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By Fathi Habashi, Michel Pagé, Farouk T. Awadalla

"Chrysotile asbestos can be dyed with certain dyestuffs to form stable coloured products whose hemolytic and cytotoxicity are greatly reduced. Examples of these dyes are Thiazol Yellow G (a monazo dye) and Trypan Blue (a diazo dye). Other dye stuffs, for example, basic dyes with triphenyl methane structure, Brilliant Yellow (a diazo dye), and Methylene Blue (a thiazine dye) colour asbestos but do not reduce its toxicity. Similarly alizarin, 8-hydroxyquinoline, and representative members of the phthalein group Bromocresol Purple and Phenolphthalein.IntroductionThere is, at present, a controversy regarding the dangers of asbestos fibres, and attempts are being made to render it less toxic. One of these attempts consisted of treating chrysotile asbestos with gaseous phosphorus oxychloride, POCI], at ambient temperature and in absence of moisture. The product had to be heated at 300°C to 500°C to expel exess entrained reagent to get a material containing 0.5070 to 5% phosphate groups and known as Chrysophosphate (Lalancette and Dunnigan, 1982). This product showed decreased toxicity as measured by its hemolytic effect on red blood cells (fable 1). In another approach, Flowers (1983) showed that when chrysotile asbestos was thoroughly mixed with a solution of ferric ammonium sulphate and the slurry was then filtered and dried, the product showed a marked decrease in cytotoxicity.In the present investigation the problem of toxicity was considered from a different point-of-view. Chrysotile asbestos is a hydrated magnesium silicate that can be represented by the structural model shown in Figure 1 from which it can be seen that magnesium hydroxide groups, Mg(OH)2, form a part of the silicate structure. Certain organic reagents that are known to react with magnesium ion in solution to form chelates were reacted with asbestos to find out whether a chelate was also formed on the fibres, and if so , what will be the hemolytic action and cytotoxicity of the product."

Jan 1, 1991

Surface contamination of minerals during fine grinding may occur due to coating of one material on the other. This can alter the surface chemical properties and adversely affect the separation of minerals by physico-chemical processes. In dolomite-silica system, selectivity was completely lost (compared to a synthetic mixture) after wet grinding of the minerals in spite of using a dispersant. Adsorption and surface characterization studies were conducted on silica particles separated after grinding with dolomite. SEM-EDAX analysis indicated the presence of dolomite on silica particles, which could cause the loss of selectivity.

Jan 1, 1993

By C. R. Kuhn

From 1968 to 1975, most work in surface modification of inorganic materials involved silane coupling agents. A silane coupling agent can be described simply as an oganosilicon chemical having a general formula RSi-X3 wherein the R group is attached to a silicon in a thermally and hydrolytically stable manner, and X is a hydrolyzable group usually having an alkoxy functionality. About 1975, Kenrich Petrochemicals brought into the market place titanate coupling agents. Titanate coupling agents usually consist of one alkoxy group and three functional groups attached to a central titanium atom. Zircoaluminates became available in about 1982. Zircoaluminate organometallic coupling agents, which vary principally in their respective organofunctionalities, arise from a basic technology in which two different types of organic ligands are selectively bound to a low-molecular weight zircoaluminate backbone.

