Search Documents

By M. Katzer, R. Klimpel, J. Sewell

The effect of using selective dispersants as wet grinding aids for ores is demonstrated on laboratory scale batch and continuous grinding equipment. A complete characterization of behavior is performed on a given ore to demonstrate correlations involving torque, % solids, net production rate, and slurry weight and volume loading. The relationship between such laboratory data and industrial scale testing results is very consistent.

Jan 1, 1982

By A. W. Allen

Progress in the art of amalgamation in recent years has been negligible, partly because a copper plate, though it occupies extensive floor space, requires frequent attention and invites theft, is a simple piece of apparatus that gives visible results; partly because the impression prevails that amalgamation is too primitive a process to merit consideration by an up-to-date metallurgist. Both these objections can be overruled. Plates can and will be superseded by more efficient, theft-proof amalgamating units. Improved methods of application other than by settlement or by impact, neither of which is effective for removal of fine gold, will be developed, and the process given wider opportunity. As A. F. Crosse aptly remarked, neglect to utilize amalgamation when free gold can be recovered thus is comparable to the decision of a storekeeper to deal only with credit customers. Usual practice is to follow amalgamation with cyaniding. Rarely is attention paid to the possibility of reversing the order—of extraction of the fine gold first by cyaniding; the coarse, subsequently, by amalgamation. Such a sequence avoids the alleged hazard that amalgamated gold particles may be unacted upon by cyanide, whereas cyanided gold particles are readily amalgamated. Research has indicated, however, that the mercury coating on a gold particle is easily soluble in cyanide solution, probably because such coating is a compound of gold and mercury. Comparative-test results at one plant, of cyaniding a ground concentrate before and after amalgamation, showed total extractions of about 90 and 100 per cent, respectively, indicating high solubility of the mercury-gold particle, if present, or the advantage of preliminary impoverishment before cyaniding, or both. The contention that a loss in residue from an amalgamation-cyanidation plant is occasioned by presence of amalgamated gold that escapes action by solution is not supported by adequate evidence. The function and scope of mercury as an aid to extraction of gold by cyanide is deserving of attention. It is a powerful desulfurizer. To restrict an extractive process to a concentrated product is logical and economical, if preliminary concentration will segregate a high per-

Jan 1, 1935

By R. Hogg

The mathematical description of solids transport in mills is an important aspect of the development of comprehensive models for the analysis, simulation and control of grinding systems. The basic mechanisms of particle transport and mixing, including gravity flow, carrier fluid transport, and "diffusion", are reviewed and their relative importance in wet and dry ball mills is discussed. Specific models for transport and mixing in dry, grate-discharge and wet, overflow ball mills are described. The limitations of the models, parameter estimation problems, scale-up criteria etc. are discussed and the conditions which lead to particle size dependent transport, and hence to internal classification in the mill, are described in detail.

Jan 1, 1984

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By Robert B. Hill

A history of gravity classification shows the development of many types of equipment with several prominent types continuing in use today. Part of the development and evolution is the spiral classifier. Data will be presented showing characteristic size separations in a closed circuit grinding operation. Comparisons with hydro- cyclone operation will be shown including operating cost comparisons. Effects of variables will be shown in spiral classifier operation. Finally, other uses for spiral classifiers will be described.

