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By Gerhard Derge

The rapidity of oxygen steelmaking has created renewed interesl in the mechanisms and kinetics of the various processes involved. These studies can now be approached with increased confidence because of the more adequate thermodynamics, physical chernislry, and relevant engineering infornzation available. These combine to offer promise of useful control and automation if the details of each specific problem can be sufficiently well-defined. The hot filament microscope provides new insig-hi into many of these problems by direct observation at temperature, allowing the appraisal of the relative importance of thermal gradients, convection, and intermediate phases. All of these have a direct bearing on the overall rates and control of most pyrometallurgical processes. It is one of the special privileges of the Howe Lecturer to become better acquainted with this distinguished man. All of us interested in the metallurgy of iron and steel have developed some sense of his widespread influence by the annual reference to his work in these Memorial Lectures. Each lecturer since 1923 has been able to identify his personal specialty with the broad interests of Professor Howe. This has become even more rewarding with the background information from Professor Gensamer's monograph, "Henry Marion Howe's Contributions to Metallurgy, which brings out his happy combination of intellectual and professional activities. Beyond this, I found my personal bond with Professor Howe in his book on The Metallurgy of Sleel first published in 1891.' After a detailed discussion of the dephosphorizing action of slags, he relates the mineral species identified in the frozen sample to the chemistry of the fused slag with the question, "Is it not most philosophic to hold that these independent entities were wholly integrated in the initial magma; that their presence in it was wholly

Jan 1, 1968

By T. J. Woodside

Prior to 1927 the lead blast furnace charge at El Paso consisted principally of direct-smelting carbonate ores, very low in zinc, and the resulting slag seldom carried more than 4.0 pct. With the exhaustion of the mines in Northern Mexico which supplied these ores, they were supplanted with a much smaller tonnage of sulphide concentrates containing appreciable amounts of zinc, and the zinc content of the slag rose to 10.0 pct. The Anaconda Company's slag fuming plant at East Helena, Montana, had then been in successful operation for several years, and it was immediately recognized that, while at that time the production of high zinc slag was small, if the grade held, a plant for the recovery of zinc from the accumulated slag might some day be practical. The grade not only held but became increasingly higher so that by 1946 suffcient slag had been accumulated to warrant the construction of a fuming plant regardless of future slag production from the blast furnaces, and with the removal of Government restrictions on construction at the end of the war the project was undertaken. The general design of the plant follows that at Bunker Hill, with waste heat boiler, unit coal pulverizers and even more extensive instrumentation and automatic control. The area around the lead blast furnaces is rather congested, being cut off from the nearest feasible site for the fuming plant by the copper plant, so that the most practical route for hot slag transfer is through the converter aisle. For this reason and also to make use of the existing converter cranes to serve the fuming furnace, an unused reverberatory at the north end of the converter building was dismantled and the fuming furnace and boiler located in its place. A flue at right angles to the furnace and boiler runs northward to the U-tube coolers and baghouse (Fig 1). From the bag-house a steel flue runs eastward to an existing and long unused 300 ft con- Crete stack. The coal handling system and de-leading plant lie north of the furnace and east of the cooling tubes and baghouse. The furnace is conventional, 8 X 21 X 33 ft high inside and completely water jacketed (Fig 2). There are 21

Jan 1, 1950

By Ellis Clark

Within the last ten years the progressive party of China, headed by Li Hung Chang, the Viceroy of Chi-Li, has been making great efforts to develop the mining resources of that country, and particularly those that are within reasonable distances of the sea-board. Attention was first paid to the coal-deposits, especially those at KaiPing, which have been placed on a profitable basis with an output of 1500 tons per day, under the energetic management of Mr. Claude Kinder, M.I.C.E., and the successful financiering of Tong King Sing. These coal-mines were described in a report by Kwong Yung Kwang, edited as a paper for the Institute (Duns., xvi., 95.) The attention of the leaders of the progressive party has for the past five years been turned also toward the development of the precious and related metals—gold, silver, copper and lead. De-

Jan 1, 1891

By C. W. Pritchett

Several years ago, during a trip from Jojutla to Huauatla, in the abate of Morelos, Mexico, I was told by my guide of the ruins of an old smelter near by, and my curiosity was excited to such an extent that I went out of my way several miles to see them. I found them very interesting; and, as I fortunately