Jan 1, 1995

By E Mielczarski

Determination of the adsorbed layer composition and structure at molecular and atomic levels and understanding adsorption mechanisms and dynamics are vitally important for the preparation of surface layers with specific functions. Direct information, at a molecular level, about mineral surface composition, its structure and surface distribution is crucial to perform an efficient separation process for mineral beneficiation. This information is equally important for modifying surface properties of industrial minerals for specific applications such as: fillers, composites, weathering resistance, etc. An understanding of the mechanisms and kinetics of the interaction of first adsorbed organic molecules with mineral surfaces is a fundamental requirement for the prediction and control of the macroscopic surface properties governing the efficiency of separation technologies or new material formulations. The developed infrared external reflection technique has a unique ability to study interface phenomena, at a molecular level, on heterogeneous substrates. The variety, precision and reliability of information about the interface phenomena delivered by this technique is superior to any other single technique. The experiments are fast and non-destructive. High sensitivity (starting from 20 per cent of the monolayer) in situ collected information in a multiphase system, even in the region of strong absorption of the substrate, makes this technique a very valuable experimental tool. The complexity of the recorded reflection spectra, their sensitivity to variations of the optical properties of all bulk and surface components and their spatial distribution in the system under investigation, are in fact the major strengths of this technique. A few examples of the application of this multi-diagnostic technique, for monitoring surface modifications of semi-soluble minerals for selective flotation, will be discussed in detail in this paper.

Jan 1, 2005

By A. Zhecheva

A commercial titanium alloy Ti-6Al-2Sn-4Zr-2Mo has been gas nitrided in this work, in pure nitrogen atmosphere in order to improve its surface properties. The nitriding was performed at two different temperatures, 950 and 1050°C, and for different periods of time. The influence of the initial surface roughness on the diffusion process and on the surface properties of this material was studied. The influence of the processing parameters of gas nitriding on the surface roughness, phase modifications and the microstructure of the nitrided layers has been analyzed using atomic force microscopy (AFM), X-ray diffraction and optical microscopy. Microhardness profiles were obtained on cross-sections of the samples after gas nitriding applying a Knoop indenter.

Jan 1, 2004

By John C. Draper

Little precise information is available on the effect of mining on the surface topography. It is often assumed that after mining the surface will simply sink. This is not an infallible conclusion as is well illustrated in two of the three examples herein. This paper describes the results of an attempt to precisely measure the surface movement in the area around coal pillars left in place for three oil wells in a completely mined and caved area at the Harwick Mine of the Duquesne Light Company. The dates when the various measurements were made are shown on the data sheets and indicate the rate of surface movement. These oil wells are identified as wells Nos. 2, 3, and 6. This mine property is located on the north side of the Allegheny River at Cheswick, Pennsylvania, and extends in a northerly and westerly direction about five miles. The three well pillars are situated on the westerly side of the Bessemer and Lake Erie Railroad some 2,000 feet from Rural Ridge, Pennsylvania (Fig, 1).

Jan 1, 1964

By Cao Shenggen

Experiences in the developed countries have shown that continuous increase of panel width (or face length) is one of the major technical trends for high production high efficiency mines. Increasing the panel width will increase not only the panel output, simplify the gateroad layout, facilitate high concentration of production, but also increase resources recovery and facilitate protection of surface structures. This paper uses the No.4326 super- wide panel, Wangzhuang Coal Mine as an example. This mine employs the fully-mechanized top-coal caving longwall mining method. Through surface subsidence monitoring, the dynamic characteristics of surface movement were obtained. The dynamic surface movement during mining and the final surface movement after mining were predicted using the Mining Subsidence Prediction System. The results indicate that after mining, the surface above the super-wide panel reached a state of full subsidence, So it can ensure the No.309 National Highway above is located in the flat bottom of the subsidence basin, and there is little impact on the national highways when panels on both sides of 4326 Panel are mined.

