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By S. Frederick Ravitz

FOUR liquids are ordinarily present in the lead blast furnace during lead smelting. At the bottom is the lead bullion, which is metallic lead containing about one per cent of impurities, including gold, silver, copper, bismuth, arsenic and antimony. Above this is the speiss, which consists essentially of arsenides and antimonides of iron and copper. The speiss is followed by the matte, which consists principally of sulfides of iron, copper and lead1. The top layer is the slag, of which the major constit-uents are silica, lime, alumina, zinc oxide and iron oxide. Similar products are obtained from the dross furnace, which treats the dross obtained in decopperizing lead bullion. The distribution of gold and silver among these various products is of considerable importance in the smelting of lead. In general, the matte and speiss cannot be treated in the lead smelter, and usually are sent to a copper smelter. It is usually desirable, therefore, to keep their gold and silver contents as low as possible, and to collect the precious metals in the bullion. If the bullion, speiss, matte and slag exist together in equilibrium, the gold and silver should distribute themselves among these four liquids in a definite manner, which, other conditions being equal, should depend only on the amounts of gold and silver in the charge to the furnace. It is thus apparent that a knowledge of whether such equi-librium exists is necessary before attempting to study the effects of various compositions of matte and speiss on the distribution of gold and silver among the furnace products2. Moreover, systems consisting of four liquids in equilibrium are very rare, and are of considerable scientific interest.

Jan 1, 1936

By R. K. Waring

A KNOWLEDGE of the mutual liquid solubility of zinc and lead is of importance in various phases of zinc metallurgy. The determination of this solubility has been the subject of numerous investigations, but unfortunatel, the results vary widely, particularly at higher tempera-tures, and it has been impossible to decide what data are most reliable. It was decided to investigate the matter and in view of the disagreement in the published results, it was felt necessary to take rather unusual precautions to insure the reliability of the data. For this reason deter-minations were made by four different methods, and the procedures of several of the previous investigators were duplicated. The previously used methods can be divided into two classes: methods involving freezing the entire melt and taking samples of the lead-rich and zinc-rich phases in the solid state, 1,2 and methods in which the. samples are taken while the bath is liquid and at the desired temperature. 3,4 Data obtained by methods involving freezing the entire melt show much lower solubility of lead in zinc than methods in which the liquid is sampled at temperature. The latter method was used by Spring and Romanoff5 and by Hass and Jellinek.6 The results of these two investi-gations are in agreement at temperatures near the melting point but at higher temperatures Hass and Jellinek find a higher mutual solubility.

Jan 1, 1934

In ilmenite smelting, the FeO content of the feed material (nominally FeO.TiO2) is decreased by reduction with carbon. In a parallel reaction, a significant amount of the TiO2 is reduced toTi2O3. One of the striking features of these reactions is a consistent relationship between the extents of FeO and TiO2 reduction; this relationship is independent of furnace size. It was recently proposed that this relationship follows from the solidification behaviour of the slag, where the final slag composition corresponds to the minimum melting point (?eutectic groove?) in the FeO-TiO2-Ti2O3 phase system; the hypothesis is that solidification equilibrium with the freeze lining stabilizes the slag composition. If this is the case, the system of slag and freeze lining must be capable of correcting two types of disturbances: thermal and compositional. Thermal disturbances result from incorrect power input, for the feed rates of ilmenite and reductant. For example, excessive power input will tend to overheat the slag, causing the freeze lining to melt partially, establishing a new steady-state heat loss from the furnace. Compositional disturbances result from an incorrect reductant input for the given power and ilmenite input. In this work, the dynamic response of the slag and freeze lining to different inputs (flow rates of ilmenite and reductant, and power input) is modelled. The model is based on solidification equilibria, and quantified heat loss through the freeze lining. The conclusion is that the solidification equilibrium cannot constrain the composition to the eutectic groove for typical operating conditions. Keywords: ilmenite smelting, freeze lining, solidification, high-titanium slag