Jan 1, 1902

Under the joint auspices of the Illuminating Engineering Society and the University of Pennsylvania there will be given about 20 lectures covering the general principles of illumination and the aspects of lighting practice. They will be held at the University of Pennsylvania in Philadelphia, from Sept. 21 to 28, 1916, inclusive. The subject of illumination of mines will be included in this series, which will be delivered by men selected on account of their qualifications to deal authoritatively with the several phases of the subject. In connection with the lectures there will be an exhibition of the latest developments in illuminating appliances, including lamps, accessories, photometers, together with novel applications of light. There will also be an inspection tour which will include visits to manufacturing establishments, laboratories, lighting companies and notable lighting installations. For further particulars apply to the Illuminating Engineering Society, 29 West 39th Street, New York City.

Jan 6, 1916

By Fred T. Williams

The Park City mining-district is distinctively a camp of few properties, 5,000 acres, or one-third of the entire district, being under the management of but three companies. As a rule, the ore-bodies lie deep, with no outcrop, except where erosion has formed the deeper canyons and gulches. Ontario canyon exposed the famous Ontario ledge, and Woodside gulch showed the first ore of the Silver King Coalition mine. The Quincy ore-bodies were first brought to light in upper Empire canyon, and Thaynes canyon was instrumental in aiding the prospector during the early days of the camp. There are 22 shafts which have reached a depth of at least 500 ft., ten a depth of 1,000 ft., five a depth of 1,300 ft., and two a depth of 2,000 ft. The amount of lateral development has been proportiorlally extensive, including six long tunnels, four of which are in 3 miles, with a fifth now being driven. The Ontario lower drain-tunnel is now more than 4 miles long. The formations are sedimentary, dipping about 30° NW. and N., and traversed by many fissures, dikes, and faults. The principal ore-bodies are found. associated either with the contact of the basal Ontario quartzite and the overlying limes, or on a quartzite stratum within the limes, or in the fissures, or along some of the porphyry dikes. The district covers the intersection of the Uintah and Wasatch ranges, which explains the existence of large folds and faults, and fissures of great length, width, and depth. In a general way, the geology of the district consists of a basal quartzite dome, which has been exposed by erosion at the Ontario property. The Ontario fissure lies entirely within this formation. Flanking this dome on the west, north, and east lie

Jan 1, 1912

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By Sage B. H., Lacey W. N., G. W. Billman

The composition of the coexisting phases in the methane-ethane-n-pentane system was determined at 100°F. This was accomplished by withdrawing samples of the coexisting phases under isobaric-isothermal conditions. The relative amount of each of the components present in the liquid and gas phases was determined by conventional analytical fractionation methods. The phase behavior of this system approximates that estimated from generalized correlations which take into account the influence of the nature and amount of each of the components present upon the equilibrium. It was found that for particular pressures and temperatures the equilibrium constant of each of the components was influenced significantly by the composition of the system and this effect was more pronounced at the lower pressures for methane than for the components of greater molecular weight. However, at the higher pressures approaching the maximum two-phase pressure for the system at this temperature the composition markedly influences the equilibrium constants of all the components at a particular pressure and temperature. The results of this study are presented in graphical and tabular form. Introduction The phase behavior of many of the binary systems containing parafin hydrocarbon components from methane through n-pentane has been investigated during recent years. In addition the compositions of the coexisting phases in mixtures of crude oil and natural gas have been studied.' However, these results do not establish the influence of the nature and amount of the other substances making up a multi-component system upon the gas-liquid equilibrium constant of any one component. A preliminary correlation on the basis of values for binary systems was made2 utilizing such experimental information as was available. However, there is need for much additional information regarding behavior in systems containing more than two components. Study of the phase behavior of ternary systems offers a feasible attack upon the determination of the influence of composition as well as of pressure and temperature upon the several equilibrium constants concerned. An investigation of the phase behavior of the methane-propane-n-pentane system at 100°, 160°, and 220°F was reported.".' This work served to illustrate the marked influence of concentration of the other components upon the equilibrium constants. Variations of as much as 50 pct in the equilibrium constants for methane for fixed temperature and pressure were observed in regions remote from the critical state. Likewise there was a marked variation in the equilibrium constants of propane and n-pentane as a result of changes in the composition. These results indicated the desirability of investigating additional ternary systems. The present paper deals with a study of the methane-ethane-n- pen-tane system at 100°F, which is similar in many respects to the work upon the meth-ane-propane-n-pentane system cited above.

