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The Froth Flotation Century

D.W. ~uerstenau*

In mineral processing, the last century of the current millenium has been the century offrothflota-
tion. The process did not resultfromfundamental research, but was developed over the years by
empirical methods. In more recentyears, our understanding of the fundamental principles of the
flotation process have made significant strides. This paper reviews some of the historicalperspectives
of developments in flotation reagents, the development and application of experimental toolsfor
delineatingflotability and interfactial phenomena, advances inflotationfundamentak, and the
development offlotation kinetics, both macroscopic and microscopic subprocesses. Through the
application of surface chemistry, theflotation process has permitted economic utilization of a vast
array of complex ores.

Froth flotation, as practiced today, had its beginnings in Australia nearly a century ago.
The first flotation plant in the United States, the Timber Butte Mill at Basin, Montana,
began operation in 1911. By 1980 (Martin et al., 1985), 440 million tons of ore were
treated in 239 flotation plants consuming 772 million kg of reagents and 6560 million
kwh of energy. In 1980,205 million tons of copper ores were concentrated to 4.2 million
tons of concentrates, consuming 383 million kg of reagents. The second largest tonnage
of ore treated was phosphate ore-109 million tons, from which 26.6 million tons of
concentrates were produced at a reagent consumption of 227 million kg. Also, major was
the flotation processing of iron ores, where 21.5 million tons of concentrates were
produced from 38.9 million tons of ore at a reagent consumption of 61 million kg.
Because nearly 2 billion tons of ore are treated worldwide by flotation, froth flotation is
clearly one of the most important applications of surface chemistry in technology-
particularly for control of the solid-liquid interface. Successful flotation separations
depend on selective interaction between solid particles and gas bubbles in aqueous media.
How to modify the interaction of water molecules with mineral surfaces through the
judicious additions of reagents and pH control is at the very heart of making selective
mineral separations from the vast tonnages of complex ores that are the source of our

* Department of Materials Science and Mineral Engineering, University of California, Berkeley,

The first inventor to break away from the use of either acid or oil and to make a clear claim for air as the sole flotation agent was Norris. Much of the basic research. contained an article by three senior students at the University of California titled. such as molybdenite or graphite. 1916). as we know it. especially in acid or salt solutions. There is some early academic research that surely could have led to the first froth flotation patent (Rickard. This throws the oil into afioth. The process depends upon the fact minerals with a metallic lustre. Flotation. where dissolved air was used to levitate the oiled sulfide particles using as little as 2 kg of oil per ton of ore..first. adhere to oil. making it possible to use thin oils instead of the viscous oil required by the Elmore art." Progress in flotation fundamentals has been based on experimental investigation in the laboratory. combined with keen insight into the meaning of the findings. or as Fleming and Kitchener (1965) so nicely put it. EARLY FLOTATION RESEARCH The start of modern froth flotation might be considered to be the 1904 Elmore vacuum- oil flotation patent. The oil in this condition assumes a certain load of mineral and holds it in a verystable condition. when treated in the form of a wettedpulp. the oil being kept in a single lake. The November 1903 issue of the college magazine. gives agreatly increased buoyantforce. they wrote: The charge may be agitated very gently. . while earthy minerals do not. Picard and Ballot. The froth flotation process did not come about as an outgrowth of fundamental research but evolved over this century by empirical developments. full of air bubbles: thus a very thorough contact of oil and pulp is obtained . which in 1903. Thefoam effect is best adapted for light flaky minerals.mineral raw materials. has been occupied with explaining why the existing process works so well. which is heavily charged with air or other gases. the separation of the metallic mineralfrom the gangue by means of oil. as outlined in his 1907 patent. was considered to be the hope of the metallurgical world. Concerned mainly with the second step. "Experiments on the Elmore Process of Oil Concentration." In introducing their paper. and broken up as little as possible consistent with a thorough contact of pulp and oil. Essentially all of the early research in flotation was directed toward patents.. if virtually not all of it. "science in pursuit of technology. Part of the levitating gas was carbon dioxide liberated by acidifying the pulp. The California Journal of Technology. The foam effect is produced by a violent agitation. In 1906. of course. This gas. Kirby was granted a patent that specified gentle agitation and the specific use of air. second. But there was a beginning of academic research in this field. progress in understanding the details of flotation science has resulted from application of new research techniques as they have become available over the passing decades. However. who used an oily frothing agent together with agitation to disseminate air bubbles into the pulp. Two distinct operations are involved. as reviewed by Rickard (1916). all of this had been preceded by the successful Elmore Bulk Oil Flotation process. the extraction of the mineralfrom the oil. The charge does not settle and overload on standing as in the case of the lake effect. Much of the basic research in mineral processing and process metallurgy can be characterized as post-mortem research. or the charge may be agitated so violently as to dash oil up into a foam orfroth. they stated. As will be discussed. really began with the 1905 Minerals Separation patent of Sulman.

