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By T. T. Chen

Secondary copper anodes are generally rich in Sn, Pb, Ni and Sb, but are notably deficient in Se, Te and Ag. In the secondary copper anodes, most of the Ni, virtually all of the Ag, slightly more than one-fifth of the Pb, about one-third of the As and Sb, and approximately one-tenth of the Sn are in solid solution in the copper. The remaining impurity contents occur as 1-5 µm grain-boundary inclusions in the anodes, and these are mainly Cu2O, SnO2, Cu-Pb-As-Sb-Bi oxide, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide, Cu-Sb-Ni oxide (Kupferglimmer) and trace Cu2(Se,Te). Barium sulphate, which originates from the mold wash used in casting, is also present in the anodes. During electrorefining, the BaSO4, SnO2, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide and Cu- Sb-Ni oxide inclusions are liberated and accumulate in the slimes layer. Solid solution Ni dissolves and the Ni accumulates in the electrolyte. Solid solution Sn and Pb dissolve, but partly reprecipitate as Sn arsenate and PbSO4, respectively. Solid solution Ag dissolves but rapidly reacts to form Ag2(Se,Te), Ag powder, Ag-bearing Cu2O, (Cu,Ag)SO4 or a complex oxidate phase. Partial dissolution of the Cu-Pb-As-Sb-Bi oxide particles takes place; the Pb component is converted to PbSO4, whereas Cu, As, Sb and Bi dissolve. The reacted particles retain the morphology of the original Cu-Pb-As- Sb-Bi oxide phase. Some of the solubilized As, Sb and Bi remains in solution, but much reprecipitates as SbAsO4, As-Sb-Bi oxide, and as a poorly defined oxidate phase which consists mostly of Cu-Ag-Pb arsenate-sulphate. The high Sn contents of secondary copper anodes do not seem to affect the behaviour of the anodes during electrorefining.

Jan 1, 1999

By I. Van de Voorde

In this paper, results are presented concerning the search to implement Supported Liquid Membranes (SLM) Technology for the recovery of copper, nickel and zinc from electroplating and other effluents to prevent metal waste. A study of the influence of the individual parameters and of their combined effect on mass transfer in small-scale laboratory equipment has been performed, enabling to set forward the appropiate operating conditions for a pilot plant installation. The SLM pilot plant has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that the SLM technolgy is applicable for solutions containing 800 mg/L of metal ions, but also to the treatment of solutions with low metal content of origin other than plating shops. It was demonstrated by system analysis that the recycled salts are usable to produce metal electrolytes (for example Watt's nickel bath).

Jan 1, 2003

By Hirokazu Narita

The extractability for Pd(II) using MOTDA and DHS and their durability against a mixed solution of HNO3 and HCl was investigated by solvent extraction and FT-IR measurements. Both MOTDA and DHS selectively extracted Pd(II) over Pt(IV) from 0.75 M HNO32.25 M HCl solutions. The extraction rate of Pd(II) with MOTDA was much greater than that with DHS. In the durability test, the extraction percentage of Pd(II) and the FT-IR spectra were measured using MOTDA and DHS after stirring with 0.75 M HNO32.25 M HCl solutions. The extraction percentage of Pd(II) with MOTDA hardly changed during the two-month stirring; however, that with DHS decreased with an increase in the stirring time. The FT-IR spectra showed the sulfoxide formation by the oxidation of the sulfide in DHS, but not in MOTDA. Consequently, it was found that MOTDA is more durable than DHS.

Jan 1, 2006

By Zhang Chuanfu

Keywords: modified coprecipitation method, Ni-Co alloy powders, solid-solution oxalate, growth mechanism Homogeneous solid-solution oxalates of Ni2+ and Co2+ ions were synthesized by modified coprecipitation method and the composition and morphology of the fibrous solid-solution oxalates precursor were characterized by XRD, IR, DTA/TG and SEM analysis. The effects of feeding methods, pH values, precipitation temperature, reactant concentration, addition surfactant, alcohol washing and drying process on the morphology and dispersion of the precursor were investigated in detail. The experimental results showed that the coprecipitated powders have characteristics that are different from those of the mechanical mixtures with the same stoichiometry. Based on the observations of precursors growth and SEM morphology of the precursor, the oriented attachment was proposed for the well-aligned growth of the fibrous Ni-Co alloy precursor particles.