Jan 1, 1982

By W. D. Forgeng, R. E. Grace

The rate of copper corrosion in liquid lead was studied as a function of flow rate and temperature in a closed isothermal loop system between 350" and 500°C. Kinetic data were interpreted with the Nernst-Brunner equation and the Chilton-Colbum mass transfer analogy to heat transfer. Over the range of temperatures and flow rates employed the solution rate constant varied from 2 x 10-3 to 20 x 10-3 cm per sec. The rate constant was found to vary with the 0.76 power of the Reynolds number in the range 7500 < Re < 40,000. The results of this investigation indicate that the Cu-Pb corrosion process is controlled largely by diffusion across a boundary layer. particularly at the higher temperatures. The effective boundary layer for diffusion is found to be approximately three to four times smaller than the momentum boundary layer. CORROSION by liquid metals has long been a problem during melting, static containment, and casting. Recently, considerable emphasis has been placed on the understanding of liquid metal corrosion mechanisms in an effort to prevent mass transfer and eventual failure in liquid metal heat exchangers and in liquid-metal-fueled nuclear reactors. The present investigation was conducted to determine the relationships which exist between corrosion kinetics and hydrodynamic conditions in an isothermal loop containing a simple liquid metal-solid metal corrosion system. The Cu-Pb system was chosen for its simplicity and ease in handling. Previous isothermal Cu-Pb corrosion studies1-3 have been conducted in both static and dynamic systems but not under conditions which allow easy "scale-up" to engineering systems, such as liquid metal heat exchangers. On the other hand, most liquid metal loops which have been used to evaluate mass transfer rates4 have been driven with temperature gradients under conditions of natural convection and unknown flow rates. The primary contributions of this research are twofold: 1) to evaluate the design of a simple isothermal loop corrosion system and 2) to investigate liquid metal corrosion behavior under well-defined hydrodynamic conditions. MATERIALS AND EXPERIMENTAL WORK The apparatus used to measure the Cu-Pb corrosion rates is shown schematically in Fig. 1. The loop system consisted of 1) a reservoir made of Type 316 stainless steel containing a centrifugal pump and 2) stainless-steel tubing containing a removable copper test section. The copper test section was OFHC hard-drawn tubing, 11.0 0.05 cm in length and 0.775 ±0.005 cm ID. A Type 316 stainless-steel venturi meter* was inserted in place of the copper test sec- tion in order to determine the lead velocity as a function of pump speed at each temperature. The Cu-Pb system was chosen for this study because the solubility of copper in liquid lead is large enough to measure accurately but small enough that the diameter of the copper tubing was not changed significantly by corrosion. There are no intermediate phases formed in the system, and the solid solubility of lead in copper is vanishingly small so that back-diffusion cannot occur. Molten lead (corroding grade; 99.94+ pct Pb, 0.0015 max pct Cu) was charged from an auxiliary melting furnace into the system under an argon cover to minimize oxidation. The lead was then maintained at constant temperature by a stirred molten salt bath in which the loop was immersed to a depth just above the lead level in the reservoir, Fig. 1. The total volume of lead in the system was 320 2 cu cm.

Jan 1, 1969

Discussion of the paper of G. Howell Clevenger and Bhupendranath Ray, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2437 to 2475. ALLERTON S. CUSHMAN,* Washington, D. C.:-I am very much interested in the subject matter of this paper. I have had occasion to speak to this question before. There has recently been so much written and said and claimed about the effect produced by the addition of small quantities of copper to steel that there is certainly an impression abroad that a new and wonderful cure-all has been discovered. Are we facing a method of alchemy by which, at the expenditure of very little trouble and only a few cents&apos; worth of copper per ton, the well-known characteristics of steel with respect to some features are so marvelously changed as in effect to produce a new metal ? I am a great believer in the future of the iron and steel alloy field. I do not think that with all the advances we have made in metallurgy we have begun to scratch the possibilities of usefulness to mankind in the exploration of the alloy field, and I include in that alloy field even what might be designated as the dilute alloy field; that is to say, where a very small quantity of a metal alloyed with iron and steel confers upon it some new or extraordinary qualities. With respect to many of the physical characteristics of the copper-iron or copper-steel alloys I am not particularly competent to speak. With respect, however, to the investigation of corrosion problems and with respect to claims made with regard to resistance to corrosion, I am competent to speak insofar as I have specialized to some extent in that field and have given up a great deal of my time for a great many years to a study of it. Some years ago, being particularly interested in the study of corrosion problems, I received the very generous permission of a large manufacturing concern to use their large open-hearth furnaces any way I saw fit for exploring this particular field. There is not a metallurgist in this room who will not realize the generosity of a manufacturing company who would permit a man to pursue a theory and give him as his material to work with 60 tons of molten metal. At all events, I threw copper into the open-hearth furnace. I explored this alloy field, not in a ittle crucible in which I had to take out portions and have them

Jan 12, 1913

By John C. Calhoun, Raymond G. Loper

Theoretical calculations for the decline of pressure and the variation of instantaneous producing gas-oil ratio with increased cumulative production have been made for reservoir systems under various producing drawdown values and for various spacings. These variables have been included by a modification of previously Published techniques. This consists essentially of utilizing a radial system flowing gas and oil in a succession of steady state calculations. The results of the calculations do not show any variation in the predicted behavior of the internal gas drive reservoir when either the drawdown or the spacing are changed. The prediction of performance on an internal gas drive reservoir has been presented by various authors. &apos;,"&apos; These predictions are in the form of a pressure decline and an instantaneous producing gas-oil ratio as a function of cumulative oil withdrawal. In making these predictions a basic assumption has been that the saturation of the reservoir is uniform throughout at any time, or that the pressure differential imposed on the reservoir system is zero. Because of these assumptions the validity of such predictions has been questioned. Their application to actual systems, where saturations are not uniform and where producing differentials exist, has been a hazardous procedure. The authors cited have used different methods of approach to the derivation of equations for making their predictions and for arriving at a solution of both equations, but basically the same relationships are utilized in each case. In all instances the instantaneous producing gas-oil ratio is calculated from the equation: In utilizing this equation an average reservoir pressure and an average reservoir saturation must be known, the former to define ß, v, s, and uo/ug and the latter to define kg/ko. Predictions can be made, therefore, only for the conditions of a uniform reservoir saturation and a uniform reservoir pressure. This restriction of requiring a uniform oil saturation can be resolved by applying two-phase steady state flow for the radial system to the reservoir&apos;s history. Radial steady state flow is defined when the ratio of phases flowing,

