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The following list of corrections has been compiled from the thirty-five volumes, with some additions: VOLUME I. Page 160. The first two sentences of the second paragraph should read as follows : " For No. II we find that 2.33 percent. A1,08 take 4.07 per cent. 8109, leaving 3.48 per cent. 8102 free, which requires 3.25 per cent. CaO." Page 160, line 14, 3.79 should be 3.25; and in the 15th and 18th lines, 48.44 should be 46.98. VOLUME VI. Page 59. The discharges of the miners' inch per second, given as .2624 and .2499 cubic feet, should be .02624 and .02499, respectively. The discharges per minute, hour, etc., are correctly given. VOLUME VIII. Page 214. 16th and 25th lines, ferric carbonate should be ferrous carbonate. Page 486, 16th line, 10,000 should be 5,000. [ ]

Jan 1, 1907

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10'3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey' to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N's are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen's computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.' The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By J. Chipman, J. C. Fulton

Reduction of silicon from blast-furnace-type slags by carbon-saturated iron is a very slow reaction even under conditions of rapid stirring. Equilibrium under atmospheric pressure of carbon monoxide was approached from both sides, and the silica-silicon relation was established at temperatures of 1425º to 1700°C for slags containing up to 20 pct Al2O3. Silicon carbide is formed by reaction of graphite with high silica slags and the conditions for its formation were determined. Activities of SiO2 and of CaO in their binary solutions at 1600°C were determined. The effects on the activity of SiO2 were established for additions of 10 to 20 pct AI2O3 and of 10 pct MgO. STUDIES of chemical reactions between blast-*>-5 furnace slags and metal have been focussed on the transfer of sulphur from metal to slag. The important role which silica reduction plays in this process' has led to a study of the transfer of silicon from slag to metal and the equilibrium represented by the equation SiO2 (in slag) + 2C (graphite) = Si + 2CO (g). [I.] The authors2 have published an account of the experimental method employed in attacking this problem and of three series of experimental results at 1600°C. This paper contains data on some additional compositions and extends the observations to cover the temperature range 1425° to 1700°C. The data are used to determine the activity of silica in the slags. As in the earlier experiments, the atmosphere was carbon monoxide which flowed through the furnace at 150 ml per min. In certain heats designated in the tables and figures, the gas was bubbled through the melt using a graphite tube. The latter increased in porosity during a run and in some cases bubbling ceased as indicated by cessation of surging. Some results were discarded for this reason. Experimental Results The new data are shown in Tables I through V and both old and new data are plotted in Figs. 1