Jan 1, 2003

By J. R. Schneider

INTRODUCTION Landowners in Texas for many years have freely granted, reserved and leased "oil, gas and other minerals" or interests therein. In recent years we have witnessed much litigation concerning what sub- stances should be included as "other minerals" within the phrase "oil, gas and other minerals," and this question has received the attention of numerous legal scholars. At the South Texas Uranium Seminar held in Corpus Christi, Texas, in September, 1978, Mr. William R. Dodson presented a paper dealing with this very subject and entitled "Uranium - Mineral or Surface? Who Owns It?" In his paper, Mr. Dodson reported on two recent Texas Supreme Court decisions, Acker v. a, 464 S.W.2d 348 (Tex. 1971) and Reed v. Wylie, 554 S.W.2d 169 (Tex. 1977). which held that the particular substance in question in each case is not a mineral within the phrase "oil, gas and other minerals" if substantial quantities of the substance lie so near the surface that production will entail the stripping away and substantial destruction of the surface. Since that time another chapter has been written in the Texas saga of "When is a Mineral not a Mineral?" and it is the intent of this paper to present an update of the Texas law. A review of the early Texas cases so ably covered by Mr. Dodson in his paper will not be repeated, except as is necessary to illustrate the evolution of the legal doc- trine which has been so aptly named "The Surface Destruction Test". BACKGROUND In order to appreciate the genesis of the problem, one must consider that oil and gas production commenced in Texas many years ago, Spindletop came in in 1901. As oil and gas became more valuable, land- owners with considerable frequency sold interest in the oil, gas and mineral estates in their lands, and reserved interest in the oil, gas and mineral estates in their lands when they disposed of their property. Due to the oil and gas background, and perhaps be- cause oil and gas was paramount in the minds of the parties, the traditional language employed in these grants and reservations was "oil, gas and other minerals" or variations thereof. There are literally hundreds of instruments employing this language constituting a link in the chains of title to thous- ands of acres of Texas land. In addition, there are thousands of acres of Texas land held by oil, gas and mineral leases, the primary terms of which have been perpetuated by production, containing similar language in their granting clauses. The severance of the mineral estate from the surface estate results in two separate and distinct estates, each having all of the incidents and attributes of an estate in land. with the surface estate being the serviant estate, and the mineral estate being the dominant estate and having certain easements in the surface estate to explore. produce and remove the minerals. Harris v. Currie. 176 S.W.2d 302, 305 (Tex. 1943). As observed by the court in the Harris case, this is because a grant or reservation of minerals would be wholly worthless if the grantee or reservor co~lld rwt enter upon the land in order to explore for and extract the minerals granted or reserved. Although the Texas law has recognized that an oil and gas lessee has the right to use so much of the surface as is reasonably necessary to produce the minerals. Warren Petroleum Corporation v. Monzingo, 304 S.W.2d 362, 363 (Tex. 1957), recent decisions of the Court have qualified this doctrine. In Getty Oil Company v. Jones. 470 S.W.2d 618 (Tex. 1971). Getty's pumpine, units were interfering with ones self-propelled sprinkler system utilized for irrigating the premises, and Jones sought to require Getty to install the-pumping units in cellars so that the sprinkler system could pass over them. In an effort to accommodate both the surface estate and the mineral estate, the court held (page 622) "...where there is an existing use by the surface owner which would otherwise be precluded or impaired, and where under the established practices in the industry there are alternatives available to the lessee whereby the minerals can be recovered, the rules of reasonable usage of the surface may require the adoption of an alternative by the lessee". Bearing in mind that the "reasonable use doctrine" grew up in the oil and gas industry involving sub- stances which can be produced by methods that do not destroy or deplete the surface estate, the question presented is whether the Texas courts will extend this doctrine to situations where claimants of "other minerals" seek to produce shallow deposits of iron ore, coal, lignite and uranium by surface mining methods which do destroy or deplete the surface estate? The surface destruction test has answered this question in the negative, at least as to iron. coal and lignite. However, the multitude of mineral estates in Texas which have been created by a grant. reservation or lease of "oil, gas and other minerals" will, doubtlessly, continue to fuel the fires of litigation. EARLY TEXAS DECISIONS In view of the evolution of the Surface Destruc- tion Test, an exhaustive review of the early Texas