Jan 1, 1949

By John C. Calhoun, Raymond G. Loper

Theoretical calculations for the decline of pressure and the variation of instantaneous producing gas-oil ratio with increased cumulative production have been made for reservoir systems under various producing drawdown values and for various spacings. These variables have been included by a modification of previously Published techniques. This consists essentially of utilizing a radial system flowing gas and oil in a succession of steady state calculations. The results of the calculations do not show any variation in the predicted behavior of the internal gas drive reservoir when either the drawdown or the spacing are changed. The prediction of performance on an internal gas drive reservoir has been presented by various authors. &apos;,"&apos; These predictions are in the form of a pressure decline and an instantaneous producing gas-oil ratio as a function of cumulative oil withdrawal. In making these predictions a basic assumption has been that the saturation of the reservoir is uniform throughout at any time, or that the pressure differential imposed on the reservoir system is zero. Because of these assumptions the validity of such predictions has been questioned. Their application to actual systems, where saturations are not uniform and where producing differentials exist, has been a hazardous procedure. The authors cited have used different methods of approach to the derivation of equations for making their predictions and for arriving at a solution of both equations, but basically the same relationships are utilized in each case. In all instances the instantaneous producing gas-oil ratio is calculated from the equation: In utilizing this equation an average reservoir pressure and an average reservoir saturation must be known, the former to define ß, v, s, and uo/ug and the latter to define kg/ko. Predictions can be made, therefore, only for the conditions of a uniform reservoir saturation and a uniform reservoir pressure. This restriction of requiring a uniform oil saturation can be resolved by applying two-phase steady state flow for the radial system to the reservoir&apos;s history. Radial steady state flow is defined when the ratio of phases flowing,

Jan 1, 1949

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.&apos; Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions.&apos; Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation.

Jan 1, 1955

By Madan M. Singh, William J. Courtney

Pneumatic stowing is commonly employed in European coal mines, but is not used in the United States. This paper reports a study conducted to analyze the conditions under which pneumatic stowing might be advantageously used and the techniques and costs involved in order to effect this. Although stowing may reduce the subsidence in a mining area, this does not entirely eliminate the surface damage. Besides, the cost of stowing will run about $1.50 to $3 per ton of coal mined not including the cost of fill material, if it has to be bought and transported to the mine. Stowing my, however, be economically viable under special circumstances such as in thick, steep, or contiguous seams.

Jan 1, 1976

By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,&apos; commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators&apos;-&apos; have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

COMMITTEES Committee on Arrangements DAVID H. BROWNE, Chairman BRADLEY STOUGHTON, Vice-Chairman LAWRENCE ADDICKS BURR A. ROBINSON PERCY E. BARBOUR E. MALTBY SHIPP GEORGE D. BARRON JOSEPH STRUTHERS J. V. N.. DORR E. B. STURGIS J. R.. FINLAY T. T. READ Louis D. HUNTOON R. H. VAIL

Jan 4, 1916

By Henry Louis

The object of the present paper is to describe a primitive method of gold-extraction, practiced by a small colony of Chinese in the district of Tomoh, one of the Siamese-Malayan States. This district has been worked for gold about 150 years, but has been only twice or thrice visited by Europeans, who are looked upon with a good deal of jealousy by the miners. The gold-district, covering not more than 10 square miles, is situated about Lat. 5&apos; 47l N. and Long. -101&apos; 39 E., on the headwaters of the river Teluban. It is a very mountainous region, lying on the northern flanks of the great range that forms the watershed between the rivers Patani, Kelantan, Teluban, etc., on the north and Perak on the south. The gold occurs in narrow veins and leaders of quartz, intersect- &apos; ing and intercalated among irregularly upheaved and contorted, highly metamorphosed, micaceous and chloritic schists. These veins vary between 3 inches and 3 feet in thickness, and are sometimes very rich. The geology of this region is thus very similar to that characterizing gold-regions all over the world; if must, however, be.