it is intended to show that there are certain molecular attractions between widely different substances which would seem to be nothing more or less than the force of cohesion acting at sensible distances. . In 1915. 1916). thus. In discussing concepts of bubble-particle attachment in flotation. they. for the first time in the history of the metallurgy. There can be no doubt that there is a close parallelism between the angle of hysteresis of the contact angle and the ability of a mineral to float. Aglance at Clerk Maxwell'sfamous paper on capillarity will suggest immediately the explanation of contact angle. gave to the world the foam effect. That is quite remarkable. was fostered by selfrsh interest and. the process will become more valuable and of more general application.In my opinion.. and. Adsorption. and as these come to be worked out. implies the unequal distribution of substances at the boundary between two heterogeneous phases: solid-gas. those three students understood how research begets new research: The work above outlined suggests many lines offurther investigation. which is the heart or the centre of the important mining interests on the Pacifc Coast. It is remarkable that it was buried and lost. gave to the world. We now have a new principle to apply to a bubble.. and that it took threeyears of litigation to unearth it. Full disclosure as to a mode of operation which would produce an oil foam. afresh surface always has a greater surface tension than an old one. to wit: on account of adsorption. . (The author refers to Gibbs' treatise on thermodynamics!) In this article. an excess of concentration in the surface layer diminishes the surface energy. Taggart (1945) wrote of his contempt of all these early lawsuits with his great style: This idea. solid-liquid.. for thefirst time. The litigation surrounding the birth of froth flotation abounds in the early flotation books. the students discovered something else. especially that it should have been buried and lost in the University of California. unfortunately. and that it is the result of a certain equilibrium of interfacial tensions of air. was copied into some textbooks. and in the Great West. It never had any technical utility . If the dissolved substance diminishes the surface tension of the solution. ifit is stretched locally by conditions to break it. it is automatically reinforced at that point. conceived in ignorance and born in litigation. in its most general sense.. citing that same paper (Rickard. These attractions are shown . it is of interest to note some of the early studies and discussions on flotation fundamentals-concepts familiar to modern flotation scientists (1916) : The contact angle of various minerals with water was examined tofind at what angle the mineral had to come in contact with a water surface before it was wetted and could sink. Moving on to early approaches to the theory of flotation. water and solid. Miami Copper: Incidentally. Counsel Henry Williams stated in the case of Minerals Separation vs. and liquid-gas...

These quotations certainly apply to concepts and research topics being undertaken today. bubbles have never received the attention from flotation researchers suggested by Rickard. Rickard (1916) concludes his introductory chapter: .. Did Gaudin foresee the control of oxidation in sulfide mineral flotation through the use of nitrogen in flotation? It was not until 1958. the chemical effects of dissolved gases-has received scant attention. Many efforts were directed toward explaining differential flotation in terms of the relative occlusion of gases. directly and through an interveningfilm of oil. or the apparatus. . not every approach to explaining flotation involved reliable science. In 1916. and between water and air. However. edited by T.. we know that the key to theflotation process is to be found not in the oil. Rickard in 1916. and Rickard (1916) suggested how progress in flotation would be made: . Through the years.. we must look forguidance. bubbles usually play an inert role in flotation and merely provide a means for levitating the desired mineral particles into a froth layer. The Flotation Process. between glass and water. To the physicist. I t is not unlikely that control offlotation can be exercised through control of the gases. bubbles were considered to be at the heart of flotation science. All questions of the treatment of ore-slime should be studied in this new light. Most interesting is that they were written only four years after the establishment of the first flotation plant in the United States by James Hyde. and now a particular branch of physical chemistry-colloid chemistry-is beckoning us alluringly. Recent theories have shown thatgases are of extreme importance in many instances. it dependsfar more on physical than on chemical considerations. the acid. Gaudin commented: Developments inflotation have been so rapid that one of the essentialfactors at play-namely. which would be driven out to nucleate bubbles. although little used by most of them. to exist between glass and oil. not the chemist. as a result. The results of an application of this idea in our laboratory have been astonishing. As important a component as they are in the process. between glass and air. The metallurgist hitherto has depended on chemistry to guide him. in a study of the effect of chemical reagents on the motion of air bubbles in water. Although in 1934. 1916) : Physical chemistry has been a recognized tool of metallurgists for some time. he must now go back to school and acquire something more than a smattering of physics if he expects to understand the problems of the new process. but in the bubbles. And in 1915. thereby giving rise to selective flotation. Ralston wrote with great foresight (taken from Rickard. They can be found in the book. A.. that Fuerstenau and Wayman published the first results that clearly showed that the adsorption of organic surface-active agents (frothers) retarded the velocity of bubbles. The man who understands the physics of a soap bubble has mastered the chief mystery offlotation.

