Rheol Acta (2005) 45: 2332 DOI 10.

1007/s00397-005-0439-2

ORIGINAL CONTRIBUTION

Konraad Dullaert Jan Mewis

A model system for thixotropy studies

Received: 18 October 2004 Accepted: 23 October 2004 Published online: 2 July 2005 Springer-Verlag 2005

K. Dullaert (&) J. Mewis Department of Chemical Engineering, K.U. Leuven, de Croylaan 46, 3001 Leuven, Belgium E-mail: jan.mewis@cit.kuleuven.ac.be Tel.: +32-16-322676 Fax: +32-16-322991

Abstract Many constitutive equations have been proposed for thixotropic materials but the supporting experimental evidence has usually been rather fragmentary. To a large extent this is due to the diculties involved in measuring thixotropic systems. These systems normally display various phenomena that result in poor accuracy and poor reproducibility of the measurements. Therefore, it has been attempted here to formulate a robust thixotropic system that allows accurate measurements and that would be suitable for detailed studies of thixotropy. The system that has been developed is based on a matrix liquid that consists of a high boiling paran oil and a low molecular weight poly(isobutylene). A suitable type of fumed silica is used as the dispersed phase. The various

rheological parameters of the material can be altered by varying the concentration of the components and, if necessary, the molecular weight of the polymer. The relative humidity around the sample turns out to be an important factor in controlling the yield stress, and its eect is shown to be reversible. The selected system can be measured accurately over a wide range of measurement conditions. These include stress jump measurements, which can be used to separate viscous and elastic contributions. The highest possible shear rate is limited by the occurrence of a peculiar phenomenon that shows up in the normal stresses. Keywords Thixotropy Flocculated suspension Fumed silica Wall slip Measurement accuracy

Introduction
Colloidal dispersions can display a wide range of rheological features, including shear thinning, shear thickening, yield stresses and time eects. In many cases the dispersions are weakly occulated, meaning that the particles stick together in ocs that can be reversibly broken down when subjected to ow. The shear rate dependence of the oc structure can cause pronounced shear thinning, including the appearance of a yield stress, even at very low particle volume fractions. Upon a sudden change in shear rate, the resulting change in

oc structure might take a signicant amount of time. As a result the viscosity will also evolve over time, causing the suspension to be thixotropic. Thixotropy is dened here as a gradual decrease over time of the viscosity after a sudden increase in shear rate. The original viscosity should be recovered eventually when the initial shear rate is applied again. As discussed below these time eects do not necessarily imply the presence of viscoelastic phenomena. Mewis (1979), and more recently Barnes (1995), have presented extensive reviews on the subject.

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The basic mechanisms for the formation and breakdown of ocs in colloidal suspensions are rather well understood. Yet, a detailed analysis of thixotropic systems is still lacking. It is known that, even in model systems, the ow-induced microstructure can be quite complicated, explaining the diculties involved in modelling its kinetics. For real, industrially used thixotropic systems it cannot be expected that their rheological behaviour could be obtained from ab initio calculations. For describing such systems phenomenological constitutive equations are essential. In principle, developing constitutive equations for thixotropic materials is quite straightforward. Starting from Newtons law, or from an arbitrary model for generalized Newtonian uids, the model parameters can be assumed to be a function of one or more internal structural parameters. Together with kinetic equations that express the eect of ow on the structural parameters, a phenomenological model description for thixotropy is obtained (Mewis 1979; Barnes 1997). Mujumdar et al. (2002) compiled an extensive list of thixotropic models that have been generated in this manner. When starting from a linear viscoelastic model rather than a viscous one, the same procedure can be used to generate nonlinear viscoelastic models (Phan Thien and Tanner 1977). Thixotropic systems are characterized by pronounced, specic time eects that dier from those normally encountered in nonlinear viscoelastic systems. This can be illustrated by the stress transients resulting from a sudden reduction in shear rate. In nonlinear viscoelastic systems the focus would be on the resulting relaxation of the stresses. In thixotropic systems the stress relaxation is not the dominating eect but rather the subsequent slow increase in shear stress. Also, the other usual emanations of viscoelasticity, such as normal stress dierences, are often negligible in these materials. Although the qualitative modelling of thixotropic phenomena is easy, generating models that accurately describe real thixotropic materials turns out to be more challenging. From the large number of models that have been proposed it can already be deduced that an adequate generic model, applicable to a wide range of materials, has not been developed yet. In addition, available models have not been thoroughly and critically tested. Validation has often been based on small data sets of questionable reliability, covering only a limited range of ow conditions. As the models normally contain a rather large number of tting parameters, their real predictive power remains uncertain. Thixotropic systems are notoriously dicult to measure. Instrumental artefacts such as wall slip, heterogeneous shear rates and gap size eects are not always properly taken into account and can aect the results substantially (Magnin and Piau 1990; Coussot et al. 2002). In part, these diculties are inherent to the