Jan 1, 2005

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades. EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized.

Jan 1, 2003

By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Chan. C. L., Zehr. R., M. M. Chen, J. Mazumder

"Two three-dimensional models of a surface tension gradient driven flow during laser surface heating are developed. The first model is based on a perturbation solution. The basic solution corresponds to the stationary axisynwnetric case and perturbation is based on a small scanning velocity. The advantage of seeking a perturbation solution, as it turns out, is that the three-dimensional flow is modeled by two sets of two-dimensional equations which are presumably much more tractable than the original three-dimensional equations. Numerical solutions are obtained and discussed. The second model is a full three-dimensional numerical solution of the Navier-Stokes equations, using a point-by-point partially vectorized iteration scheme. Surface shape is also determined in a self-consistent manner. The effect of the presence of convection on pool geometry, cooling rate and solute redistribution is presented and discussed.IntroductionThe existence of fluid flow and convection and their effects were first reported in the fifties (1,2). The role of convection in controlling pool geometry such as pool shape, undercut and ripples, and defects such as variable penetration, porosity and lack of fusion and weld properties such as weld homogeneity and bead formation is studied by a number of researchers and is reviewed by the authors in a recent paper (3).Recently, surface tension gradient driven flow has been identified as one of the forces responsible for convection within the molten pool (4,5). It is postulated that surface tension gradient driven flow is responsible for the surface ripple formation in the weld pool (6-8). Oreper, et al. (9) developed a two-dimensional convection model. Buoyancy, electromagnetic and surface tension gradient forces were considered. The formulation was based on a specified pool profile. It was found that the surface tension gradient is the dominant force in most cases. However, the solid-liquid interface is not known a priori. In fact, the solid-liquid interface, i.e. the pool shape, is a piece of information that the model should be able to predict. A two-dimensional transient self-consistent (i.e. the solid-liquid interface is solved as part of the solution] model for laser surface melted pool was first developed by Chan, Mazumder, and Chen (3)). This model predicted a non-uniform cooling rate, hence non-uniform microstructure. Depending on the Prandtl number (i.e. material) and surface tension number, the shape of the molten region as well as the cooling rate changes. It was also predicted that the recirculating velocity is of one or two order of magnitude higher than that of the scanning velocity. This model provides the detail of the flow field and heat transfer on a plane perpendicular to the scanning direction. However, the front-to-back motion and its effect on heat transfer also play important roles in the physical process, especially for the fact that the recirculating velocity is so much higher than the scanning velocity. Such a motion cannot be obtained from two-dimensional models."