With some early researchers having the concepts of how to approach flotation research. and the process variables (Figure 1). the very basis of flotation is a physical process involving the relative interaction of three phases: one solid and two fluid. why was it so slow in getting under way? Perhaps the number of persons loolung at the fundamentals were too few (below a critical mass) and the process as a whole was really too complicated. It is through chemical additives which modify the interfaces involved in flotation that it is possible to control wettability. Ralston (Rickard. Mechanical Factors wettability bubble generation frothing particle dispersion particle interactions macroscopic kinetics FIGURE 1 A schematic representation of the three elements of flotation science and engineering For example. This mutual interaction can be illustrated schematically with a triangular representation of these three elements of flotation science and engineering. flotation is far more complicated than the study of bubbles. etc. which broadly controls flotation kinetics. particle dispersion or aggregation. These interactions control which of the two fluids will wet the solid phase (its wettability). and mechanical factors in the system. Successful flotation separations depend on the interrelation among the various physical. It is impressive that Reinders (1913) clearly showed how conditions for equilibrium in S/WL systems was controlled by interfacial thermodynamics. . Phvsical Phenomena wettability phenomena bubblelparticle interactions particle/particle interactions Chemical Control . As was recognized early on. Factors involved in the processing of ores by flotation also can be represented by a triangle that shows the interrelation between the mineralogical characteristics of the ore. the chemical variables that can be used to regulate the process.The third part of the triangle involves flotation engineering. bubble stability. chemical. FLOTATION SCIENCE AND ENGINEERING Clearly. 1916) was well aware of Reinders' 1913 classic work on the role of interfacial tensions in the liquid/liquid extraction of colloidal solid particles in oillwater systems and suggested that there would be a similar role for interfacial tensions in froth flotation. . flotation kinetics.

too. and the ability of one fluid phase to displace another from contact with the solid. Langmuir measured contact angles not only on clean glass but also on quartz. flotation was one of the most major metallurgical developments of the 20th century. galena. Taggart and Gaudin." delivered before the Faraday Society. This triangular behavior shows why Wark wrote in 1938: So many variables inJuencej7otation that it will be long before every one ofthem can be investigated and its influence on the process be determined. Historically. calcite. This is because it is the interfacial interaction of collectors with the different minerals that determines whether or not a flotation separation can be achieved. Clearly. and ii) the nature of the particle/bubble aggregation process. A first start in this direction had been made in 1919 by the great American surface chemist Irving Langmuir. the chemical variable. and sphalerite and proposed explanations for his findings. This. and modifiers. degree in metallurgical engineering from Columbia. When one considers how little was known in 1919 about the basic mechanism of flotation. Langmuir's first degree was a B. 1955) that slightly water-soluble chemicals containing nitrogen and sulfur were effective flotation collectors.The effective flotation processing of an ore of given mineralogy is regulated by control of the bulk chemistry of the pulp." Here we are today. FUNDAMENTAL FLOTATION RESEARCH Given that the process has so many variables. and . a very large one. 75 years later. "The Mechanism of the Surface Phenomena of Flotation. and the process variables. which perhaps led him to give a little of his attention to flotation.S. it is the characteristics of the ore being processed that control the other two corners of the triangle. Let us look at the development of flotation fundamentals in its historical context. the relation of the contact angle to the surface constitution of the solid. and that their action was chemical and entirely divorced from frothing that initiated detailed study of flotation fundamentals as we know it. But in this case. of course. Research in the broad area of flotation theory has been concerned with two principal aspects of the overall processes: i) the physico- chemical characteristics of mineral/collector interactions. can'be represented by a triangle. depressants. and will necessitate much experimental work before it becomes well understood. and is the subject well understood? By the way. "This subject is. Because he published his paper in the Faraday Society and not in a metallurgical journal. and Bartsch-papers that represented the beginning of scientific research dedicated to understanding flotation chemistry. by far most of the research has been concerned with mineral/collector interactions. with the three corners being the mineralogical characteristics. who was the first to show in a paper titled. His final comment was. his ideas never reached those in the field at that time. Langmuir had made impressive gains from a small number of experiments carried out in a brief period of time. which in turn controls the surface chemistry of the particles and bubbles in the system through use of collectors. that an adsorbed monolayer of oleic acid could change the contact angle on a solid in water (1919). activators. No doubt it was the 1921 discovery of Perkins (Sutherland and Wark. let us now discuss some aspects of the historical development of flotation theory. It was not until the early 1920s that the first detailed papers on adsorption phenomena in flotation were published by Fahrenwald.