Jan 1, 1980

By C. A. Oestreicher

For sulfide minerals, the presence of dissolved oxygen in the water phase is an influencing factor for separation by flotation. Klassen and Mokrousov(I:217l distinguish three stages of oxygen adsorption; namely, reversible adsorption, activated adsorption and, finally, surface oxidation. While contraversial, limited adsorption of oxygen is believed to improve the interfacial reactivity between collector and mineral. Intensive surface oxidation of sulfide minerals usually results in unsatisfactory flotation with collectors of the xanthate type. The influence of dissolved oxygen in the water phase has received consideration for sphalerite, galena, chalcopyrite, arsenopyrite, chalcocite, and covellite(2,3,4,5,6). However, the nature of surface oxidation products of sulfide minerals has received very limited investigation(6,7). Lightly oxidized galena promotes the adsorptive reaction of surfactant (xanthate or dixanthogen). Tolun and Kitchener(8) state that limited interaction occurs between galena and xanthate under relatively reducing conditions. And, that exposure to oxygen raises the electrochemical potential of the galena to that required for reaction with xanthate or dixanthogen. In the latter condition, the galena has an "effective flotation surface". On the other hand, intensive oxidation of galena reduces the chemical reaction with xanthate collectors (9) . Complete flotation with xanthate-type surfactants with increasing oxygen content in the water phase has been determined to have the following sulfide mineral sequence(3): galena, pyrite, sphalerite, chalcopyrite, pyrrhotite and arseno-pyrite. The work of Cusack(4) suggests that some threshold amount of oxygen is necessary for flotation to occur, but heavy oxidation hinders flotation with xanthates. According to Tolun and Kitchener(8) catalytic oxidation of xanthate to dixanthogen occurs. From infrared studies, Poling and Leja(IO,II) found that in the absence of oxygen in solution, xanthate ions do not adsorb either on

Jan 1, 1972

By M. R. Yalamanchili, C. A. Young, J. J. Kellar, W. M. Cross, J. D. Miller

Introduction Researchers have long speculated regarding the adsorption state of collectors on mineral surfaces. Only recently have analytical techniques become available that allow direct in situ analysis of adsorbed layers. With reactive internal reflection elements (IREs), Fourier transform infrared spectroscopy coupled with internal reflection spectroscopy (FT-IR/IRS) allows for unobtrusive investigation of the adsorbed layer (Harrick, 1979). This technique has been used both for the in situ identification of adsorbed species and for the direct calculation of collector adsorption density in real time from infrared spectral data (Miller and Kellar. 1988). The reactive mineral IRE serves both to internally reflect the infrared light and to act as a substrate at which collector adsorption can be monitored. Shown in Fig. I is a schematic of light being internally reflected in an IRE. As the light is totally reflected at the interface, an evanescent wave propagates a short distance (typically a few microns) away from the IRE, and sampling of the interfacial region occurs. Because of multiple internal reflections, great sensitivity can be obtained. Flotation systems for which this method has been demonstrated include CaF2/oleate, Al2O3/dodecylsulfate, CaCO3/oleate, ZnS/xanthate and KCI/octylamine (Miller and Kellar, 1988; Kellar et al., 1989, 1990; Miller et al., 1990). Of particular interest to flotation chemists is the conformational behavior of the alkyl chain of adsorbed collector molecules. In the simplest sense, conformation can bethought of as the relative flexibility of the hydrocarbon chain caused by rotations about carbon-carbon single bonds. The flexibility is described by the amount of gauche/trans conformations in the alkyl chain. Figure 2 shows examples of gauche and trans conformations (rotational isomers or rotamers) in a hydrocarbon chain. These two conformations are observed when the terminal methylene groups in any four-carbon subchain are on the same side (gauche) or opposites sides (trans) of the plane of the middle carbon-carbon bond. A gauche conformer (rotamer) is thus a state of maximum potential energy, whereas a trans conformer is a state with minimum potential energy. The difference between these states has been found to be approximately 0.5 to 0.8 kcal/mole (Mead et al., 1986). The relative number of butane molecules present as gauche conformers with respect to trans conformers can be calculated from the Boltzmann equation (Mead et al., 1986). At 25° C approximately 66% of the butane molecules are trans rotamers. [ ] However at 100° C, only 33% of butane molecules are trans rotamers. Exposing the hydrocarbon chain to a polar, rather than an a polar, medium should also cause an increase in the number of gauche butylene groups in a hydrocarbon chain, although this effect has been difficult to observe experimentally (Mead et al., 1986). Forming a crystalline hydrocarbon is equivalent to decreasing the temperature, which greatly increases the amount of trans butylene groups present in the chain. From the preceding discussion, a picture of the solution species of concern can be developed. The collector monomer should exhibit the greatest number of gauche rotamers and most likely will look crumpled or balled-up to reduce the surface area in contact with water. The micellar form is expected to be aggregated, with the hydrocarbon chain existing in a less polar environment. These characteristic conformational features have been examined by FT-IR spectroscopy for various liquid phases of alkanoic acids (Umemura et al., 1981; Cameron et al., 1982a; Yang et al., 1986; Wong, 1987; Wong and Mantsch, 1983; Cross et al., 1992), phospholipid membranes (Fringe Ii, 1980; Casal and Mantsch, 1985: Wong et al.. 1988;