phenomenon under investigation: by denition the systems can be far from equilibrium and therefore assessing reproducibility and reversibility is far from trivial. The major intrinsic cause of diculties is the fact that oc size is not necessarily a sucient descriptor of microstructure: the internal oc structure can also change. Various authors have for instance reported compaction of ocs due to shearing (Sonntag and Russel 1986; Hoekstra et al. 1992; Wolthers et al. 1996a). This causes complex shear history eects in the rheology of such systems (Mewis et al. 1975). The availability of accurate data covering a wide range of experimental conditions, would be extremely useful in solving the many remaining problems related to thixotropy. The extensive literature on the subject, however, contains surprisingly few useful data sets (Mylius and Reher 1972; Mercer and Weymann 1974). The problems mentioned in the previous paragraph are in part responsible for this situation, but thixotropic samples frequently display other phenomena that interfere as well, with the accurate measurement of their properties. Obvious eects that cause continuous but non-thixotropic changes over time of the apparent viscosity are the evaporation of solvents (Magnin et al. 1990) and sedimentation of particles (Wolthers et al. 1996b). Related to the latter is delayed sedimentation (Stars et al. 2002; Kilfoil et al. 2003). It occurs mainly during rest periods or after a decrease in shear rate whenever the interparticle forces are not strong enough to bear the weight of the particulate network that has been developed. During rest periods inhomogeneities might also develop because of syneresis (Van Vliet et al. 1991). This happens when the interparticle forces are strong enough to cause shrinkage of the particulate network, thereby expelling the medium. In this manner a layer of suspending medium without particles is formed at the outside of the sample. Except for structural heterogeneities, there can also be homogeneous but irreversible changes in time that confound thixotropy measurements. These can be caused by changes in the degree of dispersion, often resulting from eective changes in the surface conditions of the particles. The latter is illustrated by changes in wetting or in adsorption on the particles of certain components from the suspending medium, e.g. polymers (De Groot and Macosko 1991). Changes due to the formation of an additional component in the system have also been reported (Baudez and Coussot 2001). The purpose of the present work is to develop a suitable model system in which the various sources of interferences that have been discussed above could be avoided as much as possible. In addition, such a system should satisfy certain other requirements. In particular, the stress evolutions during transient experiments should be suciently pronounced and suciently slow to permit accurate measurements of

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ow-induced changes. Systems might have limits beyond which no meaningful and accurate measurements are possible, these limits should be known and should not be too narrow. Clearly, the present system need not necessarily represent all possible types of thixotropic materials.

