homestake Mining Company began milling operations at the Bulldog Mountain Mine near Creede, Colorado in 1969. The Bulldog Mill, rated at 350 tpd, produces a bulk flotation condentrate assaying about 180 oz/T Ag and 20% Pb, from heads of about 16 oz/T Ag and 2% Pb. The circuit is straightforward with two-stage grinding to 1-5% plus 65 mesh, followed by rougher and cleaner flotation. Reagents used are Z-6, Z-11, Aerofloat 242 and Aero Promoter 404, with an Aerofroth 65-MIBC mixture for a frother. Additional information on the geology, mine and mill are available in references (1) and (2). A flow sheet for the mill and CIP plant together is attached as Figure 1. Final flotation tailings normally vary from 1.5 - 2.0 oz/T Ag. These tailings are cycloned to produce sand for underground backfill. After cycloning, the sands are repulped and given a final scavenger float. This sand scavenger recovers a small additional amount of silver which recycles back to the main flotation circuit. The tailings are recycloned and pumped to the mine or, if the mine cannot accept sand, to tailings. The majority of the silver in the flotation tailings exists in the fine fractions; cycloning upgrades the slimes and lowers the assay of the sand. The sand, after scavenging, typically assays 0.5 oz/T Ag, and the slimes assay about 3.0-3.5 oz/T Ag. From 1969 to 1976 all of the slime tailings and the sand tailings not used underground were impounded in a tailings pond located about

Jan 1, 1983

By Johnston, T. L.

BISMUTH is found as native metal associated with tin, copper, cobalt, silver, gold, or other metals and in a variety of ores. The more important ones are: bismuthinite (bismuth glance), Bi2S3; bismite (bismuth ochre), Bi2O3.3H2O; and bismutite (bismuth carbonate), Bi2O3CO3?H2O. Of lesser importance are the arsenate, telluride, and vanadate. The sulfide is the most common; the others are often oxidation products from this mineral. Bismuth minerals have been found in various places in the United States, principally in Colorado and Utah, but no ores are mined solely for bismuth. In the Granite mining district of Beaver County, Utah, a stratum of limestone about 6 ft. thick has been almost completely replaced by contact minerals in which bismuthinite associated with pyrite and molybdenite was found intergrown with silicate minerals. In the early days a few small lots of ore assaying 7 to 10 per cent bismuth were shipped from this district. Native bismuth has been found in the Clifton and Tintic districts of Utah. Bismuth is produced as a byproduct in the refining of lead, copper, gold and silver ores, it being recovered from the anode mud from the Betts process. Deposits of bismuth minerals exist in Argentina, Aus¬tralia, China, Japan, Germany, Spain, Peru, Bolivia, and Canada, but Bolivia is the principal, producer and could easily supply all of the present world's demand.

Jan 1, 1933

By E. H. Rose

IN a year of sober reflection and stocktaking after the mineral-squandering spree of World War II, the role that beneficiation of low-grade must henceforth play in American mineral industry has become unmistakable. From the volume of research and development progress in mineral engineering during 1946, mineral dressers evidently have ample resoluteness to meet the challenge. Perhaps ,the most conspicuous trend of the year was the renascence of interest in gravity concentrating methods and more serious effort than ever before to make them effective in finer size ranges down to 200 mesh. This has been forced by the problem in iron ores where the low value of the product will not support a high flotation reagent cost, however good flotation pilot plant results may have been and however well the acute problem of variable feed may be met. The race is on between rabbit flotation and tortoise gravity methods and a surprising amount of betting money is being laid on the tortoise which already is showing previously unsuspected talent for speed. Mostly, however, a wait-and-see attitude prevails during the present preliminary heats. As evidence of the latter, two magnetic plants are now on the boards for magnetic taconites on the eastern Mesabi to establish a reprieve against the time when nonmagnetic taconites must be addressed. Incidentally, these operations will force the blast-furnace issue on preparation of fine material since a minus-100-mesh grind is contemplated.

Jan 1, 1947

By Paul M. Tyler

ROUGHLY one-half the value of mineral products at mines or quarries must be spent for wages. In view of the steady increase in hourly wages that continued for several decades prior to the onslaught of the recent depression, it is perhaps surprising to discover that labor's share of the gross proceeds of the mining and quarrying industries of the United States declined to 46.8 per cent in 1929, compared with 52.2 per cent in 1919 and 53.2 per cent in 1909. The actual percentages vary in different branches of the industry and in different localities but the downward trend is unmistakable. For the period 1909 to 1919 it was quite marked in every industry and from 1919 to 1929 it was apparent in all but six: namely, gold and silver lode mining, placer gold mining, crude gypsum production, marble quarrying, asbestos production, and fluorspar Tninino mining