This diagram illustrates the expansion of flotation technology with the invention of new reagents. The start was the oil collectors. There were significant early developments involving the use of inorganic modifiers.THIONOCARBAM. which shows the ascension of the mountain of flotation reagent progress during this century. OLUBLE N-Ill S-I1COLLECTORS (Perkins) Thiocarbanild FIGURE 2 Historical perspective: ascending mountains represent flotation reagent developments several sketches are presented to illustrate this century of progress in flotation fundamentals. Let us look briefly at the development of flotation reagents in terms of the diagram given as Figure 2. etc. . The Historical Perspective on Reagent Development The discovery of soluble collectors appears to have been the catalyst for major progress in flotation technology and for initiating fundamental research in flotation. containing creosote. fatty acids. Good sources of information about early flotation developments are Sutherland and Wark (1955) and Gaudin (1957). Modi.. followed by oleic acid itself. the great leap upward occurring during the 1920s.

for example.01 to 0. we will finally have reagents that will be selective. at the same time. real progress was made through the use of fairly simple techniques. until the 1950s there was little new in the way of reagents when Tveter developed polypropylene glycol ether frothers and Harris invented 2-200. The ascent of the next mountain in flotation (Figure 3) shows the development and application of techniques for studying flotation behavior and probing interfacial reactions. in many cases. This has led to definite progress in understanding the fundamental basis of flotation. The Historical Perspective on the Development of Experimental Methods Because of the complexity of the interactions between minerals and reagents. and cationic amines. 4. Taggart was the person who by brilliant deduction recognized that all collectors have polar and nonpolar groups within the same molecule. Experimental techniques for assessing wetting behavior and flotation response have played their part in this process. flotation was extended to the processing of nonmetallic minerals. Since 300 million tons of copper ore at 0. basic research has made progress when working with simplified and idealized experimental systems. Subsequently. this gave the world an additional 40 million kg of copper in that year alone! The need for new flotation technology in copper ore processing is still there. Years later1 could still mark the area as Ipassed by on the highway.5% (Martin et al. A brief discussion of the impact of 2-200 (a thionocarbamate) will illustrate how a new flotation collector can indeed still have major impact (Harris. each step resulting from the application of more sophisticated instrumentation for probing interfaces. but when the rougherfroth got through two cleaning steps neither the launders nor thefloors could hold the resultingfroth and it literally ran out of the windows over a length of perhaps 40 feet and to a depth of3 or 4 inches. at the pinnacle.02 kg/t . and the increase in copper recovery when using 2-200 as collector was two percentage points (Harris. The impact of Keller's discoveryin 1925 of xanthates as sulfide mineral flotation collectors is self-evident-it was the monumental beginning of modern-day flotation technology.such as lime for depression and copper sulfate for activation. in that in 1985 the recovery of copper by flotation in the United States was still only 82.7% copper were treated worldwide. increasing the frothing to an uncontrollable degree. using soap collectors with depressants. handle all particles in the comminuted ore. 1998). and not be too costly. In the 1930s. The recollections of James Bean (1971) are particularly interesting: Thiocarbanalidfor thefirst time gave the laboring metallurgist something that he could add which would improve the collection ofthe sought-for mineral without. The discovery of water- soluble collectors was the real advance in flotation. 1987). In 1979. 1998).. That this was no small triumph was demonstratedpractically to me while I waspotation operator at the Athur mill of Utah Copper Company which at the time (1 922) was using Utah Copper's own particular concoction of Barrett oils and sulphur stewed up together. first thiocarbanalid and particularly Keller's discovery of xanthates.5 million kg of 2-200 were produced at a reagent consumption of 0. Hopefully. . hoping to lower the mill tailing. However. Late on a sleepy afternoon an operator unduly increased the 'oil'being fed.

