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Minerals Engineering 19 (2006) 1462–1464 This article is also available online at: www.elsevier.

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Technical note

On the fundamentals of kaolin rheology applied to the paper industry
F.O. Cunha *, M.L. Torem, J.C. D’Abreu
ˆ ´ DCMM, PUC-Rio, Rua Marques de Sao Vicente, 225-Gavea, 22.453-900 RJ, Brazil ˜ Received 31 July 2005; accepted 16 March 2006 Available online 19 May 2006

Abstract Laminar movement of concentrated kaolin pulps is difficult without the use of dispersing agents. The aim of this work was to contribute to a better understanding of the fundamental aspects of kaolin pulp rheology using colloidal chemistry theory. Zeta potential and rheology were evaluated with and without a dispersant as a function of pH and dispersant concentration. Total interparticle interaction energy was calculated by means of DLVO theory. Finally, rheological data was coordinated with the calculated data from DLVO theory. It was concluded that DLVO theory was qualitatively related to the rheological behaviour of kaolin pulps. Ó 2006 Elsevier Ltd. All rights reserved.
Keywords: Industrial minerals; Oxide ores; Thickening; Surface modification

1. Introduction Concentrated kaolin pulps are utilized in the paper industry as coatings. Elevated shear rates during pulp application produce high viscosities, which inhibit laminar movement producing bubbles or even tearing of the paper. In order to minimize this effect, pH adjustment and dispersant additions are made to pulps (Murray et al., 1993). Suspension rheology can be affected by: volumetric solids fraction particle size distribution, particle shape, floc and electroviscous effects (Ortega et al., 1997). It should be noted that apart from the nature of the particles and their concentration, interparticle interactions have an important role in the rheology of the suspension, especially at colloidal sizes (Hunter, 1993). Such particles are small enough to be unaffected by gravity and particle interactions and their behaviour is controlled by a range of attractive (van der Waals) and repulsive (electrical double layer) forces, as defined by DLVO theory (Israelachvili, 1992; Johnson et al., 2000). Various types of interaction
Corresponding author. Tel.: +55 21 34167504; fax: +55 21 31141236. E-mail addresses: fabcunha@dcmm.puc-rio.br (F.O. Cunha), torem@ dcmm.puc-rio.br (M.L. Torem). 0892-6875/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2006.03.010
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can occur under the combined action of these two forces. Depending on electrolyte concentration and surface charge density or potential, these can range from strong repulsion to rapid coagulation (Israelachvili, 1992; Laskowski and Ralston, 1992; Hunter, 1993). The aim of the present work was to evaluate the pulp rheological data of kaolin from electrokinetic properties by the DLVO theory. 2. Materials and methods The raw material was a beneficiated kaolin sample from Mineracao Monte Pascoal LTDA (named Coat 90). This ¸˜ sample essentially contains kaolinite of pseudo-hexagonal crystals and with bimodal distribution (80% less than 2 lm and 34% less than 0.2 lm). Sodium hexametaphosphate P.A. was the dispersant used. Electrokinetic studies were carried out in a Malvern Zeta Master. The zeta potential data obtained was used to estimate the total interparticle interaction energy (TIIE) by means of DLVO theory. Israelachvili approach (1992) was used, which accounts for spherical particles with the same size, where R ) H (particle radius is much bigger than interparticle distance of closest approach):

4 · 10À20 J (James and Williams. The detailed experimental procedure is described elsewhere (Cunha.. 1993.O. TIIE as a function of separation distance at different pH for (A) no dispersant and (B) 3 kg/t dispersant concentration. while f =pffiffiffiffiffiffiffiffiffiffiffiffi zeta potential (mV) Debye length¼ 0:304= qð1Þ (nm) interparticle distance of closest approach Hamaker effective constant = 4. 3. apparent viscosity properties were obtained at constant temperature (25 °C). It can be seen that the zeta potential values become more negative with increase in dispersant concentration (Fig.. building three-dimensional structures that increase rheology. 2003). generating edge-face interactions.F. Finally. 1(B). Cunha et al. time interval (280 s) and shear rate (100 sÀ1) for comparison purposes. rheological DGINT ¼ 4:61  10À11 Rc2 expðÀjH Þ À 20 A Zeta Potential (mV) 0 IEP 10 M -2 -3 -4 20 B Zeta Potential (mV) 0 -20 -40 -60 10 M 10 M No Dispersant 1 k g /t 3 k g /t 5 k g /t 7 k g /t -20 -40 -60 -80 -80 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11 pH pH Fig. 2004). 2(B)).1. 1(A) shows the zeta potential curves for kaolin particles at three different KCl concentrations. For 1:1 electrolytes: AR ð2Þ 12H Viscosity values were obtained from a Haake Rheo Stress Rheometer using concentrated kaolin aqueous suspensions (50 w/w% with no dispersant addition and 70 w/ w% with dispersant addition) with pH adjustment (NaOH 10% w/v solution).e. Results and discussion 3. This behaviour suggests specific adsorption. i. / Minerals Engineering 19 (2006) 1462–1464 1463 DGINT ¼   64pkTRqð1Þc2 AR expðÀjH Þ À 12H j2 ð1Þ where DGINT = TIIE k T R q(1) c 1/j H A Boltzmann’s constant temperature (298 K) mean radius (kaolin particle) = 2. Total Interparticle Interaction Energy (kT) 600 500 400 300 200 100 0 -100 A pH4 pH5 pH6 pH7 pH8 pH9 pH10 Total Interparticle Interaction Energy (kT) 600 500 400 300 200 100 0 -100 0 10 20 30 40 50 B pH 4 pH 5 pH 6 pH 7 pH 8 pH 9 pH 10 0 10 20 30 40 50 Distance (nm) Distance (nm) Fig. as a function of pH. Kaolin electrokinetic properties Fig. permanent (negative charges on faces) and nonpermanent (negative or positive charges depending on solution pH) (Murray et al. 1998. . Kaolin zeta potential properties are shown as a function of pH and dispersant concentration. 2. The profiles of the curves result from the kaolinite surface charge.0 · 10À7 m bulk electrolyte concentration tanh(f/103). Since these pulps are thixotropic fluids. 1982) data were coordinated with those calculated from DLVO theory. 1. When the edges are negative.. Hu and Liu. Huertas et al. Kaolin zeta potential properties as a function of (A) pH and KCl concentration (IEP = isoelectric point) and (B) pH and dispersant concentration. particles are attracted to each other. The modifications of the kaolin surfaces due to dispersant addition are shown in Fig. particularly chemisorption of the anion originating from the dissociation of the dispersant on the kaolin.