Components
An ideal thixotropic model system should satisfy the various requirements discussed above. To ensure accurate measurements it is of primary importance that the stress levels are suciently high and that the thixotropic transients extend over a suitable time period. The medium viscosity and the particle concentration can be used to adapt these characteristics within a certain range. To avoid interference from other reversible time eects, the suspending medium should be inelastic. Irreversible time eects should be eliminated, or at least reduced to a suciently low level. This includes the changes caused by evaporation, therefore low volatility, non-aqueous media are preferred. The exact nature of the medium will also depend on the kind of particles used, as the medium/particle combination determines the interaction forces among the particles. Adequate interparticle attraction is required in order to generate ocs that cause thixotropy. Very high attraction forces, however, are not desirable either, since they shorten the recovery time scales of the thixotropic transients. Such large forces could also induce syneresis phenomena. As far as the particles are concerned, a suitable representative of the commonly used thixotropic agents is preferred. Due to their transparency, roughly spherical shape and availability in a wide range of surface treatments, fumed silica particles were selected, in this case Aerosil R972 from Degussa (Eisenlauer and Killmann 1980, Degussa 1993). This material has a density of 2,200 kg m)3 (Barthel 1995). The elementary particles are rather monodisperse and rather spherical, with an average diameter of 16 nm (Martin and Keefer 1986). This particular type of fumed silica has been made hydrophobic by substituting a signicant fraction, i.e 90% (Aranguren et al. 1997), of the silanol groups on the particle surface. The substitution has been achieved by adding dimethyldichlorosilane during the hydrolysis (Donnet et al. 1986). With the type of particles specied, a non-volatile medium should be selected that ensures a suitable viscosity level and properly tuned interparticle attraction forces for the given particles. Too strong an interaction force can be avoided in these fumed silica dispersions by keeping the dierence in hydrogen bonding capacity between the particles and the suspending medium, rather small (Barthel 1995; Raghavan et al. 2000). A suitable starting point for the suspending medium is a paran oil, the one used here (Riedel-de Ha e n 18512) has a density of 827 kg m)3 and a viscosity of 0.16 Pa s at 20C. A predispersed mother batch of 4 vol% Aerosil R972 in this particular oil was provided by Degussa (Germany). No preconditioning was applied to the particles prior to the dispersing process. For the latter, a high-speed dissolver (8,000 rpm) was used in a rst step,

Experimental
Steady state and transient experiments were performed on a stress-controlled rheometer (MCR 300, PaarPhysica) and on a rate-controlled device (ARES, Rheometric Scientic). The eect of shear history on the apparent steady state was studied on the stresscontrolled instrument. This instrument has the advantage, in comparison with the ARES, that no automatic adaptation of the zero torque is applied after each programmed sequence. Hence, no ambiguity exists about the origin of the measured changes of the stress values. For the normal stress measurements the ARES has been used. All data have been taken at 20C. It is essential here to separate eects of time and shear rate, which are coupled in thixotropic materials. Therefore, the shear rate should be constant throughout the sample during transient measurements. A cone and plate geometry with a suciently small cone angle is suitable for this purpose. On the MCR 300, two dierent cone and plate geometries in stainless steel were used, both having a radius of 12.5 mm, the cone angles being 0.035 and 0.07 rad. A single geometry was used on the ARES (radius of 12.5 mm and cone angle of 0.04 rad). Even in such geometries the shear rate is not absolutely constant: the maximum cone angle that ensures nearly constant shear rates decreases to zero when the material becomes very shear thinning, i.e. with a power law index tending to zero (Cheng 1966). As the materials to be used here have a yield stress, the constant shear rate assumption will fail, below a critical shear rate. The most direct way to identify possible slip eects is by visual observation of the ow eld. This has been done by applying a thin line of powder on the outer sample surface, and the deformation of this marker line then recorded with a camera. TiO2 powder provided a suitable marker material, a digital camera (Hamamatsu) was used for observing the marker. Other visualization techniques are possible (Persello et al. 1994; Magnin and Piau 1990). The eect of slip was also evaluated by comparing results with dierent cone angles. Finally, slip can be eliminated or reduced by using roughened surfaces. For the MCR 300 a cone and a plate with a radius of 12.5 mm (cone angle of 0.07 rad) were sand blasted to obtain a roughness of 200 lm.

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followed by a homogenisation step in an Ultra-thurax ultrasonic device. Addition of a low molecular weight poly(isobutylene) (PIB: Oppanol B3 from BASF) provides a means to control the high shear viscosity and, to a certain extent, the interparticle forces. The PIB is Newtonian over the range of shear rates used in this study, having a density of 894 kg m)3 and a viscosity of 45 Pa s at 20C. The most suitable particle volume fraction is limited at the lower end by the appearance of sedimentation and the weakness of the resulting particulate network. At the upper end, wall slip and yielding start to interfere substantially with the measurements. In the present case, an optimum level was between 2.5 vol% and 3.0 vol%, depending on the other parameters. For the nal experiments the medium viscosity was adjusted to a level of 0.65 Pa s by mixing in a suitable amount of PIB (i.e. 27 wt%). The weight percentage of PIB refers to the amount calculated on the total weight of the sample. The composition of the mother batch has to be suitable for the dispersion process used. Its particle concentration was also selected to be above those of the nal formulations. The nal concentration levels were then achieved by diluting the mother batch with the required amounts of paranic oil and PIB. In this process all ingredients were premixed in a mechanical agitator, followed by a thorough mixing stage on a laboratory roll mill. The ow conditions on the latter device are milder than those that had been applied during the original dispersion process. In this manner the original degree of dispersion was not altered significantly during the dilution stage. It is known that small dierences in the degree of dispersion can result in substantial rheological changes at a given particle volume fraction (Potanin et al. 1998), but this was avoided by the procedure followed here. Finally, the samples were heated at 40C and placed under vacuum to eliminate most of the air bubbles.