It was Wark and his colleagues who developed the technique to reliable accuracy. the modified Hallimond tube. Starting with the captive-bubble device of Taggart. EDANCESPECTROS. In the early 1950s. Gaudin and his coworkers extensively utilized radioactive tracer techniques to determine adsorption isotherms of flotation collectors and activators on purified minerals.) In the late 1940s and 1950s. Wark worked out the detailed flotability response of sulfide minerals. DWF) FIGURE 3 Historical perspective: development of experimental tools for delineating flotability and interfacial phenomena Progress was first made in understanding flotation behavior by Gaudin and his coworkers through study of the flotation of pure minerals using miniature flotation machines. electrochemical flotation devices were conceived of for investigating the electrochemical aspects of sulfide mineral flotation. Electrokinetic measurements (zeta potentials) were found to be a very useful tool in flotation surface chemistry. (Warkstated that contact angle data published before 1931 were unreliable. several micro-flotation devices were developed and used for studying small-scale flotation: bubble pick-up. . EADY-STATE POLARIZATION ICROCALORIMETRY (Mellgren) D SPECTROSCOPY (Wadswofth) TITRATION (deB~yn) NTIALS (Salamy 8 Nion) ECTROKINETICS (Sun. induction-time measurement devices. In the early 1970s. etc.

which shows tubes for testing flotation response published by ~ a l s t o nand Allen in 1916 (Rickard.. Because the floating mineral particles are not removed from the flotation medium in Hallimond tube flotation tests. the physical chemistry of flotation can be delineated if the experiments are conducted with . as can be seen in Figure 4(a). 1916). W. 1955) in Australia modified the Hallimond tube so that it could be used for experimentation in flotation systems [Figure 4(b)]. Fuerstenau et al. exsitu and insitu. (b) the Hallimond flotation tube as modified by Ewers in 1 9 5 2 (Sutherland and Wark. 1916). Although not shown here. (a) Ralston and Allen's 1916 test-tubes for flotation u (b) E w e r s ' 1952 modification of t h e Hallimond flotation t u b e . and (c) the Hallirnond flotation tube as modified by Fuerstenau in 1 9 5 5 (D. The modified Hallimond tube has provided a widely used means for delineating correlations of surface chemical conditions with flotation response in pure systems.-. but offset by about two decades. 1957). Fuerstenau (1957) further modified the Hallimond tube so that it could easily be operated reproducibly under closely controlled aeration and agitation conditions [Figure 4(c)].+ PATH OF FLOATED PARTICLES CONCENTRATE STEM . the apparatus that Hallimond (a mineralogist) constructed in 1944 to separate mineral grains by their differences in flotability almost had its beginnings some 80 years ago. 1957) Parallel to this. In 1952. MAGNETIC STIRRING BAR POROUS FRlT -GAS INLET FIGURE 4 (a) Test-tube devices used by Ralston and Allen in 1 9 1 6 (Rickard. has been the application of techniques for measuring directly the interaction of reagents with mineral surfaces and for probing the structure of adsorbed films at the interface. Ewers (Sutherland and Wark.

and the contact angle. and flotation response for quartz at neutral pH with dodecylammonium acetate as collector (after Fuerstenau et al.. Ralston wrote (Rickard.FIGURE 5 Correlation of contact angle. 1964) high-purity samples and reagents (Fuerstenau. . the zeta potential. 1916) : It is a scientificfact that when a solid particle is suspended in water. adsorption density. Figure 5 illustrates the precise correlation of the Hallimond tube flotation response of quartz with dodecylammonium acetate collector with the adsorption isotherm. and that thefroth is charged negatively and so attracts the positively charged orflotable minerals (such as galena and sphalerite) and repels the negatively charged or nonflotable ones such as silica or limestone." Of this. in 1914. . It is through this type of experimentation that significant progress was made in working out the physical chemistry of flotation during the last 40 years. The Historical Perspective on the Developments in Flotation Fundamentals The third ascent of the historical flotation mountain (Figure 6) illustrates how progress has been made toward understanding flotation fundamentals. 1957). that is the fundamentals of reagent-mineral interactions. However. the amount and polarity of which will depend upon the nature of the particle surface and the electrolyte in which it is suspended. which really started only after 1920.It has been demonstrated thatflotable particles have charges of one polarity (positive) and that nonflotable particles have charges of opposite polarity (negative)... the water will form around the particle a contactfilm that generally possesses an electric charge. zeta potential. Ralston and others proposed what was termed "the electrical theory of flotation.

This same period has seen real progress made in the flotation of fine particles and in understanding the complex surface reactions involved in the flotation of sparingly soluble salt minerals. unfortunately. "This theory. and Taggart. Gaudin even commented that." Interestingly.Wark. modern theories of bubble/particle interaction contain elements of these ideas.. The period starting in the 1950s was another one of major advancement.FIGURE 6 Historical perspective: ascending mountains represent advances in flotation chemistry fundamentals In 1927. Periods of marked progress in understanding the surface chemistry of collector adsorption were made in the 1930s (mostly toward delineating sulfide flotation behavior). in the 1950s (mostly in understanding oxide flotation behavior) and in the 1970s and 1980s (where much attention was readdressed toward delineating the electrochemical nature of sulfide mineral flotation). characterized by the application of the fundamental principles of surface and colloid . was not developed as fully as it seems desirable. largely through the seminal contributions of Gaudin. The broad period of the 1930s decade was one of pronounced advancement in flotation fundamentals and particularly in delineating the chemical aspects of flotation.