Jan 1, 1948

By Sage B. H., G. W. Billman, Lacey W. N.

The composition of the coexisting phases in the methane-ethane-n-pentane system was determined at 100°F. This was accomplished by withdrawing samples of the coexisting phases under isobaric-isothermal conditions. The relative amount of each of the components present in the liquid and gas phases was determined by conventional analytical fractionation methods. The phase behavior of this system approximates that estimated from generalized correlations which take into account the influence of the nature and amount of each of the components present upon the equilibrium. It was found that for particular pressures and temperatures the equilibrium constant of each of the components was influenced significantly by the composition of the system and this effect was more pronounced at the lower pressures for methane than for the components of greater molecular weight. However, at the higher pressures approaching the maximum two-phase pressure for the system at this temperature the composition markedly influences the equilibrium constants of all the components at a particular pressure and temperature. The results of this study are presented in graphical and tabular form. Introduction The phase behavior of many of the binary systems containing parafin hydrocarbon components from methane through n-pentane has been investigated during recent years. In addition the compositions of the coexisting phases in mixtures of crude oil and natural gas have been studied.' However, these results do not establish the influence of the nature and amount of the other substances making up a multi-component system upon the gas-liquid equilibrium constant of any one component. A preliminary correlation on the basis of values for binary systems was made2 utilizing such experimental information as was available. However, there is need for much additional information regarding behavior in systems containing more than two components. Study of the phase behavior of ternary systems offers a feasible attack upon the determination of the influence of composition as well as of pressure and temperature upon the several equilibrium constants concerned. An investigation of the phase behavior of the methane-propane-n-pentane system at 100°, 160°, and 220°F was reported.".' This work served to illustrate the marked influence of concentration of the other components upon the equilibrium constants. Variations of as much as 50 pct in the equilibrium constants for methane for fixed temperature and pressure were observed in regions remote from the critical state. Likewise there was a marked variation in the equilibrium constants of propane and n-pentane as a result of changes in the composition. These results indicated the desirability of investigating additional ternary systems. The present paper deals with a study of the methane-ethane-n- pen-tane system at 100°F, which is similar in many respects to the work upon the meth-ane-propane-n-pentane system cited above.

Jan 1, 1948

By W. H. Pelton, P. G. Hallof

Outlining small pods of high-grade, massive sulfide, copper-zinc mineralization was the object of an intensive exploration program by Long Lac Mineral Exploration Ltd., near York Harbour, Newfoundland, Canada. Efforts to define the ore zones using surface dipole-dipole induced polarization techniques were not entirely successful due to the poor size-to-depth ratio of the targets and widespread disseminated mineralization. Additional information on the size and shape of the sulfide bodies was obtained by placing a current electrode directly within a mineralized drill intersection and systematically measuring the resultant potential on the ground surface. Some simple potential field sources were interpreted from the data and their validity has been shown by an extension to the underground workings.

Jan 1, 1973

By B. Y. Ekber, A. S. Gorbachev

The development of economically effective and safe methods of mining thick coal seams allow considerable coal reserves to be used as an energy resource all over the world.