Jan 1, 1986

By Nicholas Zabaras, Deep Samanta

"Solidification of metal aluminum and aluminum alloys is modeled on uneven surfaces characterized by sinusoidal curves. Wavelengths and amplitudes of these sinusoidal surfaces are varied to study their effects on processes like solidification, macro-segregation and inverse segregation. Solidification and macro-segregation are modeled using a slightly modified form of a stabilized finite element method developed recently to model high Rayleigh number solidification and porous media flows. For pure metal solidification, the effect of varying amplitudes and wavelengths is observed in heat transfer, fluid-flow ~nd phase change processes. The relative importance of shrinkage driven flow and solutal convection on the redistribution of solute for an alloy solidifying in a rectangular cavity is compared. The analysis is then extended by modifying one of the surfaces to a sinusoid. In this case the effects of varying amplitudes and wavelengths are studied in heat transfer, fluid flow, phase change, macro-segregation and inverse segregation processes.1 IntroductionTransport phenomenon during solidification of alloys is a major cause ofcasting defects such as segregation, micro-voids, hot tears, porosity, internal and surface cracks. Heat flow across metal and mold surfaces directly affects the phase change process and plays an important role in determining freezing conditions within the metal. In alloys, natural convection and shrinkage play an important role in determining the final solute redistribution, macrosegregation and evolution of solid macromorphology. Surface unevenness plays an important role during the early stages of solidification. It influences the heat transfer rate and fluid flow in the melt, which in turn affect the morphology and shape of the solid-liquid interface. The effect of surface unevenness on solute redistribution is important during solidification of alloys, where solute driven flow in the mushy zone is prominent. Thevik and Mo in [7] and [8] used a one dimensional model for studying surface segregation and macrosegregation in alloys under the influence of exudation and solidification shrinkage. Air-gap formation in their model was expressed through a variable convective heat transfer coefficient at the boundary. Tsai et al. in [3] and [4] have modeled macrosegregation in an aluminum-copper alloy driven by shrinkage and solutal convection. They used a single domain model based on mixture theory and solved the transport equations using finite difference methods. Our aim is to model solidification of aluminum followed by macrosegregation and inverse segregation in aluminum-copper alloys on uneven surfaces by finite element methods. These surfaces are modeled as sinusoids characterized by amplitudes, ?s and wavelengths, As, By varying As and ?s, changes in heat transfer, fluid flow, phase-change and macrosegregation are studied."

Jan 1, 2004

By José Carlos D?Abreu

The Tecnored process is a new ironmaking technology, developed on a unique approach that combined empirical and theoretical knowledge backed by extensive tests carried out in a dedicated pilot-plant and with close support of universities and research centers. Campaigns in the pilot-plant focused on operate different reactors of different sizes, including a full size slice of the industrial furnace. This approach provided actual conditions to develop the main features of the process such as the internal dimensions, raceway pattern, thermal and gaseous profiles, etc, besides provide reliable data to feed and calibrate a specific mathematical process modeling. This paper presents the first computer model used by the Tecnored technical staff, focusing the behavior of a self reducing agglomerate in the upper shaft of the furnace (zone of solid state reduction). Some results of this model are given and discussed.

Jan 1, 2006

By B. Zeytuncu, O. Yucel, O. H. Celik, M. H. Morcali

"The Taguchi method was used as the experimental design to determine the optimum conditions of cementation behavior of the ruthenium chloride solution. Cementation was carried out using metallic zinc powder. The experimental conditions were studied in the range of 25-45°C for reaction temperature (A), 30--60 min for reaction time (B), 0.5-1.5 for pH of solution (C), and 30--50 mg for zinc powder (D). Experimental parameters and their levels were determined in the light of preliminary tests. Orthogonal array (OA) L9(34) consisting of four parameters each with three levels, was chosen. The optimal conditions found for ruthenium, such as a reaction temperature, reaction time, pH of the solution and mass of zinc, are respectively: 45°C, 45 min, 1.5 and 50 mg. Under these conditions, the ruthenium cementation efficiency obtained by theoretically and experimentally was in good agreement, which were 99.8% and 99.7% respectively."

Jan 1, 2013

By Achilles J. B. Dutra, Carlos M. Juarez

"The use of thiourea as a gold leaching reagent has been extensively studied by many researchers, and it has proved to be promising for some cases as refractory ores. Otherwise, the recovery of gold from these solutions did not receive so much attention. In this paper the electrowinning of gold in acidic thiourea solutions was studied by voltarnmetry and chronopotentiometry. An adsorption step was detected prior to Au(I) reduction and the diffusion coefficients at 25°C for Au-TU complex and FD were found to be 1.00 x 10.5 cm2 S-I and 1.98 x 10-5 cm2 S-I respectively. At -0.350 V (SCE) a passivation probably due to TU adsorption was observed. For higher overpotentials hydrogen evolution was the main reaction.IntroductionThe use of acidic thiourea solutions for the extraction of gold and silver has shown to be a promising alternative to the traditional process of cyanidation, specially for certain refractory ores (1-3) and electronic scrap (4). In some cases, the industrial scale was reached (1,5). The thiourea leaching of precious metals presents advantages over cyanidation, as faster kinetics, lower toxicity and lower sensibility to base metals; however the costs due to high thiourea consumption impairs its use.The majority of the publications on thiourea processing of gold is on leaching. Many are review papers (5-7). Recently, the adsorption and desorption of the gold-thiourea complex on activated carbon and ion exchange resins have been studied (8-11).Little research has been done on the electrowinning of gold from acidic thiourea solutions, most of it has been carried on the seventies and beginning of the eighties in the former USSR (12-17) and concerned the eletrolytic extraction of gold in tridimensional cathode cells.The present paper concerns the cathodic behavior of the gold-thiourea complex in the presence of formamidine disulfide in order to provide information on the electrowinning of gold from solutions obtained directly from leaching or from an elution process."