Fig. 1 Eect of PIB on the ow curve of a 1.5 vol% fumed silica dispersion in a mixture of paran oil and PIB

viscosity is not very critical but the medium viscosity should be suciently large to ensure accurate measurements. High values of the medium viscosity are also important in controlling sedimentation at rest or at low shear rates. Adding PIB has a greater eect as it can also aect the interparticle forces. The low molecular weight of the polymer avoids a signicant depletion eect but polymer adsorption on the silica surface reduces the interparticle attraction. This can be used to manipulate the recovery time scales, at least in part. Figure 2 illustrates this for suspensions with 1.5 vol% silica particles using stress transients after a stepwise decrease in shear rate from an initial value of 10 s)1 to a nal value of 0.1 s)1. The " reduced shear stress, rt; in Fig. 2 is dened as:

Sample formulation
The components strongly interact with each other and therefore their individual contributions cannot be fully isolated. PIB mainly aects the medium viscosity. The latter governs the high shear viscosity of the dispersion, as the particle volume fraction is always very low in these samples and as all the ocs are broken down at high shear rates . This is illustrated in Fig. 1 where the ow curves are shown of samples containing 1.5 vol% fumed silica particles dispersed in a mixture of paran oil and dierent amounts of PIB. The high shear viscosity of the sample containing 50 wt% PIB is approximately 15 times larger than the sample without added PIB, proportional to the change in medium viscosity, i.e. from 0.14 Pa s to 2.05 Pa s at 20C. The high shear

Fig. 2 Eect of PIB on the build-up behaviour after a stepwise reduction in shear rate from 10 s)1 to 0.1 s)1 on a 1.5 vol% fumed silica dispersion in a mixture of paran oil and PIB

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" rt

rt ri re ri

where r(t) is the transient stress at time t, and ri and re are the stresses at respectively, time zero and steady state. From the gure it can be concluded that adding 5 wt% PIB increases the time constant for structure build-up by a factor of approximately 5. Hence, PIB clearly reduces the interparticle attraction forces, for which adsorption of the polymer on the particle surface seems the logical mechanism. Adding more PIB hardly changes the structure build-up under shear, indicating that adsorption is already close to its maximum at a bulk concentration of 5 wt%. Higher concentrations of PIB will increase the medium viscosity, though the eect of the latter on structure recovery during shear seems limited. Adsorption depends on temperature and therefore temperature eects do not obey simple scaling laws here. This can be illustrated by the following experiment. A sample consisting of 1.5 vol% fumed silica particles dispersed in a mixture of paran oil and 50 wt% PIB is sheared at 0.1 s)1 until the steady state is reached. Subsequently, the temperature is raised from 20C to 50C. Temperatures above 60C have been avoided as they induce an irreversible increase in viscosity. After the sample is thermally equilibrated it is sheared again at 0.1 s)1 after a short preshearing at 10 s)1 to ensure a homogeneous structure. A constant stress is reached at 0.1 s)1 after 500 s and the temperature is then decreased again to 20C. The stress response resulting from this temperature drop is shown in Fig. 3, together with the evolution of the temperature in the sample. The stress increases while the sample cools down, following the increase in medium viscosity. Once the sample is at

