Journal of Colloid and Interface Science 297 (2006) 312316 www.elsevier.

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Dynamics of shear-thinning suspensions of coreshell structured latex particles

Hiroshi Nakamura , Kazuyuki Tachi
Toyota Central Research & Development Laboratories, Inc. 41-1, Yokomichi, Nagakute, Aichi-gun, Aichi, 480-1192, Japan Received 31 May 2005; accepted 5 October 2005 Available online 9 November 2005

Abstract The rheological behavior and microstructure of shear-thinning suspensions of coreshell structured carboxylated latex particles were examined. The steady shear viscosity of the suspension increased with increasing dissociation of the carboxyl groups or increasing particle concentration, however the critical shear stress c and inter-particle distance of the microstructure did not change. With increasing particle diameter, c increased and decreased. These results were consistent with a Brownian hard sphere model, in which competition exists between the bulk mass transfer due to the applied eld and diffusion of the particles. We conrmed that c depends on , as expressed by c = 3kT /4 3 . This relationship is consistent with the dynamics of a Brownian hard sphere model with particle diameter . Thus the dynamics of shear-thinning suspensions of coreshell particles can be explained by a Brownian thermodynamic model. 2005 Elsevier Inc. All rights reserved.
Keywords: Suspension rheology; Coreshell particle; Carboxylated latex; Critical shear stress; Inter-particle distance; Brownian dynamics

1. Introduction Coreshell structured particles consisting of a hard sphere and an adsorbed or grafted soft layer display characteristic behavior in terms of particle swelling and suspension rheology. Coreshell structured latex particles with a mantle core polymer and a shell polymer layer having carboxyl groups swell with addition of base in an aqueous medium [1]. An aqueous suspension of these swelling particles displays shear-thinning ow at low concentrations; for non-swelling particles, Newtonian ow would normally be observed. This characteristic rheological behavior enables control of the rheological behavior of paints, inks, foods and other products [24]. It is well known that when acrylic acids containing latex polymers are neutralized to an alkaline pH, there is a marked increase in the viscosity of the system [48]. Verbrugge measured viscosity versus pH for a large number of methacrylic acids containing latexes of high and low Tg and similar hydrophilicity [5,6]. Quadrat demonstrated that changes observed
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E-mail address: nakamura@mosk.tytlabs.co.jp (H. Nakamura). 0021-9797/$ see front matter 2005 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2005.10.006

in the ow curves of carboxylated acrylate latex suspensions during alkalinization could be described in terms of parameters of the Cross theory of aggregation of disperse particles, and described the ow mechanism of latex suspensions in which the particles have dissociable groups [7,8]. In previous work, we have found that shear-thinning ow suspensions of coreshell structured carboxylated latex particles display elastic solid-like behavior in dynamic rheological testing [9]. Moreover, from small angle X-ray scattering (SAXS) measurements, the pseudo-lattice structure was detected in the suspension. However, this lattice-like microstructure was not permanent but instead was a metastable structure deformed by thermal motion, the behavior was represented by timetemperature conversion as represented by the Arrhenius equation [9]. This behavior of the coreshell particles is thus similar to that of hard spheres or polymerically stabilized particles [1017]. The shear-thinning rheological behavior of polymerically stabilized colloidal suspensions are usually predicted and correlated on the basis of data and scaling laws for Brownian hard sphere models. In Brownian hard sphere models, the rheological behavior is explained based on the correlation between bulk mass transfer and diffusive mass transfer. If the applied elds are greater than the particle diffusion, the viscosity