Jan 1, 1955

?ADAIR, ARTHUR C., Corp 4th Co., 1st. Training Bat., 154th Depot Brigade. ADAMS, HENRY, Major: Chemical Warfare Service. ARLUCK, A. A Headquarters, 1st Corps of Artillery. ASKIN, THOMAS B. H Ensign. BANKS, H. R., 2d Lieut Canadian Engineers. BAYLESS, G. E. S Supply Dept. U. S. Submarine Base. BELL, L. R Co. C, 302d Engineers. BELLIS, ARTHUR E., Capt Ordnance Reserve Corps. I BIRRETT, HOWARD, Lieut., Aviation Section, U. S. Signal Corps, Ellington Field. BOISE, PAUL T 2d Regiment, 24th Squadron. ?BRADLEY, CLARENCE I Convois Automobile Section 585. BROWN, GEORGE M Co. G lot Engineer Replacement Regiment. BUCKINGHAM, ALBERT U. S. S. " Coronet," S. P. 194, Section Base No. 7. BURNS J. J Co. 1-B, E. R. O. T. C. BURT, Co. B, let Engineers Replacement Regiment. ||BYERS, WHEATON B., 2d Lieut Ordnance Dept. CANTON, WILLIAM R., Sgt Headquarters Co., 80th F. A. CARSON, JOSEPH A., Capt A.S. S. R. C.' CHAPMAN, LEWIS C. Corp 29th engineers. CHETNEY, P. C., 2d Lieut 15th Bat. Headquarters Co. CHEVRILLON Louis French Red Cross. CHIDESTER, W. B., 1st Lieut 24th Machine Gun Bat. CHURCH, JOHN L., Capt 308th Engineers. CLAGHORN, D. MONTGOMERY, 1st Lieut 45th Engineers. CLAQHORN, JAMES L., Lieut Aviation Section, Signal Corps. CLARKE, ALEXANDER F U. S. Naval Aviation Service. COMINS, WALDO H. Ca t 41st Co., 164th Depot Brigade. COOK, FREDERICK A., Capt., Engineer Reserve Corps, Asst. to Div. Engr. 79th Division. COOPER, CLAUDE H. Capt C. A. R. C., 50th Artillery. COPELAND, N. R., Lieut. ||CORBY H.. G., 1st Lieut Co. D, 109th Supply Train. CORSA, BEAN, Capt Co. D, 612th Engineers. CORTESE, EMILIO Italian Army. COULDREY PAUL S., Corp British Expeditionary Forces. || CRAGIN, RODNEY S Co. E, 115th Engineers. CURRIE, JOHN M., Ca t Royal Engineers. || CUTTING, G. W., 2d Lieut U. S. Reserves, Field Artillery. V DARRINGTON, PAUL N., 1st Lieut U. S. Infantry. DAVIS, ANGUS W., Lieut-Col British Expeditionary Forces. || DAVIS, THORNTON, 1st Lieut 13th Field Artillery. ELAND, FREDERICK A., Major Engineer Reserve Corps. DOUGLAS, JAMES $ American Red Cross. DOVE, D. R., Candidate 21st Training Battery, F. A. C. O. T. C. Dover JAMES J 6th Co. C. B. DOWS, DAVID,Capt Coast Artillery, Officers Reserve Corps. || DRAKE, M. 6., 2d Lieut Headquarters Co., 325th Infantry. I || EMMERSON, E. Roy British Navy. EVERIT, RICHARD STURTEVANT Heavy Artillery Officers' Training Camp.

Jan 1, 1923

In high-volume mining operations, preventive maintenance programs that include standardized replacement wear parts can boost equipment availability and lower unit costs. Meeting the daily production targets depends heavily on keeping equipment working as close to full time as possible. This is the case at one medium-sized western surface coal operation producing approximately 2.7 million t/y (3 million stpy). The mine, located in western Wyoming, removes in excess of 8 million m3 (10.5 million cu yd) of highly abrasive overburden each year. According to the mine superintendent, "Abrasion at this mine is some of the worst I've ever seen. Shovel points can wear out in little more than one shift. Dozer blades some- times last two weeks, but can wear out sooner. And ripper points really take a beating. If we can replace this fast-wearing iron with small pieces that go on quickly, we think that's the way to go."