20C, the stress starts to decrease as a result of readsorption of PIB. The steady state stress at 0.1 s)1, before the temperature changed (indicated by a dashed line on the stress curve), is recovered after a time of the order of 104 s. In addition to the concentration of PIB, an adequate level of silica particles has to be determined. The particle volume fraction does not aect only the apparent yield stress or the shear modulus of the network (Buscall et al. 1988; Van der Aerschot and Mewis 1992), the eect on the thixotropic time scales should be considered as well (Fig. 4). The stress reduction of Eq. 1 and the experimental protocol of Fig. 2 have been applied. For the very low-volume fraction used here, the time scale decreases approximately inversely proportional to the particle concentration. This is less than could be expected on the basis of the increased collision rate and reects the interference eects of stress level and microstructure on the thixotropic time constants. Composition and temperature are not the only parameters that can be varied, and should be controlled, when studying the system at hand. Thixotropy in nonaqueous media can be sensitive to the presence of water at the surface of the particles (Khan et al. 1991; Van der Aerschot and Mewis 1992). Therefore, the eect of the humidity of the surrounding air on the rheological properties of the fumed silica dispersion is investigated. In order to investigate this eect a sample, containing 2.7 vol% fumed silica particles dispersed in a mixture of paran oil and 30 wt% PIB, was exposed to a humid atmosphere and subsequently dried by heating at 60C in the presence of silica gel for 12 h. Parts of this sample were conditioned for 72 h at ambient temperature in

Fig. 3 Stress evolution at a shear rate of 0.1 s)1 during a quenching experiment from an initial temperature of 50C to 20C at constant relative humidity on a 1.5 vol% fumed silica dispersed in paran oil and PIB (50 wt%)

Fig. 4 Eect of particle volume fraction on the build-up behaviour during a stepwise reduction in shear rate from an initial value of 10 s)1 to a nal value of 0.1 s)1 for samples, containing fumed silica particles dispersed in a mixture of paran oil and PIB (30 wt%)

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dierent controlled environments, using saturated solutions of NaBr and KNO3. These solutions produce a relative humidity of respectively 59% and 95% at 20C. A third sample was kept in a dessicator lled with silica gel. Afterwards, ow curves were measured on the three samples (Fig. 5). This conditioning did clearly did not aect the high shear behaviour, where ocs are essentially broken down. The eect at low shear rates, however, is substantial. Figure 5 shows that the apparent yield stress can be varied over more than a decade by changing the humidity of the environment. By keeping the sample in the dessicator the ow curve was similar to that obtained after drying at elevated temperatures. The original ow curve could be recovered after humidifying the heated sample. This reversibility is important to ensure a robust model system where dierences in the history of the sample can be eliminated. It has apparently not been reported before for this kind of material. The nal formulation, further referred to as 2.9%P+PIB, consisted of 2.9 vol% fumed silica particles dispersed in a mixture of paran oil and 27 wt% PIB (calculated on total sample mass). The sample was stored at ambient temperature in a controlled environment (NaBr). It was tested for reproducibility both in steady state and transient ow and an extended period of time. Measurements were also performed with different cone angles and on dierent instruments in an environment where the relative humidity was controlled with a saturated solution of NaBr in the solvent trap. The results are shown in Fig. 6. Up to 100 s)1 the data points are real steady state values. At higher shear rates the sample displayed an instability (see below). Therefore, at these shear rates data were taken as soon as the viscosity levelled o but before the instability was initiated. The data of Fig. 6 demonstrate that the sample did

Fig. 6 Flow curve of a 2.9 vol% dispersion of fumed silica in a mixture of paran oil and PIB (27 wt%) stored at constant relative humidity. Eect of sample life times, measurement geometry and instrument used

not change over several weeks and that the results did not depend on the measurement geometry. The ow curves of dierent samples prepared from the same mother batch deviate less than 5% from the average values. For thixotropic studies it is also essential that the transient behaviour is highly reproducible. Again, samples were tested at dierent times after sample preparation and on dierent instruments (Fig. 7). The data indicate a reproducibility within the measurement accuracy of the rheometers. The initial part of the transients, i.e. below approximately one second, is not as reproducible because here the characteristics of the individual instruments interfere.

Fig. 5 Eect of thermal history and relative humidity of environment on the ow curve of a 2.7 vol% dispersion of fumed silica in a mixture of paran oil and PIB (30 wt%)

Fig. 7 Stress response to a stepwise reduction in shear rate from 10 s)1 to 1 s)1 (sample as in Fig. 6). Eect of sample life times, measurement geometry and instrument used