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does not change; however, if the particle diffusion dominates, the viscosity falls. At this critical shear stress c , the bulk mass transfer due to the applied eld is greater than the particle diffusion. In this article, the rheological behavior and microstructure of shear-thinning suspensions of coreshell structured carboxylated latex particles are examined under various degrees of neutralization, and various concentrations and particle diameters. The dynamics of the shear-thinning is analyzed based on Brownian hard sphere models using the critical shear stress c . 2. Experimental 2.1. Preparation of suspension of carboxylated coreshell particles Carboxylated coreshell particles CS-1, CS-2, CS-3, and CS-4 were obtained by semi-continuous two-stage feed emulsion polymerization [1,9,18]. In all particles, mantle core polymers were crosslinked and shell polymers were linear and grafted to the core. The crosslinked core was synthesized using methyl methacrylate (MMA), n-butyl acrylate (n-BA) and allyl methacrylate (AMA), and the linear shell using methacrylic acid (MAA), containing carboxyl groups, 2-hydroxyethyl acrylate (HEA), n-BA and MMA. The weight ratio of monomers of the core polymer/shell polymer was 100/29.5. Monomer compositions are shown in Table 1. Though core and shell compositions of all the particles were the same, particle diameters were varied by controlling the initiator weight. These particles swelled with addition of a base in aqueous medium. Table 2 shows the diameters of non- and fully neutralized particles as measured using dynamic light scattering (Otsuka Electronics ELS-800) in dilute suspension (0.1 wt%). The alkaline agent used for neutralization was 2-dimetylaminoethanol (DMAE). Suspensions of the coreshell particle were prepared with various degrees of neutralization up to the full amount of carboxyl groups in the shell polymer and at various particle concentrations. The neutralized agent was DMAE and the degrees of neutralization ranged from 0100%. The particle concentration was varied from 1522 wt%. 2.2. Measurements of rheological behavior and microstructure of the suspension Steady shear rate viscosity was measured by changing the shear rate from 1 102 s1 to 1 103 s1 . Shear modulus G was measured using an oscillation frequency from 1 102 rad s1 to 1 102 rad s1 in the linear region. These experiments were measured using a rotational type rheometer (Rheometrics ARES) equipped with a conical-cylinder xture. The critical shear stress c at which the ow behavior of the suspension changes from Newtonian to shear-thinning was estimated as the intersection point of the low shear rate Newtonian region and the shear-thinning region in a plot of versus (= ).

Table 1 Monomer compositions of the coreshell particles Weight ratio First stage (core) MMA n-BA AMA MAA HEA 47 50 3 Second stage (shell) 24 38 18 20

Table 2 Diameters of the coreshell particles non-neutralized (d0 ) and fully-neutralized (d100 ) by 2-dimetylaminoethanol as measured by dynamic light scattering Diameter (nm) d0 CS-1 CS-2 CS-3 CS-4 109 35 65 191 d100 176 55 103 291

Table 3 Conditions of SAXS measurements Target K lter Voltage, current Angle range Step angle Slits Cu Ni 50 kV, 300 mA 0.01500.15 0.003 Entrance slit 0.015 mm Receiving slit 0.02 mm Scatter slit 0.08 mm Height limitter 25 mm 50 s (10 s 5)

Sampling time

The microstructure of the suspension of the coreshell particles was estimated by small-angle X-ray scattering (SAXS) measurements. The conditions for SAXS are shown in Table 3. The inter-particle distance , which measures between adjacent particle centers in the lattice-like microstructure, was derived from the rst peak position in a plot of the scattering vector Q versus X-ray intensity. 3. Results and discussion 3.1. Rheological behavior and microstructure of the suspension of coreshell particles Fig. 1 shows the steady shear rate viscosity of a 20 wt% suspension of the coreshell particles as a function of shear rate with various degrees of neutralization. With increasing degree of neutralization, and the degree of shear-thinning increased. For the non-neutralized suspension, Newtonian ow was obtained. At intermediate degrees (3080%), the suspensions moved from Newtonian at low shear rates to shearthinning at high shear rates. At high degrees (90100%), these suspensions indicated shear-thinning only. Fig. 2 shows the storage modulus (G ) of a 20 wt% suspension of the coreshell particles as a function of frequency for various degrees of neutralization. At non-neutralized and lower

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Fig. 1. Steady shear rate viscosity of a 20 wt% suspension of the carboxylated coreshell particles as a function of shear rate for various degrees of neutralization of the carboxyl groups: (") 0, (Q) 30, (2) 60, (F) 70, (!) 80, (P) 90, and (1) 100%.