Jan 3, 1978

By Pablo Hadzeriga

Great Salt Lake brine was subjected, in laboratory scale, to conditions simulating solar evaporation. Solid phases and the variation in composition of the liquid phase throughout the potassium salts crystallization zone are presented. These experimental results are discussed and compare with stable equilibrium data of the quinary system Cl-, SO4, Na+, K+, Mg + + and H2O. The Great Salt Lake brine in Utah is a vast reserve of several potential chemicals which has attracted much attention in the recent past. From the standpoint of an ore reserve, it may be said that the lake contains a low grade ore which has to be concentrated by evaporation of water. Because of the fairly favorable weather conditions in the Great Salt Lake area, it seems reasonable to consider solar evaporation as an economical means of concentration. From the view of phase chemistry, the main constituents of Great Salt Lake brine make it belong to the five component system: C1-, SO4=, Na+, K+, Mg++ and H2O. Because of their low concentration, the presence of other elements may be regarded as having little effect on the equilibrium of the five main components. Equilibrium data for the quinary system of our interest has been available for many years. Using these data, it is possible to calculate how the brine of the lake will concentrate when subjected to solar evaporation. In practicing solar evaporation, the weather factor and supersaturation conditions cannot be ignored, but their introduction into calculations using equilibrium diagrams is almost an impossible task. With the experimental work presented in this paper, an attempt is made to compare the stable equilibrium data of the quinary system as applied to the case of the Great Salt Lake brine and the dynamic equilibrium when that brine is subjected to continuous solar evaporation. Sea water brine belongs to this quinary system when only the major constituents are considered. The study of this system has been carried on since the last decades of the nineteenth century. The reason for these intensive studies was to give a geological explanation to the underground potash deposits. AS a result, many theories were presented trying to relate the equilibrium data with the geological formation, paragenesis and metamorphism of these deposits. Two main approaches were followed for the equilibrium studies of this quinary system. One of them, and the best known to us, was the school started in Germany in the last century by J. H. Van't Hoff. The other one, which started about the same time, was the school of N. S. Kurnakov in Russia. Both approaches were different and as a consequence generated opposite theories about the geological formation of potash deposits. The Van't Hoff school studied the quinary system of sea water under careful laboratory control, resulting in stable phase diagrams. During these studies, Van't Hoff recognized the difficulties in crystallizing some double salts.' ". . . . we unexpectedly found that some compounds whose formation in the solutions under investigation was possible at 25°C, nevertheless totally failed to put in an appearance. These, not to mention the calcium salts, were leonite, MgSO4 . K2SO4 4 H2O; kainite, KC1-MgSO4 . 3 H2O; and kieserite, MgSO4 .H2O. Even exceedingly slow crystallization with the addition of the compounds themselves did not remove the condition of supersaturation in the case of these bodies." However, those salts (leonite, kainite, and kieserite) were included in the stable phase diagram at 25°C as shown in Fig. 1 using D'Ans data.3 The figure also shows the sequence of crystallization of the Great Salt Lake brine according to the stable diagram. In later studies by the Van't Hoff school, especially by D'Ans,3 Karsten,4 Autenrieth,5,6 attention

Jan 1, 1968

By W. L. Chen

The Batac jig was first introduced in the US for fine coal cleaning in 1973 (Tackett, 1977; Hake, 1976). Since then, a total of six such jigs of various sizes have been installed in five US plants for a total capacity of 2346 t/h. The raw coal size ranges from 19 mm x 0 to 9.5 mm x 0-fraction sizes previously fed to heavy medium cyclones, Deister tables, or water only cyclones. Growing interest in the Batac jig as a replacement for the above equipment is due to the following reasons: • Unlike heavy medium cyclones, no magnetite is required. As a result, the operating cost of the plant is reduced. • The compactness of equipment is unique on a unit ton per hour basis as compared to other equipment. • Solid state electronic control of jig stroke length, frequency, and jig bed depth makes the equipment highly efficient. Installations of Batac jigs in the US as of June 1980 are shown in [Table 1]. Use of the Batac jig is even greater outside the US (Anonymous, 1980; Chen, 1980). Its use is not limited to fine coal but is applied to coarse coal as well, with 102 mm size in the feed (Zimmerman, 1975). In countries where consumption of magnetite associated with the heavy medium system of coal cleaning is considered a waste of iron ore resource, the Batac jig is regarded as the primary choice in the selection of cleaning equipment (Chen, 1980).

Jan 1, 1981

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,&apos; who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,&apos; and Duwez and Taylor&apos; reported its existence. Rostoker&apos;s study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker&apos; seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo&apos; and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker&apos;s compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker&apos;s analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.&apos;" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll&apos;s and Dr. Schlecten&apos;s recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh&apos; Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By Andrew S. McCreath

THE manufacture of pig iron for conversion into steel by the Bessemer and open-hearth processes, is now one of the most important industries of the United States. It is necessary that iron intended for this purpose should be very pure, and especially must it be comparatively free from phosphorus. Great care must therefore he exercised in the selection of proper ores, flux, and fuel. Only such ores as are practically free from phosphorus can be used, and pure fuel is as much a necessity as pure ores; though hitherto iron men have paid comparatively little attention to this point. During the course of my work as chemist for the Second Geological Survey of Pennsylvania, I had occasion to examine some of the bituminous coals of the State for phosphorus, and the results obtained are so interesting that I venture to present them to the notice of the members of the Institute. The coals are arranged in geological order according to the different beds, and the table shows the percentage of phosphorus in the coal and also in the coke. The greatest number of specimens have been selected from the Pittsburgh bed, because it is the principal coal-bed of Southwestern Pennsylvania, and most of the mineral fuel which is mined along the Youghiogheny and Monongahela rivers, to be used in the coke ovens of the Connellsville region and in the blast furnaces and mills of Pittsburgh and its vicinity, and to be shipped to Western and Southern markets, comes from this bed. It will be noticed that many of the specimens examined contain