Jan 1, 1979

Jan 1, 1937

By J. S. Billheimer, H. H. Reamer, B. H. Sage

Jan 1, 1949

By H. H. Reamer, B. H. Sage, J. S. Billheimer

Jan 1, 1949

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By T. Guilford Smith

In presenting the subject of " Armored Turrets for Coast Defense " to this Institute, I am indebted to the Gruson Ironworks, a company incorporated under the laws of the State of New York, for valuable information, model and plans, by which I hope to make clear the construction and peculiar merits of this class of gun-protection. I wish it understood, however, that this is not an undeveloped and untried inventor's ideal, but an advanced and fully perfected system, which has long since passed the experimental stage and has been adopted by most of the foreign governments, after years of extensive experimenting and the expenditure of millions of dollars. The present seems an appropriate time to present the matter to the scientific public, since, for the first time, it is possible to produce these turrets in this country, of American material, and made by American workmen, owing to an agreement entered into between the Gruson Iron-works and the Fried. Krupp Grusonwerk, of Magdeburg-Buckau, Germany, where they have hitherto alone been manufactured. Although its full development and present perfection have been attained at the German works, it may be of historic interest to state that the first idea of using a rotating protected platform for large guns originated with Mr. Theo. Ruggles Timby, a native of the State of New York, who filed a caveat in 1843 for a " metallic revolving fort, to be used on land or water, and to be revolved by propelling engines located within the same and acting upon suitable mechanism." This was followed in 1862 by the issuance to Mr. Timby of two patents (No. 35,846 and No. 36,593) covering the ideas described in his caveat of 1843. The first practical application of this system was made on the " Monitor," of Civil War fame, Mr. Timby receiving $10,000 for two

Jan 1, 1901

By Sandip K. Mitra, John E. Dorn

The Basinki-modified Seeger equation for deformation of metals by means of thermally activated intersection of dislocations was used to ascertain the various factors responsible for the strain hardening of poly crystalline aluminum and a series of a solid solutions of magnesium in aluminum. The analyses were based principally on the rate of change of strain rate with stress and the Cottrell-Stokes ratio. From measurements of these quantities on a series of strain-hardened states, the force displacement diagram for intersection, the density of dislocations in the entanglements, and the contributions of the athermal local stress and long-range stress interactions were deduced. Poly crystalline aluminum was observed to have the same force-displacement diagram for intersection as single aluminum crystals, and the corresponding diagram for the magnesium alloys differed in a manner that suggested that small amounts of magnesium may decrease slightly the stacking fault energy of aluminum. Although poly crystalline aluminum had about the same initial density of dislocations as the single crystals, the density of dislocations increased much more rapidly with strain in the polycrystals. This factor and the higher back stresses generated in the poly crystalline aluminum were the major factors responsible for the higher strength of the poly crystalline aluminum, As the magnesium content of the alloys was increased, the initial density of the dislocations also increased. Most of the alloy strengthening arose from this factor; alloying effects due to short-range order strengthening, Suzuki locking, Cottrell pinning, and so forth, were estimated to be quite small. The gveater rate of strain hardening in the alloys was deduced to be due primarily to the greater increase in the density of the dislocations with strain as the magnesium content was increased. It is the purpose of the present investigation to shed additional light on the average plastic behavior of a grain in a polycrystalline aggregate, by analyses, based on dislocation theory, of appropriate experimental test results. These deductions when compared with those from single-crystal data will then serve to illustrate the major items of difference between the plastic behavior of single crystals and the average behavior of a grain in a

Jan 1, 1963

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By James W. Malcomson

The Tigre Mining Co. of Mexico, owned by the Lucky Tiger Combination Gold Mining Co. of Kansas City, decided early in 1910 to enlarge its mill, which consisted of a concentrator milling 3,000 tons of ore per month. The enlarged plant was designed to crush and concentrate 6,000 of ore and to cyanide 7,500 tons per month. The extra tonnage cyanided was to be obtained from tailings which were stored below the old mill. Power was supplied to the old mill from four boilers; a 150-h-p. Corliss engine and two Weber 60-h-p. gas-engines using producer-gas made from charcoal. The total horse-power required, including 60 h-p. used for machine-drills in the mine, was approximately 275. Cord-wood cost $4.32 per cord, 8 by 4 by 3 ft., and charcoal $15 per ton. The fuel supply in the surrounding country was approaching exhaustion; more than 150 mules and 50 men were engaged in cutting and transporting this fuel, and the unsettled political conditions in Sonora were such that it would be practically impossible to keep an organization of this kind together. The price of fuel was steadily rising and at times it became almost impossible to get sufficient fuel to operate. It was estimated that the enlarged plant, together with the mine, would require 750 h-p., as follows: Horse-Power. Old mill, which was left unchanged,..............180 New concentrator,.......................90 Cyanide-plant,........................380 Mine and other requirements,................. 100 Total,........•..................750 In a study of the best manner to obtain power the following alternative propositions were considered:

Jan 1, 1914

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970