Fig. 3. Steady shear rate viscosity of a 20 wt% suspension of the carboxylated coreshell particles as a function of shear stress for various degrees of neutralization of the carboxyl groups substituting with (= ) from Fig. 1. The critical shear stress c is about 1 Pa.

Fig. 4. Steady shear rate viscosity of a 100% neutralized suspension of the carboxylated coreshell particles as a function of shear stress for various concentrations: (") 15, (Q) 18, (2) 20, and (F) 22 wt%. The critical shear stress c is about 1 Pa. Fig. 2. Dynamic shear modulus G of a 20 wt% suspension of the carboxylated coreshell particles as a function of angular frequency for various degrees of neutralization of the carboxyl groups: (") 0, (Q) 30, (2) 60, (F) 70, (!) 80, (P) 90, and (1) 100%.

degrees, the behavior was consistent with that of an inelastic uid; i.e., G was quite low and increased rapidly with frequency. At intermediate degrees more pronounced viscoelastic behavior was seen, with G attening out at high frequencies. At high degrees elastic solid-like behavior was observed. Here, G was high and almost independent of frequency. These results support those of Fig. 1 and are very similar in form to those observed for hard sphere suspensions in the transition from liquid-like to solid-like behavior. To clarify the relationship between the rheological behavior and the microstructure, is plotted against shear stress (Fig. 3). Over the entire range, increased with increasing degree of neutralization as seen in Fig. 1 but surprisingly the critical shear stress c at the transition from Newtonian ow to shear-thinning was almost the same (1 Pa) in spite of the changing degree of neutralization. For most practical purposes this critical stress can be considered a yield stress. The above results suggest that the yield stress of the suspension of the same particle composition and diameter is constant over various degrees of neutralization.

Fig. 4 shows vs over various particle concentrations. It can be seen that increases with increasing degree of neutralization, but that c remains the same (1 Pa) despite the change in particle concentration. This behavior has been reported in the rheology of hard sphere suspensions [710]. Thus suspensions of coreshell particles of the same composition and diameter show a constant critical shear stress regardless of the degree of neutralization and concentration; in other words, the yield stress that deforms the microstructure by shear ow is constant. Because the yield stress corresponds to interaction between neighboring particles in the microstructure, the interaction between the particles must be independent of the degree of neutralization and concentration. Fig. 5 shows SAXS proles of the shear-thinning suspensions. Diffraction peaks originating from ordered particle structures were detected for all suspensions. From the peak position in the proles, the inter-particle distances of the microstructure were found to be almost identical (Table 4). This supports the assumption that the interaction between particles in the shear-thinning suspensions is almost the same. As such, the critical shear stress c correlates with the inter-particle distance of the microstructure.

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Fig. 5. SAXS proles of various degrees of neutralization and concentration: (2) 100% (18 wt%), (F) 80% (20 wt%), (!) 90% (20 wt%), (P) 100% (20 wt%), (1) 100% (22 wt%). Table 4 Inter-particle distance of the microstructures in the suspensions for various degrees of neutralization and concentrations of the coreshell particles Degree of neutralization (concentration) 100 (22) 100 (20) 90 (20) 80 (20) 100 (18) Distance (nm) 126 126 126 125 125 Fig. 6. Steady shear rate viscosity of a 100% neutralized 18 wt% suspension of the carboxylated coreshell particles as a function of shear stress for various diameters: (") CS-4, (Q) CS-1, (2) CS-3, (F) CS-2. With increasing diameter, the critical shear stress c decreases; CS-4: 0.02 Pa, CS-1: 0.1 Pa, CS-3: 0.35 Pa, CS-2: 5 Pa. Table 5 Inter-particle distance of the microstructures in the suspensions for various diameters of the coreshell particles Distance (nm)