Jan 1, 1880

By Earle C. Smith

The Chairman.—Mr. Earle Smith has kindly offered to make some remarks in connection with segregation in the product, Mr. Smith: E. C. Smith,* Cleveland, Ohio—I will start this Off by a story oF the code days of the American Iron and Steel Institute. In those days, Republic did not have a big strip mill, and the question came up of the check analysis of rimmed steel. I suggested that they let me be the chairman of the Committee on Accumulating the Information on the Variation of the Composition of the Ingots of Rimmed Steel. Somebody wanted to know why I wanted to be the chairman. I said, "we don&apos;t make any of the big ingots of rimmed steel, and no matter who makes them they are so bad that you don&apos;t dare publish the information. So if 1 collect it and hide it you can&apos;t charge me with having done anything that really disrupted the commercial situation." So, everybody furnished me with a rather complete story as to the horrible variations in big rimmed ingots. I took it out to my house and put it away, and it is still there. Now, segregation in the big ingot is no longer an "academic " matter as far as I am concerned. I am in a situation like that of the German who was told in 1956 about the coming war. He said: "until it is your throat that is going to be cut, you don&apos;t pay any attention to what is happening to the otherman." &apos;That is the way with the problem that we have in front of us. Recently I have been told that the &apos;Omptroller was questioning the payment for certain articles of stamped steel that had been made from rimmed steel, because upon check analysis of the rimmed steel it had been determined that these stamped articles were nut within the compositions that were included in the specification, and therefore he as the camptroller had no alternative. It was not meeting the specification; therefore, no payment. So I I say to all of you: You can very seriously consider this matter of segregation now and on into the future on the basis of the fact that it is actually going to cost your companies, which are making these products, money unless there is some new idea about the infallibility of quantitative , chemists who analyze some of these products or lawyers who read specifications, I don&apos;t know which man is going to be the major factor in the future. if the National Bureau of Standards could in some way show the specification writers the variation between good chemists analyzing for That they expect to be umpire eel. the writers would certainly realize that some of the to to which we have calmly signed our names as being O.K. are— well, as one man said to me, they might be filled by the devil, and they certainly could be filled by the Lord, but they could not he me by mankind. I would like to inject two or three things into a segregation study which I Want you to think about, because 1 would be a little surprised if there is very much discussion of them, In the first place, we generslly make steel in the United States in the basic open hearth, and I do not think there has bee,, nearly enough consideration given to segregation German the bath before it moves into the ladle. I am sure that any of the people who handled the 9400 series of the NE series when it contained the 0,60 per cent silicon have more respect than they had previously for the segregation that is within, the ladle; that is, before the metal reaches the ingot mold, the frozen ingots and the segregation in them. Another pint to which I think We ought to sis serious consideration is the segregation of iron oxide in the ingot-iron type of material, where the distinction between that and the steel segregation is that it is actually segregat. ing iron oxide, Normally we are segregating some form of carbon or sulphur, or something like that, with the stamping steel industry now coming down into the ranges of chemistry, where the segregation of iron oxide will be just