Jan 1, 1997

A three?stages countercurrent fluidized bed prototipe reactor to neutralize the SO2from smelter gases has been developed. For gases with 8 vol-%SO2, at 800°C and for 4 h mean reaction time of the limestone, the capture of SO2 is 99%, with off gases with 0.07 vol-%. For 2 vol-%SO2, the total capture of SO2 can be obtained at 750°C and 4 h reaction time. The calcine obtained contain a blend of unreacted limestone and calcium sulphatewith minor amounts of residual lime.

Jan 1, 2006

By Dirk Verhulst

The Altair process employs digestion of ilmenite ore in concentrated hydrochloric acid, solvent extraction to concentrate Ti in a purified stream and spray hydrolysis to produce a TiO2 hydrate, followed by final calcining and milling. HCl gas is regenerated by pressure-swing distillation and reinjected in the leaching solution. All chloride streams are recycled. Chromium compounds generally remain in the residue. Solvent extraction provides flexibility for the removal of naturally occurring radioactive elements (NORMs) present in some ilmenites. The process was previously tested at a 5 t/day feed scale. Recent work at pilot scale (40 liter reactor) led to further improvements. Recovery of Ti in solution is now at least 90% with ilmenite ores, while crystallization at lower temperature lowers the amount of Fe in solution to about 5 g/l and improves solvent extraction, which is now conducted in columns. Higher Ti and lower Fe concentrations in the SX eluate improve the economics. A new formula for pigment production via spray hydrolysis produces a pigmentary base with a narrow particle size distribution.

Jan 1, 2003

By Yong Hwan, Wang Jian-Jun, Cai Jiu-Ju, Chen Chun-Xia

"The quantity of residual-heat and its recovery in some Chinese sinter plants are investigated. The main factors affecting energy consumption are analyzed using exergy analysis combining energy level analysis. It is indicated that the “gradation recovery and cascade utilize” of discharged gas and sinter residual heat in different temperature is the direction and the available approach to reduce energy consumption of the sinter process. Taking an iron& steel enterprise as an example, the three-ranked scheme of residual-heat recovery is put forward: ?Part of the sinter gas is used for warm-up and dryness; ?The high-temperature part of the cooler and exhaust-heat boiler are actualized as a closed-circuit, which can produce high-quality steam to generate electricity. ?The waste air in low-temperature part is introduced to sintering machine to support combustion. According to the CDQ which can recover the coal heat, the assumption of pot-recovery is put forward to replace the belt cooler. The two equipments of residual-heat recovery are analyzed in the aspect of energy consumption and CO2 reduction.1. IntroductionEnergy consumption in sintering is only inferior to iron-making in iron& steel enterprises, accounting for 10%~20% of the total energy consumption. A lot of residual heat is produced during sintering, and mostly from the sinter ore and waste gas. Sensible heat of hot sinter ore and discharged gas have accounted for 60%[1] (equals to 40 kgce/t-ore), which are the key point of sintering waste heat recovery. Discharge gas of sintering is mostly composed of flue gas deriving from sinter bed’s combustion, and the content distribution of H2O and O2 and the temperature of the gas along the length of belt-type sintering are shown in Figure1[2,3]. Currently, the sensible heat of hot sinter ore is mainly recovered by circular cooler and cooled by blasting air: the temperature of cooled discharge gas brings down from 350? to about 100? along with the decrease of sinter ore temperature. It is significant to recovery and reuse the waste heat as 4000~6000m3 discharge gas per ton of ore can be produced"

