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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 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 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 W. L. Fink, H. C. Stumpf, L. A. Willey

VERY few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.l0 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. MATERIALS The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society.4 Chemical analysis of the aluminum showed the following impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectrographic standard procedures5 No. IIA and No. SII respectively. DETERMINATION OF LIQUIDUS The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano.6 As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 ½ -in. iron pipe and pipe caps. The space around the sides of the crucible was filled with 40 mesh crystalline alundum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1948

By William Fink

ZINC is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd&apos; first established the existence of a solid solution region at the aluminum end of the diagram (y phase) by specific volume and microscopic determinations. Bauer and Vogel2 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined.. The solubility was placed between 15 to 20 per cent at 600 C., 20 to 22 per cent at 140° C. and 36 to 38 per cent at 270° C. Sander and Meissner4 decidedly modified the limits of they phase field of Hanson and Gayler&apos;s diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,5 utilizing dynamic hardness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler&apos;s at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400° to 500° C., that the solubility of zinc in aluminum at room temperature is less than 5

Jan 1, 1932

By William Fink

SINCE so many different curves have been published for the solid solubility of zinc in aluminum, it seems desirable to definitely establish the correct curve by two or more independent methods. The curve published in part I1 was based entirely upon X-ray measurements because the other methods employed at that time were not satisfactory. The present paper (the seventeenth of this series on high-purity aluminum alloys) describes the determination of the solid solubility of zinc in aluminum by the measurement of electrical resistivity at temperature and by microscopic examination. Since the publication of our part I in 1932, an investigation of the solubility relations in the aluminum-zinc system has been reported by Schmid and Wassermann2, who obtained their solubility results from lattice-parameter measurements on heat-treated and quenched speci-mens. The diagram that they published is shown in Fig. 1. In this investigation they also found by X-ray measurements that the parameter of the gamma phase changed continuously with zinc content and at such a rate that it would be identical with that of the beta phase at 60 atomic per cent zinc. It was concluded therefore that the beta and gamma phases, from the point of view of structural relationship, are one single phase. They also suggested a gap of immiscibility between 270° and 350° C. The complete boundary in this region could not be deter-mined satisfactorily by the method employed and therefore was not shown in their diagram.

Jan 1, 1936

By Clarence Zener

THE heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an under- standing will involve two distinct types of inquiry: (I) the direction of the trans- formation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed here in steel such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron- alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data being obtained from the simple binary and ternary equilibrium diagrams. FUNDAMENTAL EQUATIONS In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body- centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may be regarded as filling all the lattice positions of a given type. The introduction of the fundamental equations of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1946

By Clair Upthegrove, Elbert S. Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are: obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from. 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

By Elbert Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

By G. V. Cullen, N. G. Siviour

It has previously been reported that metal loadings of up to 6.8 m. eq/g. of dry coal can be obtained by contacting brown coal or lignite with ammoniacal solutions of ammine forming metals. Application of equilibrium expressions to further experimental results indicates that the extraction is by ion exchange, that the exchange is divalent-univalent for Zn, Cd and Ni, but is mainly univalent-univalent for Cu, and that to obtain reasonably uniform values for the equilibrium constants correction formulae must be applied to compensate for multiple functionality of the coal and its pH dependence in ion exchange. The results are shown to be consistent with the hypothesis that metal ammine complex cations are exchanged for protons derived from carboxyl and/or phenolic hydroxyl groups in the coal.

Jan 1, 1981

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By T. R. A. Davey

It is often important in the study of a process to determine whether the limitations are governed by equilibrium or kinetic considerations. Sometimes it is possible to devise a design of the process or the equipment so that the apparent. limitations set by equilibrium considerations are overcome. In this paper, detailed consideration is given to the lead refining processes of sulfiir-decoppering and of vacuum dezincing to illustrate this, and possible implications for other refining processes are indicated.

Jan 1, 2000