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Shear rate window

It has been shown that the reproducibility of the rheological properties is ensured (Figs. 6, 7) and that the selected formulation shows pronounced thixotropic time eects (Fig. 7). It remains to be veried over what shear rate range the samples can be measured accurately, as limitations should apply at least at the low shear rate end. Wall slip and non-homogeneous ow at low shear rates As discussed in the introduction, thixotropic dispersions with a yield stress often suer from non-homogeneous ow at low shear rates (Magnin and Piau 1990; Coussot et al. 2002). Visualization experiments are performed to _ determine the critical shear rate, cc ; at which wall slip appears. As the time required to apply a marker line is not negligible (30 s 2 min), and no pre-conditioning step can be done once the marker line has been applied, it is dicult to achieve a controlled shear history. Therefore, the present technique is mainly suitable for investigating wall slip at apparent steady state conditions. To create a certain level of reproducibility and to ensure a homogeneous structure, the sample is sheared at a shear rate of 25 s)1 for 200 s prior to applying the marker line. The visualization experiments are performed on two dispersions, labeled as 2.7%P and 2.7%P+PIB. They consist of 2.7 vol% fumed silica particles dispersed in paran oil and a mixture of paran oil and 30 wt% PIB, respectively. Figure 8a shows the evolution of the marker line at a shear rate of 0.01 s)1 for the 2.7%P sample, using a cone with an angle of 0.035 rad. Initially the deformation of the line complies with the assumption of a constant shear rate in the gap. At larger strains, however, a pronounced slip layer becomes visible at the

rotating cone. For the 2.7%P dispersion, wall slip could be detected up to 0.25 s)1. In Fig. 8b, results of a visualization experiment on the 2.7%P+PIB sample, using a nal shear rate of 0.1 s)1 and a cone angle of 0.07 rad, are shown. Similar experiments revealed homogeneous ow down to shear rates of 0.03 s)1 for the 2.7%P+PIB sample. The appearance of wall slip and non-homogeneous ow also aects the shape of stress transients, resulting from a stepwise change to a low shear rate. For the 2.7%P+PIB sample, the stresses gradually increase up to a plateau value and this for values of the nal shear rate down to 0.03 s)1 (see e.g. Fig. 7). For samples without PIB, such as the 2.7%P dispersion, however, the stress starts to drop once the particulate structure has developed to a certain level. This is possible when the nal shear rate is smaller than 0.5 s)1. It can be attributed to the onset of wall slip, as repeated shearing at low shear rates gave no indication of sedimentation. Finally, the apparent steady state ow behaviour of the 2.9%P+PIB dispersion is investigated using smooth and roughened geometries (Fig. 9). This formulation is in the optimal range for thixotropic studies. Down to shear rates of 0.05 s)1 no dierences are found between the ow curves measured with the two geometries. At lower shear rates, however, the apparent steady state stress values measured with the smooth geometry drop systematically below those obtained with the roughened geometry, indicating the presence of wall slip. These data are in agreement with the previously discussed visualization experiments on the 2.7%P+PIB sample. Despite the slightly higher volume fraction, the 2.9%P+PIB sample has a signicant lower critical shear _ rate cc than the 2.7%P dispersion without any PIB (0.05 s)1 instead of 0.5 s)1). As discussed in the previous section, the PIB chains partially adsorb onto the particle surface, resulting in a weaker interparticle attraction. Wall slip is therefore reduced to substantially

Fig. 8 Visualization of ow eld at shear rate of a 0.01 s)1 on a 2.7 vol% dispersion of fumed silica in paran oil (2.7%P), using a cone angle of 0.035 rad and b 0.1 s)1 on a 2.7 vol% dispersion of fumed silica in a mixture of paran oil and PIB (2.7%P+B3), using a cone angle of 0.07 rad

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Fig. 9 Eect of roughness of the cone and plate geometry on the ow curve for a 2.9 vol% dispersion of fumed silica in a mixture of paran oil and PIB (2.9%P+B3)

Fig. 10 Eect of the previous shear rate on the apparent steady state at 1 s)1, 2.9 vol% dispersion of fumed silica in a mixture of paran oil and PIB (2.9%P+B3)

