Soft Matter

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High bandwidth linear viscoelastic properties of complex uids from the measurement of their free surface uctuations
Basile Pottier,abc Guylaine Ducouret,abc Christian Frtigny,abc Francois Lequeuxabc and Laurence Talini*abc e
Received 15th February 2011, Accepted 2nd April 2011 DOI: 10.1039/c1sm05258f We present a new non-invasive optical method to measure the linear viscoelastic properties of materials, ranging from complex uids to soft solids, within a large frequency range (about 0.1104 Hz). The surface uctuation specular reection (SFSR) technique is based on the measurement of the thermal uctuations of the free surfaces of materials at which a laser beam is specularly reected. The propagation of the thermal surface waves depends on the surface tension, density, and complex viscoelastic modulus G*(u) of the material. The SFSR signal results from the contribution of different surface modes, and we discuss the leading effect measured as a function of |G*| and frequency. For known surface tension and density, we show that the frequency dependent elastic and loss moduli can be deduced from the uctuation spectrum. Using a viscoelastic solid (a cross-linked PDMS), which linear viscoelastic properties are known in a large frequency range from rheometric measurements and the timetemperature superposition principle, we show that there is a good agreement between the rheological characterization provided by rheometric and uctuation measurements. We also present measurements conducted with a complex uid: a supramolecular polymer solution, formed from Hbonded molecules. At low frequencies, the agreement with rheometric measurements is again very good. We further investigate the high frequency rheology of the supramolecular polymer solution, and show that it behaves very similarly to supramolecular polymer solutions formed by wormlike giant micelles.

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Introduction
Among complex uids, some can both store and dissipate mechanical energy: they are viscoelastic. The frequency dependence of their linear complex shear viscoelastic modulus G* reects the dynamics of their microscopic components, its measurement therefore provides information on the microscopic processes at stake. Owing to the multiple lenghtscales of their structure, the involved characteristic times can extend over several decades.1 High bandwidth characterization of linear viscoelastic properties is therefore needed. Rheometric measurements are widely used to determine the viscoelastic properties of complex uids either for bulk or interfacial properties. The principle behind these techniques consists, for example, in exerting a strain and measuring the resulting stress. The growing inuence of inertia of mechanical devices at high frequencies limits the accessible frequency range; mechanical measurements at frequencies larger than about 10 Hz remain a challenge. In the past two decades, alternative methods
a UPMC Univ Paris 06, UMR 7615, Laboratoire PPMD, F-75005 Paris, France. E-mail: laurence.talini@espci.fr b CNRS, UMR 7615, Laboratoire PPMD, F-75005 Paris, France c ESPCI ParisTech, UMR 7615, Laboratoire PPMD, F-75005 Paris, France Electronic supplementary information (ESI) available. See DOI: 10.1039/c1sm05258f

have been developed to measure the linear viscoelastic properties of complex uids.2 Among them, microrheological techniques, using either the diffusion or the externally controlled motion of probe colloidal particles, have provided successful measurements of linear viscoelastic properties.3,4 The probe particles may be tracked individually by microscopy,5 or their motion can be inferred from light diffusion techniques such as diffusing wave spectroscopy.6 Non-Brownian particles can also be followed in the presence of an imposed mechanical noise that plays a role analogous to temperature.7 Microrheological measurements present two advantages over rheometric measurements: rst, they do not require a macroscopic ow in the sample, and second, the accessible frequency range is wide. However, the dispersion of colloidal particles may be experimentally difcult in some complex uids as a consequence of colloidal stability problems.8 Furthermore, the probed behaviour depends on the probe particles size, which may introduce an additional lengthscale in the measurement.9 Herein we show that the linear viscoelastic properties of complex media can be fully characterized using an optical technique, which is based on the measurement of the thermal uctuations of the free surfaces of the media, namely a surface uctuation specular reection (SFSR) technique.10 It presents the advantages of being totally non invasive, requiring no induced ow, nor addition of probe particles and providing measurements in an extended frequency range, from about 0.1 to 104 Hz.
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It can moreover be used indifferently to characterize either complex uids or soft solids. We show that the linear viscoelastic properties of those materials can be inferred from uctuation measurements. Although the results we present are for systems that do not exhibit surface viscoelasticity, interfacial properties contribute to the SFSR measurements, and the technique is promising for the characterization of interfacial viscoelasticity. In the following, we rst briey describe the technique and the measured signal. We then discuss the leading effect that contributes to the signal in a viscoelastic modulus |G*| vs. frequency diagram. We illustrate that discussion with the uctuation spectra measured at the free surfaces of a Newtonian uid and of a viscoelastic solid, a cross-linked polymer. In the latter case, we further demonstrate how the frequency dependent elastic and loss moduli can be inferred from the surface uctuation measurements; we show that the moduli are in very good agreement with the ones deduced, in the same frequency range, from rheometric data with a timetemperature superposition principle. Finally, we study the surface uctuations of a complex uid: a living polymer solution, formed from H-bonded molecules. In that case, the amplitude of the surface uctuations are driven by both elastic and surface tension effects. We demonstrate that the linear viscoelastic properties can be entirely determined from the uctuation spectrum. The agreement with rheometric data at low frequency is very good, and we further compare the high frequency behaviour to that of other supramolecular polymer solutions.