Jan 1, 2004

In ilmenite smelting, the FeO content of the feed material (nominally FeO.TiO2) is decreased by reduction with carbon. In a parallel reaction, a significant amount of the TiO2is reduced to Ti2O3.One of the striking features of these reactions is a consistent relationship between the extents of FeO and TiO2reduction; this relationship is independent of furnace size. It was recently proposed that this relationship follows from the solidification behaviour of the slag, where the final slag composition corresponds to the minimum melting point (?eutectic groove?) in the FeO-TiO2-Ti2O3phase system; the hypothesis is that solidification equilibrium with the freeze lining stabilizes the slag composition. If this is the case, the system of slag and freeze lining must be capable of correcting two types of disturbances: thermal and compositional. Thermal disturbances result from incorrect power input, for the feed rates of ilmenite and reductant. For example, excessive power input will tend to overheat the slag, causing the freeze lining to melt partially, establishing a new steady-state heat loss from the furnace. Compositional disturbances result from an incorrect reductant input for the given power and ilmenite input. In this work, the dynamic response of the slag and freeze lining to different inputs (flow rates of ilmenite and reductant, and power input) is modelled. The model is based on solidification equilibria, and quantified heat loss through the freeze lining. The conclusion is that the solidification equilibrium cannot constrain the composition to the eutectic groove for typical operating conditions. Keywords: ilmenite smelting, freeze lining, solidification, high-titanium slag

Jan 1, 2004

By L. W. Luo

Zeolite in some regions or countries of the world have been the subjects of materials for environmental remediation involving the use of removal to heavy metal ions and some organic pollutant as a sorbent because of its capacious ions exchange and huge surface area. This article addresses the equilibrium and kinetics for manganese adsorption using zeolite modified by hexadecyl trimethyl ammonium bromide (HTMAB) as a sorbent material over a range of pH between 3.4~7.2 with eight different Mn(?) solution concentrations. PHzpc (pH of zero point charge) of the sorbent was examined according to the method proposed by Tripathy and Kanungo, and a value of 6.91 was obtained. The experimental data fit langmuir?s model for the majority of pH and Mn(?) solution concentrations tested (0.92<R2<0.97). The maximal adsorption capacity, qm ascending with pH between 3.4~7.2, rise from 15.01mg?g-1 at 3.4 to 19.46 mg?g-1 at 7.2. Besides, the constant of Freundlich Kf have the same trend with qm, increases with pH ascending. And the sorption intensity, represented by parameter 1/n in Freundlich?s model, is favorable in entire range of metal ions concentration studied. Finally, kinetics data accurately fit to pseudo-second order which indicate that there must be sorption of Mn(?) behavior occurring on inner-sphere of the sorbent.

Jan 1, 2014

By Shubin Wang

Copper(II) and nickel(II) are often recovered from ammoniacal alkaline solutions by solvent extraction using hydroxyoxime extractants: both copper(II) and nickel(II) are extracted from ammoniacal alkaline solutions and, from the loaded organic phase, nickel(II) is selectively stripped with a dilute acid followed by copper(II) stripping with an acid of higher concentration. Since a small portion of ammonia is co-extracted with copper and nickel, the extracted ammonia should be scrubbed using a dilute acid before metal stripping. In the present study, a mechanistic model has been developed in order to support design and control of this process. The equilibrium distribution ratios of copper(II), nickel(II), and ammonia at 298 K using LIX® 84-I (active component, 2-hydroxy-5-nonylacetophenone oxime) as the extractant are successfully correlated by considering the relevant equilibria. Based on these results, quantitative prediction of equilibrium distribution ratios in the process has been made possible, and suitable conditions for the efficient separation of copper(II) and nickel(II) are discussed.

By Francesco Vegliò, Luigi Toro, Francesca Beolchini, Francesca Pagnanelli, Stefano Ubaldini

"Biosorption is an innovative technology used to remove heavy metals from aqueous solutions from mining waters and other industrial wastes. A wider application of this alternative process is strictly dependent on the understanding of the chemico-physical aspects involved, in order to optimize the operating conditions. Mechanistic models are the most useful tools used for understanding purposes, even if the empirical models are still widely applied for their simplicity.In this paper especially propagated biomasses of Sphaerotilus natans, calcium alginate and some waste materials were tested as adsorbents for single and binary solutions containing heavy metals at different pH. The equilibrium experimental results were fitted according to empirical and physical models with growing complexity outlining the inadequacy of the predictive models; in fact, the non-ideal interactions among metals require the insertion of additional correction parameters."