Jan 1, 2008

By Juan B. Cabezas

"The favorable characteristics and workability of plastics as a replacement of wood, lead, stainless steel, asphalt and other materials are described. Various types of plastic have proven to be the most favorable choice for handling a variety of acidic, alkaline and organic solutions, as well as pulps, chemical wastes, slurries or tailings for impoundments. The material origin of various plastics, methods of manufacturing and specifications applied to leaching solutions are discussed, including availability and costs. Examples of select plastics are considered for use as alternatives of other materials under severe environmental requirements.IntroductionHydrometallurgical processes applied to gold recovery, as well as other metals, require the use of strong solutions of alkaline, acidic or organic nature, and may also include a variety of materials with extraneous characteristics and complications for handling in storage.The technology of leaching has been in use for more than 100 years, but the applications of leaching processes in metallurgy have become more commonly used in the last 15 years. Suitable materials for the construction of containers, launders, piping, and various accessories, to be used in the handling of leach solutions or slurries, have become a serious problem. Various metals such as brass, lead, stainless steel, etc., and non metallics including wood, clays, glass, rubber, ooncrete, tars or miscellaneous compounds have been tried in the past with serious limitations in workability and resistance to wear and corrosion. For example, the use of metallic, wooden or glass piping systems would require extraordinary shop maintenance to keep such systems in operation"

Jan 1, 1997

By Pengfu Tan

A thermodynamic model has been developed to model the desilverising process of lead by the addition of zinc during lead refining, whereby silver-zinc solid solutions are formed, and floats out of the dissolved zinc/silver in the lead bath. The solubility of silver-zinc solid solutions in lead decreases with falling temperature. A number of variations and modifications of the desilverising process are modeled, and applied to a wide range of silver contents in lead bullions in the industry.

Jan 1, 2005

By Liyuan Chai

In this study, spent grain was used as an adsorbent for the removal of Hg(II) from aqueous solutions, the process parameters such as contact time, solution pH, adsorbent dose, and initial Hg(II) concentration were studied in batch experiments. The initial adsorption process was fast, 91.08% of adsorption occurred within 5 min and equilibrium was reached at around 30min. Adsorption process was found to follow pseudo-second-order kinetics. The equilibrium data were better fitted to Langmuir isotherm than Freundlich isotherm with the maximum adsorption capacity 41.36 mg/g. The structure and component of spent grain before and after adsorption of Hg(II) were investigated using scanning electron microscope(SEM) and energy dispersive X-ray analysis(EDAX), these analysis also confirmed the adsorption of Hg(II) onto spent grain. The results indicated that spent grain had potential as a new inexpensive adsorbent for Hg(II) removal from aqueous solutions.

Jan 1, 2009

By Thomas W. Chapman, Shi-Chern Yen, I-Min Lu

"An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore, local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces.The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.IntroductionRemediation of soils contaminated with toxic chemicals is a difficult and expensive task. Washing or leaching are not particularly effective if the contaminate is sequestered in small pores; hydraulic flows of water pass through larger pores leaving the smaller pores relatively untouched. Electro-osmosis appears to be the most promising new technology for removing heavy metals and organic substances from contaminated soils (Segal, 1980; Hamed et al., 1991, Masliyah, 1994).Electro-osmosis is one of several electrokinetic phenomena that occur through the interactions among an electric field, fluid motion, solute adsorption, and the existence of a net charge on a solid-fluid interface (Newman, 1991, Masliyah, 1994). Electro-osmosis refers to the fluid flow in a porous medium that results when an electric field acts on the mobile region of the electrical double layer, the solution-side region of charge separation that exists at the pore walls."

Jan 1, 1996