Jan 1, 1994

By J. J. Kellar

Researchers have long speculated regarding the adsorption state of collectors on mineral surfaces. Only recently have analytical techniques become available which allow direct in-situ analysis of adsorbed layers. Fourier transform infrared spectroscopy coupled with internal reflection spectroscopy (FT-IRJIRS) with reactive internal reflection elements allows for unobtrusive investigation of the adsorbed layer (Harrick, 1979). This technique has been used both for the in-situ identification of adsorbed species and for the direct calculation of collector adsorption density in real time from infrared spectral data (Miller and Kellar, 1988). The reactive mineral IRE serves both to internally reflect the infrared light and to act as a substrate at which collector adsorption can be monitored. Shown in Figure 1 is a schematic of light being internally reflected in an IRE. As the light is totally reflected at the interface, an evanescent wave propagates a short distance (typically a few microns) away from the IRE, and sampling of the interfacial region occurs. Because of multiple internal reflections, great sensitivity can be obtained. Flotation systems for which this method has been demonstrated include CaF2/oleate, Al2O3/ dodecyl sulfate, CaCO3/oleate, ZnS/xanthate, and KCl/octylamine (Miller and Kellar, 1988; Kellar et al., 1989, 1990; Miller et al., 1990).

Jan 1, 1992

By Hyumng Sup Choi

The role of the interfacial electrical 'Condition on the adsorption of col-lectors on mineral surfaces has been studied by electrophoretic mobility and adsorption measurements made on zircon. From the investigation of the electrokinetic properties of zircon, H+ and OH-are seen to act as potential determining ions, thus controlling the electrical nature of this mineral. The isoelectric point of zircon occurs at a pH of approximately 5.0, and it is evident, therefore, that the zircon surface would be positively charged below a pH of 5.0 and negatively charged above this pH. The adsorption of collectors therefore de-pends strongly on the pH of the solution; anionic collectors are adsorbed on positively charged surfaces and cationic collectors on negatively charged surfaces. This, in turn, de-fines the effective flotation condition, with respective collectors, for this mineral. The above results have been correlated with the flotation behaviour obtained by the simplified flotation test using a modified Hallimond tube.

Jan 1, 1963

By T. OnIin, F. F. ApIan

"A study has been made of the surface properties of coals of differing ranks, in their natural state and as modified by the addition of collectors. The evaluation of their surface properties has been done by captive bubble contact angles, water and methylene iodide sessile drop contact angles, zeta potential, point-of-zero charge (PZC) shift, and flotation. .changes in the hydrophobicity of coal is a function of both the rank of the coal and the collecting reagent.INTRODUCTIONThe chemical and physical properties of a raw coal will determine its response to a given beneficiation process. .For such processes as flotation, filtration, flocculation, dispersion, handling, dust supression and agglomeration, however, it is also necessary to consider the surface properties of the coal and mineral matter constitutents of the raw coal. In the case of a specific particle to be floated, it is also necessary to consider the properties of the coal as modified by the addition of some reagent designed to modify (usually increase) the hydrophobicity of the coal surface. General properties of the coal have been well summarized by Van Krevelen (1) and Elliott (2), while the data for the surface properties of coal are much more scattered in the literature (see, e.g.: Parekh and Aplan (3), Gutierrez-Rodrigues et al. (4), Aplan (5), Arnold and Aplan (6), Hogg and Chander (7) and Rosenbaum and Fuerstenau (8)). While a knowledge of the inherent surface properties of a sample are important, of much greater practical significance are the properties of the particle in the presence of a reagent, such as a collector, designed to enhance the hydrophobicity of the particle. This study will focus on the surface properties of coals of various ranks in the presence of a variety of collectors."