lower shear rates when PIB is present. These results agree with visual inspections of the two samples after signicant storage time, showing a distinctly reduced level of syneresis for the sample with PIB chains. Hysteresis behaviour at high shear rates Flow-induced viscosity changes have to be reversible to be meaningful in thixotropic studies. This can restrict the accessible shear rate window. Normally, reversibility is reduced at the lower shear rates in thixotropic materials. Here, real steady state data could be obtained down to the lowest shear rates reported, but deviations occurred at high shear rates. To illustrate this phenomenon, stepwise changes from various shear rates to the same nal shear rate, here 1 s)1, are performed. In Fig. 10 the steady shear stresses, obtained after a welldened time, are plotted as a function of the applied initial shear rate. A fresh sample is taken at the beginning of every measuring sequence. During each sequence the initial shear rate is systematically increased from a value of 0.1 s)1 up to a value of 1,000 s)1. For the rst sequence, where the initial shear rate is applied either for 10 s or until at least a strain of 800 is reached, the apparent steady state is constant up to initial shear rates of approximately 100 s)1. At higher preshear rates, slightly increasing stress values are obtained. This trend is amplied for the two other sequences with preshear periods of respectively 400 and 1,000 s. It can be concluded from Fig. 10 that the apparent steady state stress for a shear rate of 1 s)1 is constant within the measuring accuracy of the rheometer for initial shear rates below the critical value of 100200 s)1, irrespective of the duration of the preshear

period. Beyond this critical initial shear rate, the apparent steady state stress values strongly increase as a function of both the value of the initial shear rate and the duration of the initial shearing. The normal stress transients, measured during extensive preshear periods at these high initial rates, show another interesting feature. This is illustrated in Fig. 11, where the evolution of the transient normal stresses, divided by their initial values, are shown as a function of strain. Note that the normal stress transients were obtained using the ARES software and can therefore contain an oset constant. This, however, does not aect the general observed trend. The normal stress transients remain constant up to a strain of the order of

Fig. 11 Scaled normal stress transients on a 2.9 vol% dispersion of fumed silica in a mixture of paran oil and PIB (2.9%P+B3)

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106, after which an abrupt and steep increase can be observed. By plotting the data as a function of the strain, the time evolutions of the normal stress at dierent shear rates collapse onto a single master curve. When, after such an extensive preshear period, the shear rate is lowered, the shear stress initially goes through a maximum and then decays for a period of 12 h before reaching a steady state level, higher than the initial one. The slow recovery suggests that no ow instability is involved. Flow-induced aggregation might be a possible mechanism (Dintzis et al. 1995; Kim et al. 2002). The nature of this phenomenon has not been studied further here. The main conclusion of the study at hand is that the structural changes of the proposed model system are completely reversible up to shear rates of 100200 s)1.

Conclusions
A model system suitable for detailed studies of thixotropy has been developed. It is based on a dispersion of fumed silica particles in a mixture of paran oil and poly(isobutylene). The eect of the dierent components and of the environmental conditions on the resulting rheological behaviour have been examined. The amount of added PIB aects the medium viscosity and therefore can be used to control the high shear viscosity. A fraction of the PIB chains adsorbs on the particle surface, thus reducing the interaction force among the silica particles. In this manner the thixotropic time scales can be slowed down, also the occurrence of wall slip can also be delayed to lower shear rates and syneresis during storage can be reduced. Wall slip was identied using direct visualization experiments and rheological

measurements with geometries of dierent roughness. Experiments revealed the recovery time scales to be approximately inversely proportional to the particle volume fraction. Systematic tests indicate that the apparent yield stress of the dispersion can be varied over more than a decade by changing the relative humidity of the environment surrounding the sample. This eect is reversible. Once the thermal history and the relative humidity are controlled, the proposed system produces pronounced thixotropic time eects with an unusually high degree of reproducibility and accuracy. The shear rate window, in which meaningful and accurate rheological experiments could be performed, was investigated for a suitable formulation of this dispersion. The lower shear limit, associated with the appearance of wall slip, was experimentally determined to be 0.05 s)1 for the measurement geometry used. According to the denition of thixotropy, the apparent steady state should be independent of the applied shear history. This was satised at low shear rates until the lowest value used here. From a critical preshear rate onwards (i.e. 100200 s)1), the apparent steady state stress at lower shear rates increased with higher preshear rates and longer preshear periods. The normal stress transients during such preshear periods displayed an abrupt increase after a certain time. This could be scaled for dierent shear rates by plotting the data as a function of strain. It can be concluded that homogeneous ow and reversible structural changes of this dispersion could be ensured for a broad range of shear rates. The thixotropic phenomena are pronounced and reproducible. They can be measured with a high degree of accuracy and therefore provide a suitable means to critically study thixotropic models.

References
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