T. and separations then depend on the pH at which the surface of the different minerals is uncharged (the point of zero charge. this was strongly influenced by Professor J. In part. 1989) combines results from Modi and Fuer- stenau for corundum (alumina) with those of Iwasaki for quartz (silica) to illustrate the effect of pH on the zeta potential and flotation response of these two minerals with . adsorption phenomena. or PZC). the collector ions adsorb when they are charged oppositely to the surface itself (it should be recalled that the charge on oxide surfaces are determined by the adsorptionlreaction of hydrogen ions with surficial lattice sites). Figure 7 (after Fuerstenau and Herrera-Urbina. 1989) chemistry to flotation systems. Flotation collectors that physically adsorb on oxides (such as alkyl sulfonates or alkyl ammonium salts) function as counter ions in the electrical double layer at the minerallwater interface. That is. water/hydrocarbon-chain interactions. Perhaps the systems that are best understood today involve the flotation of oxides with ionic surfactants. Th. and solution chemistry. with the mineral engineering group of Gaudin. The behavior of oxide and silicate mineral systems depend on the char- acteristics of the electrical double at the minerallwater interface.I. Overbeek's year at M. G.FIGURE 7 Correlation of the zeta potential as a function of pH for quartz and corundum (alumina) with flotation recovery with 4 x lo-' M dodecylammonium chloride and sodium dodecylsulfonate and as collector (from Fuerstenau and Herrera-Urbina.

In such systems. The strong tendency for hydrogen bonding between water molecules to expel the hydro- carbon chains of surfactants from water is responsible for the formation of micelles in aqueous surfactant solutions. but we are unable to decide ifthis is an identity. Through the years. the published literature records the many spirited debates over collector adsorption mechanisms in sulfide mineral flotation: Gaudin (1927). flotation depends on the collector being charged oppositely to the mineral surface." Wark and Cox (1934)." Taggart (1930). the hydrocarbon chain length has a major role in surfactant adsorption. As these plots show. byfunction of the reason of chemical reactions of well recognized types between the reagent and the particle aflected. " . inflotation pulps. the mineral becomes very hydrophobic and its flotability increases markedly. 'Xll dissolved reagents which. using either the anionic or cationic collector. The history of fundamental investigation of sulfide mineral flotation has extended over many more decades that for the behavior of nonmetallic minerals. Figure 8 shows the distinct dependence of quartz flotation on the number of carbon atoms in the series of alkylammonium acetate collectors. C O N C E N T R A T I O N OF R N H 3 A c . and for the association of adsorbed surfactant ions at the mineral/water interface into hemimicelles. and the minerals can be separated at pH's where the minerals themselves are oppositely charged. 1964) 4 x lo-' M sodium dodecylsulfate or dodecylammonium chloride. Under conditions where hemimicellesform. and thereby reduces the solution concentration necessary for flotation. "The mechanism by which xanthatesfloat other suljides than galena may involve an adsorption of xanthate ions withoutfurther reaction.. Increasing the collector chain length results in an increased free energy of adsorption. "Wefind that there is a strong connection between adsorption of xanthates and the solubility of the heavy-metal xanthates. either by action on the to-be-floated or on the not-to-be-floated particles affect theirflotability. M O L E / L I T E R FIGURE 8 The effect of the hydrocarbon chain length on the flotation response of quartz at neutral pH as a function of the concentration of alkylammonium acetate collectors (after Fuerstenau et al.

"Assuming a complete or nearly complete monolayer of 'ions'on the mineralparticles. The electrochemical potential can be regulated either with a potentiostat or chemically. "Electrochemical investigations of the interaction of thiol collectors with sulfide minerals have demonstrated that each of the three anodic processes-chemisorption. reaction to form a metal collector compound.0144 m M for chalcocite and 0. which is then the species that imparts hydrophobicity to pyrite. namely." Woods (1984). going from reducing to oxidizing conditions. Nixon (1957)." There is no doubt that electrochemical reactions have a significant role in the flotation of sulfide minerals with xanthate collectors. V RGURE 9 Relationship between flotation recovery and conditioning potential for chalcocite. chalcopyrite. one would obtain a bulk concentrate with so much charge that it would explode with greater violence than an equal weight of nitroglycerine!" From this evolved Cook's neutral molecule theory of flotation collection. the adsorbed collector is readily oxidized to dixanthogen. In the case of the copper minerals. "Prominent theories could be reconciled by the electrochemical approach. the potentials are below that for the formation of dixanthogen and the hydrophobicity results from the formation (chemisorption) of cuprous xanthate at the surface. POTENTIAL vr SHE. Cook and Nixon (1950). 1985). Richardson and Walker (1985) clearly showed the dependence of the floatability of a number of sulfide minerals (Figure 9) with ethyl xanthate on the oxidation potential. which is the same idea that Barsky presented in his 1934 discussion of the critical pH curves of Wark and Cox (1934). "The data reported may be used to substantiate the view that the contact angle measured was that of a xanthic acid film. Fuerstenau and .02 m M for the other minerals (Richardson and Walker. bornite. and pyrite. In the case of pyrite. Ethyl xanthate concentration of 0. and the formation of a dithiolate-plays a role in creating hydrophobic surfaces." It should be pointed out that Cook clearly did not consider ionic adsorption in terms of the electrical double layer.