Jan 1, 1892

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick&apos;s second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method&apos; are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5&apos; could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5&apos; or Ag&apos;lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5&apos; and 0.6 N HNO3 solution for the A"&apos;), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5&apos; atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By P. T. Gallagher, W. A. Oates, J. A. Lambert

FAIRLY extensive equilibrium data exists for carbon dissolved in r iron.1-8 However the temperature coefficients of the carbon activity, ac , are insufficierltly preciseto reveal whether the heat of solution of carbon, ?HC , varies with composition. It is doubtful

Jan 1, 1970

By M. L. Jeremic

Abstract-Observations of ground behavior in mining the Choka Dulkan ore body have been described. Ore recovery was limited to approximately 60% because unconsolidated hydraulic fill did not permit either the widening of stope spans nor secondary ore recovery from pillars. Stope undercutting induced high stress concentrations. However, as extraction progressed, ground conditions improved but before extraction was complete they deteriorated again. After completion of a stope, the remnant rib and crown pillars continued to be deformed by other stresses for some time.

Jan 4, 1978

By John D. Erickson

The concepts of long-range, open pit planning presented here are not new. The new idea is how the factors that control the location of the final pit limits can be considered altogether as one large, simultaneous equation. The X, or unknown quantity that is being solved for, is a long-range pit design that fulfills the desired objectives. The objectives of a final pit plan are determination of the extent and location of ore reserves, the allowable stripping necessary to uncover the ore, the final pit surface intercept, final pit topography and the contained metal values in both ore and waste.

Jan 4, 1968

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;&apos; and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.&apos; Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively&apos; from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)&apos; which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By Y. C. Liu, W. R. Hibbard

Based on pole figure data and microstructural observations, the re-crystallization orientation found in a copper strip previously cold-rolled 99.5 pct from a single crystal with an initial (110) [112] orientation may be described as: a 30° rotation, clockwise and counterclockwise, about octahedral poles of the cold-rolled texture such that all four poles function at a low annealing temperature (400°C) and only three of them function at high temperatures (500&apos; to 1050°C). The relative intensity of deformation stresses on various slip planes can be correlated with the choice of poles affecting the rotations found in the recrystallized orientations. ROTATIONAL reorientation about the poles of densely packed crystallographic planes is an important characteristic of secondary recrystallization" in face-centered cubic metals. Some evidence has also been interpreted to show that such a rotational relationship also exists in the primary recrys-tallization process." In an investigation of the crystallographic relationships in the recrystallization process, several aspects of the experimental procedure should be considered. With cold-rolled poly-crystalline metal as the initial material, pole figure analysis leaves many ambiguities as to whether or not simple indices can be assigned to adequately represent its orientation. The rolling texture does not consist of a single texture. Minor deformation textures are usually present. In all cases, twin textures are present. The presence of both minor and twin deformation textures influences the recrystallization texture. In order to study the recrystallization mechanism, a more precise knowledge of the history of the material before recrystallization is necessary. Tensile deformation of a single crystal usually produces residual stresses which are concentrated at slip bands. Since the exact nature and orientation of these potential nuclei sites cannot be experimentally evaluated, the tensile deformation of a single crystal was not considered adequate. From the work done by Barrett and Steadman6 n copper, it appeared that cold rolling of a single-crystal specimen with an initial (110) [112] orientation would yield a specimen which fulfills the conditions required for the present investigation, namely a highly preferred single rolling texture with relatively homogeneous stress distribution. By investigating the recrystallization texture of this material, additional details of reorientation during recrystallization might be obtained. The purpose of this paper is to describe such an investigation. Experimental Procedure Copper used in the present investigation was cathode sheet with a purity of 99.94 to 99.97 pct. A copper single-crystal specimen, 1.15x0.8720x0.5322 in. (thickness) was cut from a cylindrical crystal which was grown in a Bridgman furnace.&apos; The cutting was accomplished on a horizontal milling machine operated at a very slow speed to obtain a (110) plane in the rolling plane and a [112] direction in the rolling direction. The disturbed surface was removed by electrolytic polishing in dilute orthophos-phoric acid (H3PO4) with a specific gravity of 1.14, and a current density of about 1 to 2 amp per sq cm. A 3-min polishing was needed to eliminate the disturbed surface causing Debye-Scherrer rings and a 45-min polish produced a surface which yielded sharp rounded Laue spots. It was estimated that about 1/16 in. of metal was removed from the original cut surface. The final orientation of this specimen before rolling was about 2" from the (110) plane in the rolling plane with a [112] direction aligned in the rolling direction. It is possible that a small amount of strain was still present in the cube despite the fact that the Laue spots seemed very sharp. It is doubtful, however, that this would be an important factor after a subsequent rolling reduction of 99.5 pct. This copper specimen was rolled on a laboratory rolling mill with two highly polished rolls 37/8 in. in diam in the following manner: 0.010 in. per pass to 50 pct reduction, 0.005 in. to 70 pct, 0.002 in. to 85 pct and, finally, 0.001 in. per pass to a 99.5 pct reduction. Specimens, about 1 in. sq with the rolling edges intact, were cut from the rolled strip by the electrolytic method previously described, after the strip

Jan 1, 1954