3.2. Correlation between rheological behavior and microstructure We consider that the rheological dynamics of the shearthinning suspensions of coreshell structured latex particles can be probed by the relationship between c and , which involves diffusion of the particles in the microstructure and scaling based on a Brownian hard sphere model [1017]. The ratio of bulk mass transfer to diffusive mass transfer is represented by the Peclet number Pe. In the low stress regime, the stress does not perturb the system until a critical stress c is reached and the viscosity falls. At this stress, the bulk mass transfer due to the applied eld is greater than the Brownian motion in the system and the existing order of the suspension is disrupted. Pe is expressed as, Pe = LV /D, (1)

CS-1 CS-2 CS-3 CS-4

126 37 78 225

where L is the length scale, V is the applied velocity, and D is the diffusion coefcient of the particles. If a continuous shear eld is applied with a shear rate to a suspension of particles with radius a , the following is obtained: /D. Pe = a 2 (2)

a shear-thinning suspension has not been determined. Instead, we derived the diffusion constant of the particle in the shearthinning suspension by scaling equation (4). When c was 1 Pa, the particle radius derived from Eq. (4) was 60 nm. This derived radius does not agree with but is close to /2. This indicates that the diffusion coefcient of the particle in the suspension must correlate with in a similar way to the correlation that exists between the diffusion coefcient and correlation length in a three dimensional gel [19,20]. These results indicate that the dynamics of shear-thinning suspensions of coreshell particles can be expressed by scaling the Brownian dynamics of hard spheres, and that particle diffusion corresponds to that of a hard sphere with diameter . We have determined that c is related to by c = 3kT /4 3 . (5)

3.3. Rheological behavior and microstructure with different particles For the same particle composition and diameter, c and are almost the same with changing degree of neutralization or concentration, respectively. To clarify the relationship obtained above, c and were measured with coreshell particles of various diameters. Fig. 6 shows the relationship between shear stress and viscosity with various particle diameters. and c decreased with increasing diameter along with i (Table 5). If we assume a hard sphere suspension following Brownian dynamics and apply equation [4], it can be seen that c decreases with increasing diameter. Fig. 7 shows the relationship between

Taking the diffusion coefcient as expressed by the Stokes Einstein law, D = kT /60 a , gives a 2 /kT . Pe = 60 (3) At the critical shear stress, the Peclet number should be 1, yielding the following: c = kT /6a 3 . (4)

However, this equation is based on StokesEinstein diffusion of the particle, which is concerned only with dilute suspensions. A general expression for diffusion of the particle in

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mass transfer due to the applied eld and diffusion of the particles in the suspension. It is widely accepted that at low shear rates, where there is a Newtonian plateau, the suspension microstructure is not signicantly perturbed by the shear. At higher shear rates the hydrodynamic forces begin to dominate and shear-thinning occurs. We experimentally conrmed the dependence of c on , as expressed by c = 3kT /4 3 . This relationship corresponds to a Brownian hard sphere model with a particle diameter of . These results demonstrate that the dynamics of shear-thinning suspensions of the coreshell particles is explained well by a Brownian thermodynamic model.
Fig. 7. The relationship between 1/ 3 and c for various diameters of the coreshell particles: (") CS-4, (Q) CS-1, (2) CS-3, (F) CS-2. The slope of the straight line is kT /6 .

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1/ 3 and c with various suspensions of different particle size. In the loglog plot, c is proportional to 1/ 3 and the slope of the relationship is 3kT /4 . This conrms that the diffusion coefcient of the particles in the shear-thinning suspensions of coreshell particles is consistent with a particle of diameter . From these results, the dynamics of the suspension of the core shell particles can be explained by the Brownian hard sphere model, in which there is competition between the bulk mass transfer due to the applied eld and diffusion of the particles in the suspension. 4. Summary The rheological behavior and microstructure of aqueous suspensions of coreshell structured carboxylated latex particles were examined. The critical shear stress c and inter-particle distance of the microstructure did not change with changing degree of neutralization and concentration. However, with increasing particle diameter, c increased and decreased. These behaviors were found to be consistent with the Brownian hard sphere model, in which competition exists between the bulk