1988). there is no flotation of chalcocite with hydroxamate as collector. During the last three decades. . the lower one under the conditions where copper ions hydrolyze (about pH 6) and the second where the hydroxamate hydrolyzes to hydroxamic acid (about pH 9). shear flocculation. in that we say the same today: One of the outstanding problems in need of solution for the improvement. The potential for the chalcocite system is slightly oxidizing. In the case of chalcocite. Hanson conducted a detailed electrochemical investgation of chalcocite with a collector that does not oxidize. as exemplified by the selective flocculation/flotation operation of the Tilden Mine of Cleveland Cliffs. namely a chelating compound. . there has great interest in the processing of fine particles. Again. and chelating flotation reagents. Since a major part of the present-day losses is in theform ofnear-colloidal or colloidal material. potassium octyl hydroxamate (Fuerstenau. Figure 10 shows the pH dependence of the floatability of chrysocolla (a hydrous copper silicate) and that of chalcocite. the 1934 foresight of Gaudin is intriguing. under reducing potential conditions.. The flotation response of chrysocolla shows essentially two metallurgical eficiency is that of treatment ofparticles of colloidal or near-colloidal size.. the problem assumes enhanced importance. 0 CHRYSOCOLLA 5 x M HXM I CHALCOCITE lo-' M HxM 1 FIGURE 10 The effect of pH on the flotation response chrysocolla and chalcocite with potassium octyl hydroxamate as collector. the lattice copper ions become available to chelate with hydroxamate and the behavior is now somewhat similar to that with chrysocolla. but also floc flotation. Laboratory experimentation has included not only selective flocculation. and the fine- particle investigations continue today. But under oxidizing conditions.

(Dukhin. S. Klinpel) OBABILIN MODEL (Kelsall) CHEM. who unfortunately never published his work but presented it at an Engineering Foundation . The earliest attempt to develop a theoretical basis of flotation microprocesses was by T. with the kinetics of the subprocesses determining the overall kinetics. It is the interfacial interaction of collectors with minerals that determines whether or not a separation can be made by flotation. The microprocesses depend on the surface chemistry and physics of the system. both macroscopic and microscopic models. both macroscopic and microscopic subprocesses The Historical Perspective on t h e Concepts of Flotation Kinetics The final depiction (Figure 11)of the ascent of flotation fundamentals illustrates the development of flotation kinetics. and to subject these to appropriate experimental tests. kinetic studies are concerned with rate of removal of floatable material from flotation machines. to develop kinetic equations on the basis of the model. that is to formulate a model for the microprocesses. (Huber-Panu. KINETICS (Schuhmann) INDUCTION TIME ( Sven-Nilsson) IRST ORDER KINETICS (Garcia-Zuninga) FIGURE 11 Historical perspective: ascending mountains represent development of flotation kinetics. Mika. the unit event is the formation of the bubble/particle aggregate. Dejaguin) EORETICAL KINETICS (Sutherland) PARTICLE SIZE EFFECTS (Schlechten et al. Research at the most funda- mental level in kinetics would certainly be to develop an absolute flotation-rate theory. MOD.) ONTINUOUS LAB. on the microscopic scale. On the macroscopic scale.