of 25  C. Care is taken to prevent evaporation before and during the SFSR measurements. The viscoelastic solid is a cube of edge length 1 cm; it has been cut in a PDMS sample previously cross-linked in an aluminium pan. SFSR measurements have been performed on three different surfaces of the sample: the two surfaces that had been in contact with air and pan, respectively, during cross-linking, and the surface obtained by cutting the sample at mid-height. The uctuation spectra of those three surfaces exhibited no signicant difference, thus showing that the properties of the cross-linked PDMS sample are the same at its surfaces and within its bulk. Reference rheological measurements: mechanical rheometry Reference mechanical measurements have been performed on both the viscoelastic liquid (living polymer solution) and viscoelastic solid (cross-linked PDMS). Linear viscoelastic measurements have been conducted on the EHUT solution with a stress-controlled rheometer (Haake RS600) equipped with a cone-plate. The solution is heated at 60  C, and further poured into the rheological apparatus; it is then left at rest for half an hour at the measurement temperature (25  C). That procedure ensures reproducible rheological measurements. The sample was rst submitted to a stress sweep at 1 Hz in order to determine the linear regime. The stress sweep was followed by a frequency sweep and the elastic and loss moduli G0 and G00 were measured as a function of frequency. The mechanical characterization of the solid PDMS sample has been conducted on an Anton Paar MCR 501 rheometer in simple shear strain, with plateplate geometry. The samples were cylinders of 8 mm in diameter and 2 mm thick, and were glued to the rheometer plates with cyanoacrylate glue (Loctite 406). The temperature was measured every 3 from 60  C to 30  C. At each temperature, the sample was submitted to a frequency sweep in the range 0.0150 Hz and the stress was measured. The strain amplitude was set at 0.1% for temperatures smaller than 21  C and at 1% for all other temperatures. Using time temperature superposition,13 the variations in the elastic and loss moduli in the frequency range 0.1105 Hz have been deduced from the data at different temperatures. Principle of SFSR technique The technique of surface uctation specular reection (SFSR) spectroscopy consists of measuring the height of uctuations of a free surface, using the reection of a laser beam on that surface. As shown schematically in Fig. 1, the laser beam is focused on the free surface, and its specular reection from the surface is sent to a detector constituted of a two-quadrant photodiode. The reected beam is centered on the two quadrants; each quadrant delivers a voltage (after proper current to voltage conversion and preamplication), and the difference between those two voltages, dV(t), is measured after amplication and anti-aliasing ltering. dV(t) is a uctuating signal of zero average, it provides a measurement of the position uctuations of the beam reected off the free surface. At the rst order, the free surface acts as a mirror, hence, the position of the beam is sensitive to its local slope. The uctuations of dV(t) are therefore related to the height uctuations of the free surface. Indeed, the relevant lengthscale
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Materials and methods