Jan 1, 1945

By Craig R. Barrett

The influence of the stress dependence of the dislocation density on the overall stress dependence of The steady-state creep rate is discussed. Experimental measurements of dislocation densities and creep rates jor an Fe-3.1 pct Si alloy tested over a wide range of stress are presented which indicate a close correlation between the two quantities. EXPRESSING the stress dependence of high-temperature steady-state creep rates has been the subject of numerous investigations over the past decade. From these investigations have emerged a few general equations which fit most of the available data reasonably well. Garofalo 1 has proposed that for a wide range of stress and temperature the creep rate, i, can be expressed by a relationship of the form: where A, ß, and n are temperature-dependent and is the applied stress. Eq. [I] gives a stress dependence of a at low stresses and exp(nßo) at high stresses, both consistent with experimental observation where n = 5. A number of other investigatorshave proposed a similar expression where: where m and w are in general functions of temperature. Theoretical justification for Eqs. 111 and [2J comes from two different approaches, theories based on dislocation glide3-5 and theories based on the balance between work-hardening and recovery.&apos; Dislocation glide theories predict where p is the mobile dislocation density and V is the activation volume. In order for Eq. [3] to predict a on stress dependence at low stresses with n = 5, it is necessary for p to be a strong function of stress, about proportional to u3 or u4.436 Recovery models of creep start with the general expression:&apos; where r is the recovery rate and h is the work-hardening rate, and then employ a detailed model to determine the stress dependencies of r and h. As example, weertman2 has described a model based on pile-up hardening which results in an expression similar to Eq. [2] with m = 2 and p = 2.5. A recent, seemingly more general approach suggested by McLean is to use Friedels dislocation network growth expression to calculate the stress dependence of r. This model predicts r = p 3,2 and, as h is taken to be a relatively weak function of stress, the stress dependence of i should be about proportional to p3, 2. Once again, it is required that p be a strong function of stress to yield i This recovery model is by no means complete as the stress dependence of network growth is calculated in the absence of an applied stress meaning that r should probably be a stronger function of stress than given by p3, 2 and also some recent work by Mitra and McLean8 suggests that the stress dependence of h may be as large as Because of the importance of the stress dependence of p in determining the overall stress dependence of the strain rate it seems reasonable to examine this relationship in some detail. Measurements made on dislocation densities present during high-temperature steady-state creep generally obey the following relationship a =o0 + aGVWp [5] where uo is usually called a friction stress, a is a numerical constant about equal to unity, G is the shear modulus, and b is the Burgers vector. Depending on the magnitude of uo, data obeying Eq. [5] can give rise to a range of stress dependencies of p. For example, if we assume that the expression where 6 is some constant, adequately represents the stress dependence of p over a range of o, then from Although Eq. [6] obviously breaks down when u 5uo for uo 6 can vary over a wide range of values. In particular, if u > a, > 0 then 6 will be greater than 2. As an example the data of Ishida and McLean are plotted in Fig. 1 showing excellent agreement with dynes per sq cm) and also showing good agreement with a p cc u3 dependence when plotted on a log-log basis. As oo increases 6 tends to increase and correspondingly the stress dependence of the predicted creep rate should also increase,* as-

Jan 1, 1968

Through a unique Department of Commerce program a group of US mining equipment manufacturers spent 18 fruitful days in the, Far East, meeting with government and industry leaders in Thailand, Indonesia, and the Philip¬pines. The US Mining and Exploration Equipment Semi¬nar Mission, held April 3-20, 1979, was sponsored by the Special Activities Group of the Commerce Department&apos;s Office of International Marketing. The program included a series of technical overview papers presented by the manufacturers, aimed at promoting the sale of US products and services throughout the world.

Jan 7, 1979

By E. L. Tucker

PREVIOUS investigations of E. L. Tucker and R. E. Head&apos; related in particular to the effect of cyanogen compounds on galena, sphalerite, and pyrite, and their behavior in the presence of such com- pounds. The present contribution deals with the float- ability of the copper minerals and of pyrite. All experiments were performed on minus 200-mesh material, the method of preparation being the same as that described in the previous article. Flotation tests were made in a small mechanically agitated machine of 50-g. capacity designed in this laboratory by Gates and Jacobsen." General Naval Stores pine oil No. 5 and potassium xanthate were used in constant amount in all of the experiments; these agents were selected because of their present wide use in the flotation of copper minerals. Lime additions were varied to secure four &apos;final hydrogen ion concentrations, namely, neutral, 0.0005 per cent CaO, 0.003 per cent CaO, and 0.02 per cent CaO. The variation in lime addition was introduced to include the range of alkalinities employed in actual flotation practice.