Jan 1, 1989

By K. Darcovich

The wettabilities of agglomerates made from coals of several different ranks were measured by the adhesion technique. Oil levels from 0 to 10% by weight were used. As was expected, it was found that higher-rank coals are more easily oil-wetted and that the surface properties of the agglomerates correlate with agglomeration recovery and ash removal data.

Jan 1, 1992

By Sarthak Kaushik

Zeta potential measurements show that the isoelectric point of crandallite, in aqueous solution of 10-2 N sodium chloride is at about pH 5.5. Measurements of turbidity confirm the point of zero charge or crandallite. Calcium ions specifically adsorbed on the surface and thus changed the zeta potential and turbidity. From the measured data, it is confirmed that starch acts as a flocculent for crandallite. Oleic acid, which is a collector used in phosphate ore processing is weakly adsorbed on the surface of crandallite. This results in hydrophobic coagulation of particles resulting in a lower turbidity.

Sep 1, 2012

By N. Arbiter

If two fluid phases are brought into contact with a solid, one fluid may completely wet the surface to the exclusion of the other, or both may wet it, forming a three-phase line of contact. These relative wetting tendencies are quantified by the contact angle 0 which is related by Young's equation (1,2) [12 cos? = 13 ? 23] [to the three interfacial tensions (3). No contact angle for the first fluid, indicating that it does not wet the solid in the presence of the second, means that the difference between the two solid-fluid fluid surface tensions, - 8 is greater than (or just 13 -23 equal to) the fluid-fluid tension 12; a finite angle indicates that the difference is less.*]

Jan 1, 1964

By R. L. Grayson, W. E. Wallace, J. W. Stephens, M. D. Attfield, P. S. Brower, V. Vallyathan, M. J. Keane, J. C. Harrison

Pure respirable quartz is a known pathogenic agent for lung disease. However, for mixed dusts, neither mineralogical nor in vitro cytotoxicity assays unequivocally predict the contribution of quartz to their pathogenic potential.First, although Coal Workers' Pneumoconiosis (CWP) and Progressive Massive Fibrosis (PMF) prevalence have been found to correlate with total respirable coal mine dust exposure, and with coal rank (Attfield and Morring, 1992), epidemiological studies generally have not found the quartz component of coal mine dust as measured by X-ray diffraction or infrared spectroscopy (each of which essentially measures the mass-percent quartz in a bulk sample) to be clear predictors of CWP prevalence or incidence (Walton et al., 1971). Second, the properties which distinguish the extreme fibrogenic potential of quartz are not revealed by conventional in vitro bioassay comparison with other silicate mineral dusts. As an example, quartz and kaolin (aluminosilicate) clay in vitro cytotoxicities are comparable for lavaged primary pulmonary macrophages.The studies discussed here address these two anomalies from a general hypothesis that the pathogenic activity of respired quartz particles is associated with properties of, and interactions with, the particle surfaces. One factor in the expression of toxic activity by a particle surface is the biological availability of that surface. Anomalous lack of correlation of disease prevalence with mass percent quartz in exposures to some mixed composition respirable-sized dusts suggests that individual particle surface features, invisible by bulk sample mass analysis, may alter the biological availability of a fraction of quartz particles in a dust. For pure-surfaced mineral particles, the comparably strong prompt membranolytic activities of quartz and kaolin in vitro suggest that upon deposition of such particles in the lung there must be other interactions with particle surfaces which distinguish quartz. This might be due to toxic surface-associated sites specific to silica, or to interactions of other sites on other mineral particles which affect the biological availability of their toxic functional groups. For example, alurninol groups on clays affect the availability or activity of adjacent silanol groups. Surface activities which distinguish quartz pathogenici ty might be manifest in one or more of the sequential interactions upon deposition in the lung; first with the pulmonary surfactant system, then with extracellular and phagolysosomal enzymatic digestive processes, or with subsequent cytotoxic processes.