Samples The Newtonian low viscosity uid is pure dodecane (Sigma). At 25  C, the viscosity and surface tension of dodecane are respectively 1.34 mPa s and 24.8 mN m1. The viscoelastic solid is cross-linked poly-dimethyl-siloxane (PDMS, Sylgard 184, Dow Corning), prepared with 5%w/w curing agent. Cross-linking is achieved by placing the PDMS and curing agent mixture in an oven at 70  C for two hours. The supramolecular polymers are formed by self-association of bis-urea monomers (EHUT) through hydrogen bonding.11 The EHUT solutions have been prepared by mixing EHUT at a concentration 12 g l1 with dodecane; the solutions are then shaken on a vibrating table for more than two weeks. At a temperature of 25  C and at the chosen concentration, EHUT monomers are self-associated and the laments are entangled.12 The samples are highly viscoelastic but their viscosity can be lowered by increasing the temperature up to 60  C. When left at a temperature of 25  C, the samples recover their initial viscosity within 30 min. For SFSR measurements, the liquid samples (dodecane and EHUT solutions) are poured in a cell such that the total liquid height is small (less than 2 mm), in order to minimize the inuence of the outside mechanical noise on the uctuation spectra through damping of low frequency waves. In the case of lowviscosity liquids such as dodecane, it is nevertheless difcult to perform measurements at frequencies lower than about 100 Hz, since damping of externally induced surface waves is less efcient in that case. The measurements are conducted at a temperature
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Fig. 1 Schematic representation of the principles of the SFSR technique: a laser beam is focused onto the free surface of a sample S with a lens L, and after a reection on the face of a prism P. After reection on the other face of the prism P, the specularly reected part is centered on a detector constituted of a photodiode with two quadrants, Q1 and Q2. The difference between the voltages delivered by the two quadrants is measured after anti-aliasing ltering and amplication through the amplier A. At the rst order, the position of the reected beam reects the local slope of the free surface, the uctuations of the beam position (measured through the voltage difference delivered by the quadrants) therefore provide a measurement of the free surface height uctuations, at a scale set by the beam radius.

the surface uctuations of high surface tension liquids (such as water) as well as elastic solids (such as rubber, with an elastic modulus of 1 MPa), can be successfully measured in the range 100105 Hz for the former, and 0.1104 Hz for the latter.10 Finally, the spatial information missing in the SFSR signal, is not required anyway in homogeneous systems. Experiments based on the measurement of excited surface waves have also been developed in the past decades: the surface waves are generated using electrocapillarity15 or mechanical vibrations,16,17 and the bulk or interfacial rheological properties are inferred from either the damping of the excited waves or the amplitude of the forced standing waves. In those cases, indeed, the deformation of the interface is much larger than with thermally excited waves and can be more easily measured; however, those methods are invasive and may probe non-linear regimes, in particular for systems exhibiting interfacial viscoelasticity. In addition, the accessible frequency range is limited in the case of mechanical vibrations. Data collection As previously mentioned, the sample is placed in the experimental apparatus and the light reected off its free surface is collected on a two-quadrant photodiode. In order to study the uctuation spectrum of the free surface, we compute the power spectrum density (PSD) of the uctuating part of the reected light intensity, normalised by the total reected light intensity. In the experiments presented herein, the voltage difference delivered by the quadrant photodiode is digitized at a sampling rate of 2 105 Hz. The duration T of the acquisition run depends on the desired minimum frequency of the measurement, one run typically corresponds to the acquisition of more than 106 data points. The voltage difference dV(t) is normalised by the sum of the voltages delivered by each quadrant, which corresponds to the total light intensity received by the photodiode. The power spectrum density (PSD), is computed for each run and is further averaged over a given number of runs (typically 100), in order to reduce the noise. The frequency dependent measured signal, denoted as S(u), is therefore given by: *   2 +  1 FT dV t  Su (1)  T Vtot 
ens