Jan 1, 2003

By Francesco Vegliò, Luigi Toro, Francesca Beolchini, Francesca Pagnanelli, Stefano Ubaldini

"Biosorption is an innovative technology used to remove heavy metals from aqueous solutions from mining waters and other industrial wastes. A wider application of this alternative process is strictly dependent on the understanding of the chemico-physical aspects involved, in order to optimize the operating conditions. Mechanistic models are the most useful tools used for understanding purposes, even if the empirical models are still widely applied for their simplicity.In this paper especially propagated biomasses of Sphaerotilus natans, calcium alginate and some waste materials were tested as adsorbents for single and binary solutions containing heavy metals at different pH. The equilibrium experimental results were fitted according to empirical and physical models with growing complexity outlining the inadequacy of the predictive models; in fact, the non-ideal interactions among metals require the insertion of additional correction parameters."

Jan 1, 2003

By Gary Kordosky

Equilibrium modifiers, first introduced into copper solvent extraction reagents in the late 1960?s, are widely used. The properties of various equilibrium modifiers with respect to copper extraction, selectivity, reagent stability and entrainment are discussed and some conclusions are drawn relating the structure of the modifier to the properties of the modifier. A new highly selective, low viscosity modifier is also introduced.

Jan 1, 2003

By L. S. Darken, H. A. Wriedt

The equilibria at 1 atm total pressure and 600° to 1300°C (1112° to 2372°F) between gas mixtures with various partial pressures of the reactive constituents (principally sulfur dioxide, carbon dioxide, water vapor, oxygen or carbon monoxide, and hydrogen) and coexisting solid phases (groups variously including calcium oxide, calcium carbonate, calcium sulfide, calcium sulfate, iron, ferrous sulfide, and the iron oxides) are examined. Tables and charts show the combinations of temperature, oxygen activity, and carbon dioxide partial pressure under which the various groups of the solid phases coexist and the corresponding sulfur dioxide pressures. In the presence of calcium sulfide, calcium sulfate, and calcium oxide, the partial pressure of sulfur dioxide has a peak value at each temperature which increases from 101 atm at about 800°C (1472°F) to 1 atm at about 1200°C (2192°F). With water vapor present, hydrogen sulfide may predominate among gaseous sulfur compounds, particularly at low temperatures and oxygen activities; under all other circumstances considered, sulfur dioxide is the dominant gaseous sulfur-bearing species.

Jan 1, 1974

By E. H. Jr. Dix

THE use of magnesium as an alloying element in aluminum alloys has been limited, in general, to comparatively small quantities. In duralumin-type, strong-aluminum alloys, magnesium is present to the extent of ½ to ¾ per cent. and various grades of Magnalite and the "Y" alloy of the National Physical Laboratory of England contain up to 1 1/2 per cent. In this country small quantities of aluminum alloy sheet containing 4 per cent. magnesium are produced commercially. All commercial aluminum contains sufficient silicon to convert a portion of the magnesium added to the compound Mg2Si. It is well known that the solubility of both magnesium and magnesium-silicide decrease with decrease in temperature. It is, therefore, impossible to separate the age-hardening effect of the magnesium-silicide from that of magnesium, except by the use of aluminum of such high purity that the silicon content is negligible. The present paper is the fifth1, 2,3,4 of a series from the laboratories of the Aluminum Co. of America reporting the results of investigations of the equilibrium relations in aluminum-rich alloys made from the high purity aluminum manufactured by this company .5

Jan 1, 1929

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By William Fink

THE constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunck1 analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoAl6 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer,3 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644° C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550° C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum; rich alloys prepared from electrolytically refined aluminum.4 Preparation of Alloys.-The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys.

Jan 1, 1932

By E. H. Jr. Dix

OF all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations had been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 5.25° C. to about 1 per cent. at 300° C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540° C., and that this amount decreases to about 3 per cent. at 20° C.