Dec 1, 1995

By R. Kamguem

The surface of a mechanical part plays an important role in determining performance in service. The presence of scratches left by the cutting or tearing of the material on the surface of the workpiece supports the concentration of stress and strain. This article presents the experimental study for high speed milling of the aluminum alloy 7075-T6, using cutting tools different by the nose radius and coatings (TiCN, TiAIN, TiCN + A12O3 + TiN). A multi levels factorial design of experiment (DOE) and statistical analysis was used. The roughness parameters investigated are Ra, Ra, Rv, Rc, Rsm, and Rk. The results show that the feed rate, the types of coatings and the geometry of the cutting tools have the most significant impact on the surface roughness profil. Surface finish charts according to feeds and cutting speeds were established for each tool tested.

Jan 1, 2011

By Roger J. Berdusco

Kaiser Resources Ltd. owns and operates a 5-million-tonper- year open-pit and hydraulic coal mine near Sparwood in southeastern British Columbia. Since 1969, Kaiser has maintained a field-scale reclamation program dedicated to the reclamation of disturbances associated with past and present mining and exploration activities . Since that time, over 1400 acres have been treated using modified forestry and agricultural techniques with encouraging results.

Jan 1, 1978

By E. Ilgar

"Deposition studies were conducted in acid copper electrolyte to determine the influence of chloride ions on cathode morphology. A statistically designed screening test was carried out in the absence and presence of 20 ppm CI- using a three factor, two level factorial design, in an electrolyte containing 36 gl'! Cu2+ and 150 gl-! H2S04, The independent variables evaluated were agitation; current density and temperature and their influence on surface roughness was determined. The copper deposited at current densities where activation was the primary control mechanism appeared similar in morphology whether stirring was used or not. The addition of 20 ppm CI- to the electrolyte gave rougher deposits under the same conditions. In the mixed control regions, considerably rougher, dendritic deposits were obtained when CI- was present. Agitation was effective in reducing the copper surface roughness both in the apparent activation and mixed control regions in the presence ofCI-. The results of this study showed that 20 ppm Cl- polarized the copper deposition at low overpotentials but caused depolarization at higher overpotentials.IntroductionChloride ion is inherently present in copper electrolyte, either as an additive or from other sources such as make up water. The behavior of the chloride ion is well documented in electrorefining operations, but its role in copper winning is less obvious. However in both cases there is evidence that cathode growth and solution chemistry are strongly influenced by its presence. The mechanism and electrochemical action of the Cl"" have been shown to be very complex, therefore a better understanding of its influence on electrocrystallization is essential for improved cathode deposit growth control. It was proposed that Cl"" polarizes the copper deposition reaction at low concentrations due to CuCI formation but depolarization occurs at higher concentrations due to the formation of a soluble CuCI2"" complex [1,2]. Franklin [3] reviewed the mechanism of additives in the electrodeposition process and proposed that the Cl"" complexed with copper, adsorbed on the cathode as an induced anion leading to an increase in the reduction rate. At cathodic overpotentials less than 100 mY, lppm NaCl had a polarizing effect, i.e. an increase in impedance of the charge transfer step. At higher Cl"" concentrations up to 100 ppm, depolarization occurred as evidenced by a decrease in impedance, which was attributed to soluble cuprous complexes [4]."

Jan 1, 1997