in the horizontal plane of the free surface is given by the laser beam size at that surface. That size coincides with the beam-waist and is set at R 28 mm in the present experiment. The height uctuations that signicantly contribute to the signal are the ones occurring over lengthscales close to R. In other words, the signal results mainly from surface modes k such that kR $ 1. For such modes, the height variations that can be detected are as small as a few picometers, which is smaller by two orders of magnitude than the thermally induced height variations of usual free surfaces. In summary, the SFSR signal is the integral sum of the weighted contributions of the surface thermally excited modes, the main contribution resulting from modes of wave vectors k such that kR $ 1, R being the laser beam radius at the free surface. The radius beam also sets the vertical lengthscale of the measurement, and the SFSR technique thus probes the material properties within a few tens of microns of its surface. In its principles the technique is very similar to the ones developed decades ago and based on light scattering by the thermal uctuations of free surfaces.14 In the latter techniques, however, a single surface mode is selected by measuring the scattered light at a given angle. The signal therefore contains spatial information, which is absent from the signal in SFSR. However, the scattered light intensity is very small, which limits scattering measurements to systems with large surface uctuations and/or reduces the available frequency range. The advantage of the SFSR technique over light scattering is that the SFSR signal is much larger than in the latter technique, measurements can therefore be conducted on various media, including media with small surface uctuations such as large surface tension liquids or soft elastic solids. The frequency range is also far less limited than in scattering experiments. Practically, the measurement is limited at low frequency by outside mechanical noise, and at high frequency by the electronic noise of the instruments (photodiode, amplier). We have shown in a previous work that
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where hiens denotes the ensemble average, FT the time Fourier transform and Vtot the total voltage delivered by the two quadrants. The total duration of one measurement is approximately 10 min, for a power spectrum in the frequency range 1105 Hz. Theoretical description of the spectra We have shown in a previous paper10 that the measured PSD S(u) can be expressed as a sum over the modes of the uctuating surface such that:
N

Su
0

Pk uFkkdk

(2)

Function F is a weighting function of mode k, which is independent of the probed material, but depends on the laser
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wavelength and beam size. Function F reects the weight of the contribution to the signal from the spatial modes of the surface, and is thus maximum for kR $ 1. It is given by:   k 2 R2 Fk Bk2 R2 exp (3) c where B is a prefactor and c a numerical constant (c 1.68). Prefactor B can be calibrated using liquids of different known viscosities and surface tensions, such as silicon oils. Pk(u) is the PSD of the height of the free surface of mode k, and, for a medium in thermal equilibrium, is related to the imaginary part of the medium mechanical susceptibility through a uctuation dissipation relation:
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The results are gathered in the |G*| versus frequency diagram of Fig. 2, in which four regions are delimited. In each region, the result of the asymptotic development of eqn (2) is given, such that the rst order term: S(u) Af(G*,s,r,R)un (6)

Pk u

kB T Im ck u pu

(4)

where kBT is the thermal energy and ck(u) is the mechanical susceptibility for spatial mode k. The susceptibility ck(u) has been derived by several authors.18,19 It is obtained by solving the linearized NavierStokes equation in an innite medium, surface tension effects being included in the boundary conditions; the complete expression of susceptibility depends on the properties of the medium whose surface is probed, namely the viscoelastic complex modulus G*(u) G0 + iG00 , surface tension s, and density r, following: " s 3 1 u2 r 2 k 2 * s k G u 2 4 1 2 * ck u k G u ur u2 r 2 2 * k G u !2 # (5)

Where A is a constant xed by the set-up and laser beam properties, and f(G*,s,r,R) a function of the properties of the material and of beam radius. The expression of f(G*,s,r,R) is given in each region of the |G*| vs. frequency diagram of Fig. 2, together with the value of exponent n. Note that f(G*,s,r,R) is also a function of frequency through the frequency dependent complex modulus G*(u) G0 (u) + iG00 (u). The frontiers between the different regions of the diagram depend on the uid surface tension, but also on the size R of the laser beam spot at the free surface. In addition, the asymptotic terms in each region of the diagram as well depend on R. The beam radius dependency is the consequence of the larger contribution to the signal of surface modes such that kR $ 1. The effects probed in SFSR measurements can therefore be tuned by the beam size: changing R can change the shape and amplitude of the spectrum. Although in the present work size R is xed, it could easily be modied simply by changing the focal length of the lens or expanding the beam, thus giving latitude to tune the signal according to the medium probed.

In a previous work,10 we have shown that the signal computed from eqn (2) nicely describes the experimental data obtained with either Newtonian viscous uids, or viscoelastic solids. In the former case, the thermal surface waves are capillary waves ruled by surface tension effects, whereas in the latter case elastic effects dominate and the thermal waves are Rayleigh-like waves. In all cases, the expression for S(u) given by eqn (2) cannot be derived analytically, but can nevertheless be numerically integrated. We show in the following that S(u) can as well be asymptotically developed according to the values of the frequency and of the viscoelastic modulus of the probed medium, in order to evidence the role of the different parameters.