Jan 1, 1933

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

J. E. JOHNSON, JR., New York, N. Y. (communication to the Secretary*).-The discussion of Mr. Henrich's paper took place at a meeting from which I had the misfortune to be absent, and has just come to my attention. I do not wish to let the subject pass without contributing to it a little information which has come into my possession. In 1912, I published a brief note in the Transactions on The Effect of Alumina in Blast-Furnace Slags, giving in tabular form three typical slags used in iron blast-furnace practice, one of them the high alumina slag of, which Professor Richards speaks. That table is reproduced herewith. TABLE 1.-Composition of Slays. 1 3 3 4 5 6 7 CaO by Neutral Ratio Ratio Ratio Al2z03, SiO2, Differ- Substan- Cat Ca0 a A1203 Ratio Per Per ence, ces, CaO Cent. Cent. Per Per Al2O3 + Sioz Sit: SiO2 Cecil_ Cent. Virginia practice 6.5 36.0 54.0 3.5 1.27 1.6S 1.50 Lake-ore practice 13.5 33.0 50.0 3.5 1.08 1.92 1.51 Special experiment... 36.0 24.7 36.8 3.5 0.59 2.90 1.44 It supplies what seems to me convincing evidence that, for the purposes of the iron blast furnace, alumina can be regarded only as a neutral substance, dissolving in the slag and materially altering its viscosity, but not affecting its chemical activity. In subsequent experience with charcoal furnaces, I found the same rule to hold; that the chemical effect of alumina could be disregarded, providing the ratio of the lime and magnesia to the silica were kept constant. This is exactly the experience which Messrs. Dwight and Mathewson had in copper- and' lead-smelting furnaces. I have never seen any evidence or argument adequate to support the contention of Professor Richards-that the alumina acted as a base in the charcoal iron furnace and as an acid in the coke furnace, and that the function of alumina in iron-furnace slags is inherently different from that in copper- and lead-furnace slags-and I am compelled to differ absolutely with his conclusions in that respect.

Jan 9, 1917

Following closely Marcona Corp.'s announcement of its new Marconaflo process for transporting mineral slurries by ship (see pp. 96-97, Sept. 1969 [ ]), Midland-Ross Corp. (M-R) now heralds its metallized iron pellet process which supplements Oregon Steel Mills1 (Oregon Steel) new Portland, Ore., plant. Harry J. Bolwell, president of M-R describes the company's M-R Pellet as "the most exciting advance in steelmaking in a decade, one which will profoundly affect the industry." In fact, other knowledgeable industry spokesmen believe that with these developments the mini-steel plant era is now here and that this technical development along with the Marconaflo process will revolutionize iron ore shipments and steelmaking. The M-R president predicts that electric furnaces can account for 20% of the annual U.S. steel production by 1975, compared with 14% at the present time because of these developments.

Jan 12, 1969

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. 'H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. 'E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 'C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.'

Jan 1, 1970

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By J. C. Bayles

Jan 1, 1885

By E. C. Harder

BAUXITE is known mainly as the ore from which aluminum is smelted but it has large use also in the manufacture of artificial abrasives and as a basis for certain chemical industries. A small amount is used for refractories and for other purposes. COMPOSITION Dana and others give the mineral formula of bauxite as A1203.2H20 and the composition as A12037 73.9 pct; H2O, 26.1 pct. It has been definitely shown, however, that bauxite does not exist as a specific mineral but rather as a rock. The term is now used synonymously with aluminum ore and it embraces gibbsite (hydrargillite or alpha trihydrate), A1203.3H20 (A12037 65.4 pct; H2O, 34.6 pct); boehmite (alpha mono¬hydrate), A1203.H20(Al203) 85 pct; H2O, 15 pct); diaspore (beta monohydrate), A1203.H2O(A12037 85 pct; H2O, 15 pct), and mixtures in various proportions of any two of them. Bauxite of the Mesozoic and Cenozoic in Europe is predominantly a mixture of gibbsite and boehmite, subordinately a mixture of boehmite and diaspore, or gibbsite and diaspore. The bauxite of North and South America, tropical Africa, Asia, and Australasia consists largely of gibbsite. Corundum (A1203) is not included under bauxite, although gradations from bauxite to emery or corundum exist. All bauxite, irrespective of the aluminum minerals composing it, contains certain impurities, including silica, in the form of clay minerals (kaolinite, halloysite, and others) or quartz, iron oxide (as hematite or goethite), titania (as leucoxene or rutile), iron sulphide (as pyrite or marcasite), iron carbonate (siderite), and calcium carbonate (as calcite); the last three mentioned in minor amount and of local occurrence only. Bauxite belongs to a group of partly consolidated materials called laterites, formed by surface weathering. This group includes also impure siliceous and ferruginous bauxite and siliceous and

Jan 1, 1949

By Simon D. Strauss

Production and consumption of nonferrous metals in the United States during 1950 were at peak levels for the postwar period, as is shown in Tables I, II, and III. The trend of production was upward through most of the year. At the year end, with the possible exception of the Tri-State zinc-lead district, the large mining operations in the country were running at capacity. The absence of serious labor interruptions during the year was an important contributing factor in the increased out-put of metals, since in each of the previous postwar years there had been a number of major strikes which affected production adversely.

Jan 2, 1951