Jan 2, 1926

By E. H. Jr. Dix

THE work of Merica1 and other investigators indicates that the phenomenon of age-hardening in. alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum. Company of America to determine the functions

Jan 1, 1932

By William Fink

THIS paper is the nineteenth of a series from the Aluminum Research Laboratories, presenting the results of the investigations of equilibrium relations in aluminum-base alloys made from electrolytically refined aluminum. In previous papers equilibrium) relations have been deter-mined and correlated for 12 binary systems. Equilibrium relations have also been determined for portions of the aluminum corners of three ternary systems (aluminum-iron-silicon, aluminum-magnesium-silicon and alu-minum-copper-magnesium). The object of the present paper and those to follow is to increase our knowledge of the aluminum corner of the more important ternary systems. In 1926 Dix and Keith? suggested a new method for designating the phases encountered in alloy systems. The system has been used to a very limited extent 1,2,3. The system has since been slightly modified and will be used in this and future papers. In the system as modified, a phase is designated by placing in parentheses the chemical symbols of the elements essential to the formation of that phase. The symbols in the parentheses are separated by dashes in order to clearly distinguish them from a chemical formula. Elements that are not necessary to the formation of the phase in question, but which may be present in solid solution, are not indicated in the designation. If two or more phases would have the same designation according to these rules, they are dis-tinguished by prefixing Greek letters, and are definitely identified by X-ray diffraction patterns.

Jan 1, 1936

By Dix, E. H.

THE percentage of manganese used in commercial aluminum alloys is small, and yet this element is an important addition to some very valuable alloys. When used alone with commercial aluminum containing iron and silicon as impurities, the usual percentage in wrought materials is from 1 to 1.5 per cent., whereas castings may contain as much as 2 per cent. An aluminum-manganese alloy containing nominally 1.25 per cent. manganese is much used in sheet form for the manufacture of cooking utensils and other articles requiring a little greater strength and hardness than could be obtained with commercially pure aluminum. It is also used for various purposes in the form of rods, tubes and pipes. The aluminum-manganese alloys, both wrought &apos;and cast, offer excellent resistance to many kinds of corrosion attack. The U. S. Naval Gun Factory uses an aluminum alloy containing from 1 to 2 per cent. each of copper and manganese, for both castings and forgings. Manganese is also used, up to about 1 per cent., as a minor alloying .element in several of the strong aluminum alloys of the duralumin type. It is felt that the role of this element when thus used has not been fully understood, but it is believed that the results obtained in this investigation will throw additional light on the subject. The earlier work on the system aluminum-manganese was general in nature, and no detailed investigations of the relations existent in the useful aluminum-rich alloys have been reported. Guilletl1in 1902 surveyed the system, and Hendrichs2 in 1908 published an equilibrium diagram which, although based on .few data, is often used in the literature. Fragmentary work has also been done by other investigators."

Jan 1, 1927

By William Fink

NICKEL is used as an alloying element in several complex commercial aluminum alloys, among which are found some very interesting proper-ties, such as relatively high strength at elevated temperatures, relatively low coefficient of expansion, the absence of permanent growth, ability to take a good polish, and a bright, pleasing as-cast surface. For that reason the aluminum-nickel system was included in the list of binary aluminum systems that are being studied as a preparation for the investigation of more complex commercial alloys. This paper is the fifteenth of a series from the Research Laboratories of the Aluminum Company of America reporting the results of investiga-tions of equilibrium relations in aluminum-base alloys of high purity. The aluminum-nickel equilibrium diagram from 0 to 18 per cent nickel was determined, using the purest material available.

Jan 1, 1934

By A. C. Heath, E. H. Dix

THE importance of aluminum-silicon alloys in the light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and like silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminum and aluminum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. PART I.-ALUMINUM-SILICON ALLOYS The early work on this system was largely confined to determining the general form of the diagram and in this respect the results are in good agreement. Briefly, aluminum and silicon form a simple eutectiferous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Fraenkel1 (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solution. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility does not appear

Jan 1, 1928

By E. H. Jr. Dix

THE importance of aluminum-silicon alloys in the light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and like silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts, a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminum and aluminum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys.

Jan 1, 1927