F. X. Israelachvili. James. Murray. 2003.J.E. 2(B). 3 shows the data coordination between the energy barrier and apparent viscosity as a function of separation distance and pH. J. and without dispersant addition. 3. 5 and 7 kg/t dispersant. Part I: Fundamentals. Boger. 1992. 219–232. Elsevier Science Publishing Company. 2004 (in Portuguese).O.. 1993. Huertas. Hu. pref- erentially to the edges faces. second ed. At pH 8 and 3 kg/t minimum apparent viscosity was achieved.. F. et al. References Cunha. Cunha et al. Rheological aspects and stability of ceramic suspensions. suggesting that the maximum energy barrier value (%600 kT).H. Healy. Kaolin Genesis and Utilizations.V. The Clay Minerals Society. G. Ralston..W. pH increase and dispersant addition generate increasingly negative zeta potential values (up to pH 8 and dispersant concentration 3 kg/t) exerting a liquefying effect on concentrated pulps by disruption of three-dimensional structures.C.O. 5–10 (in Portuguese). New York.. Introduction to Modern Colloid Science. London. R. this is in accordance with the zeta potential data obtained. 1982. Amsterdam.. 1279–1284. conducive to stable suspensions. A Study of Kaolin Pulp Rheology for the Paper Industry based on Prado Region Kaolin.. Chemical composition and surface properties of kaolins.. Wollast.. Hunter. 58 (1–4)... 3. A. i. Geochimica et Cosmochimica Acta 62 (3). Academic Press. Advances in Colloid and Interface Science 17. C. H. This behaviour suggests that the surfaces are so negatively charged that anions are repelled from the kaolin particles or that there are no active sites left for adsorption. Scales.J. Ceramics 43 (January/February).V. Surface chemistry – rheology relationships in concentrated mineral suspensions. . Based on these results it appears that DLVO theory qualitatively describes the rheological behaviour of these pulps. was reached..J. Minerals Engineering 16 (11).. 1998. L. Colloid Chemistry in Mineral Processing. Thesis.S.3. J.. It was observed that energy values higher than 400 kT were sufficient to repel and disperse the kaolin particles. 3..J.Sc. 1997.1464 350 F.. Harvey. Oxford University Press. Ortega. Particle interactions and rheological effects in kaolinite suspensions.e. producing highest pulp stability. S. Analyzing Fig.B. Intermolecular and Surface Forces. maximum dispersant adsorption and particle repulsion..S. D. 2000. 2 shows TIIE as a function of kaolin interparticle distance and pH with 1. 3. 4. Finally DLVO theory proved to be qualitatively related to the rheological behaviour of the kaolin pulps in the absence and presence of the dispersant used. Rheology coordinated to DLVO theory Fig. At this point particles are so distant that fluidity reaches a maximum. Conclusions The results achieved allow us to conclude that the anions generated are chemically adsorbed by kaolin. / Minerals Engineering 19 (2006) 1462–1464 600 700 700 Total Interparticle Interaction Energy (kT) Apparent Viscosity (cP) 300 A 500 400 600 B Total Interparticle Interaction Energy (kT) Energy Barrier 600 Shear Rate 100s-1 250 Apparent Viscosity (cP) Shear Rate 100s-1 500 500 400 400 300 300 200 100 0 3 4 5 6 7 8 9 10 11 200 Energy Barrier 200 150 100 50 0 0 5 6 7 8 9 10 300 200 100 100 pH pH Fig. DCMM. DLVO theory Fig. there is no significant zeta potential variation for pH values above 8 and for dispersant concentrations above 3 kg/t.N. 1992.A. D. International Journal of Mineral Processing. W.. 12. Mechanism of kaolinite dissolution at room temperature and pressure: Part I: Surface speciation. R.2.C.. P. F. Chou. Johnson. It was observed that the energy barrier (the energy necessary for irreversible adhesion in primary minimum) was improved with pH increase and dispersant addition up to pH 8 and concentration 3 kg/t. Y. Bundy. vol.. D.. Franks. PUC-Rio. 417–431. Liu. J.. T. Williams. 1993. Apparent viscosity coordinated with energy barrier as a function of separation distance at different pH for (A) no dispersant and (B) 3 kg/t dispersant concentration.M. Rio de Janeiro. Laskowski. 267–304.