The role of the hydrocarbon chain of alkyl collectors in flotation. Int.W.M. G. 4: 27 pp. Eric Forssberg. Predicting flotation rates using a rate equation derived from first principles.L.. P.H. A. 211: 694-699. No. T.W. Fuerstenau.G. Elsevier. Part A: 63-80. Mining and quarrying trends in the metals and industrial minerals indytries. & Colloid Chem. Minerals Yearbook 1985. Mao.H. 1998.. Clearly.S. 1997. Metzger. 1957.. and Yoon. D. Flotation science and engineering advances and challenges. J. A. Cook. 15: 62.M. G. D. Endeavour.. and Wayman. 135 (No. J. SUMMARY The past success of this empirically based process must be almost unique in modern technology. M.. 79: 50-77.. and Kitchener. Transactions AIME. ed. Flotation's future beset with difficult problems. we have now reached the stage when further elaboration of the flotation process will demand a more profound understanding of its fundamentals.W. Development of the theory of the flotation of sulfide minerals. Engineering and Mining Journal. Mao and Yoon (1997) did publish their derivation of a flotation-rate equation based on considerations of both hydrodynamic and surface forces in bubble-particle interactions..M. Second edition. D.H.C.. Martin. and Hyde. finer grained.D. K. Extension to new fields for separation and environmental remediation is upon us. 54: 445-459. [also 1928. Flotation.. 229: 321-325. McGraw-Hill. Gaudin. 573 pp. AIME Trans.J. 1950. . G. Effect of chemical reagents on the motion of single air bubbles in water. T. A..W. Fuerstenau.. L.U. 158: 93-95. As Paul Queneau (1973) wrote 25 years ago. M.. 1934. D.W. REFERENCES Bean. 1987... the ultimate potentialities of the flotation process will not be known until the surface chemistry of a wide range of mineral species has been completely explored.S.W. Tale of tails. Theory of water-repellent films on solids formed by adsorption from aqueous solutions of heteropolar compounds. Engineering and Mining Journal. Gaudin..1 Gaudin. Proceedings of the XVI International Mineral Processing Congress. Amsterdam. "The wealth implicit in American mineral resources is no longer a bonanza which lies in the ground for the talung-it now lies primarily in the extractive technology employed. adsorption density. Fuerstenau.W. 5 1:171-181. 208: 1365-1367. May 1971: 59.A. J. Washington: 7-65. and Somasundaran. D. Phys.. Transactions AIME. Edelstein. AIME Tech. Fleming. 1988. 1927.. Modified Hallimond tube for flotation testing.H.. I. 1958... Publ. Fuerstenau. Mineral Processing. R-H. D. 24(92): 101-105. Transactions Faraday Society. 1965. New York. 1920.. private communication.. Department of the Interior. Mining World. Recently. Harris.. The mechanism of surface phenomena in flotation. Langmuir.. and Nixon. Because many of the ores are more complex. 1971. 1964. Correlation o f contact angles. 1957. Flotation mechanism. Healy. and more refractory to treatment. zeta potentials and flotation rate.A. 1): 29-31. Transactions AIME. Bureau of Mines. J.. 1957. a discussion of the functions of flotation reagents.Conference in 1966. Fuerstenau. P." It is vital that we have the researchers available to continue this task. J. and Seele. C.

11: 198-210. Rickard. 1913. 1916. 13: 235. Wiley. 1930.XVInternationa1 Mineral Processing Congress. I. Melbourne. 40. W. K. Mining and Scientific Press.. J. A. Sutherland.. 1938. 1973.E:. Symposia Series No.L. 1934. The Australasian Institute of Mining and Metallurgy.A. N M E . Melbourne. Principles of Flotation. The flotation of chalcocite. Koloid-Zeitschrift. R. chalcopyrite. 489 pp. Principles of Flotation. Wark. Woodcock.Nixon. I-an experimental study of the effect of xanthates on contact angles at mineral surfaces.C. 91-115. 112: 189-244. T. Richardson. Queneau. Australasian Institute of Mining and Metallurgy. 1945.W. Principles of flotation.F. Chemical reactions in flotation. ed. 364 pp. G. . and Knoll.W. Schulman. New York. T.. M. H . DieVerteilung eines suspendierten Pulvers oder eines Kolloid gelosten Stoffes zwischen zwei Losungsmitteln. Journal of Metals. Modern practice and technological innovation in the nonferrous industries.. in Proceedings of the 2nd International Congress on Surface Activity. 1957. T. In Principles of Flotation-The Wark Symposium. and Walker.W. 87: 217-260. Jones and J.B.E. P. p. I. Woods. A. Taylor.F. 3: 369. Taggart. San Francisco. Cannes.. GEDIM. A. P. A. 12-52. Taggart. and pyrite in an electrochemical flotation cell. 1955. and Wark.F. Trans. 1985. Handbook of Mineral Dressing. Discussion.. ed. and Cox. Electrochemistry of sulfide flotation. 1984. The Flotation Process. N M E . of Mining and Metallurgy. I.. 15-18.. Wark. H . St-Etienne. von Reinders. London. Trans..C.. Butterworths. Parkville....W. Australasian Inst.. bomite. J.