Jan 1, 1926

By W. O. Philbrook, K. Natesan

The oxidation kinetics of spherical pellets of zinc sulfide made from Santander concentrates were studied using a thermogravimetric technique. The experiments covered a temperature range-. of 740" to 102O°C, 0-N mixtures varying from 20 to LOO pct O2, and pellet diameters between 0.4 and 1.6 cm. Mathematical models were formulated to Predict the reaction rate on the assumption that a single transport or interface reaction step was rate -controlling. Analysis of the data indicated that the process of oxidation was predominantly controlled by transport through the zinc oxide reaction-Product layer. ROASTING processes, which are reactions between solids and gases, are very important because they are employed in the production of a number of basic metals. These processes are highly complicated, and one needs to consider the transport phenomena of heat and mass between the solids and gases in addition to the kinetics of various chemical reactions involved. Because of such complications there is a lack of knowledge concerning the rate-limiting factors, which may strongly depend on temperature, particle size, gas composition, and solid structure. The oxidation of zinc sulfide, which is of commercial importance in zinc production, falls into this class of reactions. The major goal of this work was to elucidate the roles played by different process variables, such as reaction temperature, gas composition, pellet size, and pellet porosity, on the kinetics of oxidation of single pellets of zinc sulfide. Roasting of zinc sulfide single particles has been a subject of both experimental and theoretical investigations.&apos;-&apos; The reaction is exothermic and may be considered to be irreversible. Such a reaction has been found to proceed in a topochemical manner. In other words, as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,1-9 that the particle retains its original dimensions and the process requires transport of gaseous oxygen across the porous product layer for continued reaction. The reaction may be represented by ZnS(s) + 3/2 O2(g) = ZnO(s) + SO2(g) [1] The solid product considered here is only zinc oxide, since the diffraction patterns of zinc sulfide pellets oxidized partially at &apos;798" and 960°C showed K. NATESAN, Junior Member AIME, formerly St. Joseph Lead Fellow, Department of Metallurgy and Materials Science, Carnegie-Mellon University, Pittsburgh, Pa., is now at Argonne National Laboratory, Argonne, Ill. W. 0. PHILBROOK, Member AIME, is Professor of Metallurgy and Materials Science, Carnegie-Mellon University. This paper is based on a them submitted by K. NATESAN in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science at Carnegie-Mellon University. Manuscript submitted December 2, 1968. EMD lines corresponding to original zinc sulfide and the newly formed zinc oxide. OXIDATION MODEL The generalized model for gaseous oxidation of zinc sulfide is illustrated in Fig. 1. This depicts a partially oxidized sphere of zinc sulfide in a gas stream surrounded by a laminar film of gas. The spherical sample of zinc sulfide of unchanging external radius r0 is suspended in a flowing gas stream of total pressure PT and composition specified by the partial pressures of the individual components. Partial pressures of the gaseous species in the bulk gas phase, at the exterior surface of the pellet, at the ZnS/ZnO interface, and at equilibrium for Reaction [I] are identified by the superscripts b, o, i, and eq, respectively. The overall reaction involves the following ~te~s:&apos;~&apos;~&apos; Step 1. Transfer of reactant gas (oxygen) from the bulk gas stream across the gas boundary layer to the exterior surface of the pellet and the reverse transfer of the product gas (sulfur dioxide). Step 2. Diffusion and bulk flow of oxygen from the pellet surface through the product shell (ZnO) onto the ZnS/ZnO interface and the reverse transfer of sulfur dioxide. Step 3. Chemical reaction at the interface, which results in consumption of oxygen gas and generation of sulfur dioxide gas and heat; at the same time the _________ PARTICLE SURFACE / x^^^^n^X / MOVING INTERFACE core-----/ sJSNxy " /T^T^02 \ V\V$\ ^NWX/ "*/— GAS BOUNDARY x. \\ZnO SHELLV/ / \^ . / &apos; ^ BULK GAS --------N_______ _____,------p£ w \ P« / (f> \ / a \ <i) / <----------------- _(o) ^^--------------(b) °- pso, pso2 ro ri 0 ri ro RADIAL POSITION Fig. 1—Generalized model for oxidation of a sphere of zinc sulfide.

Jan 1, 1970

By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-&apos; mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962

By R. W. Shoenberger, J. A. Grina, R. J. VanPelt

The many alternatives open to coke plant operators for improving overall coke quality and strength are discussed in this paper. Programs undertaken by US Steel research and coal operations during the previous ten years to improve coke strength are described. New techniques in use, or being considered for future use, are also discussed.

Jan 1, 1982

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.&apos; Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.&apos; The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933