Results and discussion

|G*| vs. frequency diagram We have asymptotically developed eqn (2) giving the SFSR measured signal S(u), in the general case of a viscoelastic medium characterized by its complex modulus G*(u) G0 (u) + iG00 (u), surface tension s, and density r. Briey, eqn (2), expressed as a function of the different parameters using eqn (3) to (5), has been expended in powers of frequency u; the leading term has p then been determined according to the values of jG j G0 2 G002 and of frequency. The detailed calculations are presented in the Electronic Supplementary Information.
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Fig. 2 Viscoelastic modulus vs. frequency diagram. The modulus is p normalized by the quantity c1/2s/R, and the frequency by c3=4 s=rR2 in order to compare the behaviour of materials of different surface energy and density in the same diagram. The representation is a loglog one. Each of the four regions corresponds to a different leading term of the asymptotic development of the SFSR spectrum S(u), and its expression is given in each region. The slopes of the frontiers in loglogp representation are indicated. The variations of the modulus jG*j G0 2 G002 as a function of frequency are reported for the different materials studied: a cross-linked PDMS (dark grey line, as inferred from rheometric measurements); dodecane, for which |G*| uh (dotted line); the EHUT solution (light grey line, as inferred from SFSR measurements).

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In order to compare systems of different surface tensions, the diagram of Fig. 2 is shown as a loglog representation of normalized |G*| and frequency, the normalization includes both the radius and surface tension dependence. The frontiers of the diagram correspond to power law variations of the frequency dependent modulus. Hence, their slopes indicated in the log log representation are the exponents involved in the power laws. At low frequency and small |G*|, the surface uctuations are mainly driven by surface tension effects (regions I and II). Within those regions, the behaviour at lower frequency and larger modulus is ruled by dissipative effects (region I), whereas inertial effects dominate at larger frequency and smaller modulus (region II). In region III, a modulus |G*| larger than the ratio c1/2s/R is reached, the asymptotic term does not depend on surface tension but on both the dissipative and elastic parts of the complex modulus. In region IV, corresponding to high frequencies, S(u) rapidly decreases with increasing frequency, which results from the cut-off at large wavevectors described by the weighting function F. For given surface tension and density, the shape of the uctuation spectrum is therefore given by the frequency dependence of the complex modulus, which determines both the regions that are crossed and the amplitude of the measured signal. In the following section, we illustrate those results with two different materials: a low-viscosity liquid and a viscoelastic solid. Before, it must be noted that in all regions except for region II of the |G*| vs. u diagram, the asymptotic term giving the amplitude of S(u) depends on the imaginary part of the complex viscoelastic modulus. Since the real and imaginary parts of the viscoelastic modulus are not independent but are related through a KramersKronig relation,20 the viscoelastic modulus can in consequence be entirely determined from the SFSR uctuation measurement, which constitutes the main result of the present work.

Fluctuation spectra of a low viscosity liquid and a viscoelastic solid Fig. 3 display two examples of uctuation spectra measured at the free surfaces of two different materials: dodecane, a lowviscosity liquid, and, cross-linked PDMS, a viscoelastic solid. For a viscous liquid, the viscoelastic modulus is imaginary, and is given by its viscosity: G* iuh. For a low viscosity liquid such as dodecane, the variations of the complex modulus as a function of frequency cross regions II and IV of the |G*| vs. u diagram. In the spectrum displayed in Fig. 3a, the growing with frequency part corresponds to a region II behaviour, for which S (u) grows as u1/3; at larger frequencies, the decreasing part of the spectrum is dominated by the asymptotic term of region IV in which S(u) varies as G00 u5 f u4. The experimental data of Fig. 3a is in remarkable agreement with the numerical integration of eqn (2) shown by the grey line. We have used the values of surface tension, density and viscosity of dodecane at 25  C, found in the literature. The prefactor B involved in eqn (3) has been precisely determined with uids of known density, surface tension and viscosity (four silicon oils of different viscosities) that provide a calibration of the experiment. The spectrum of Fig. 3a
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Fig. 3 SFSR spectra for dodecane (a) and cross-linked PDMS (b). The peaks appearing in (b) are caused by parasitic electromagnetic radiation. The grey line in (a) corresponds to the computed signal using the values of surface tension and density at 25  C found in the literature, and with no adjustable parameters. The prefactor is the one determined with a set of silicon oils of different viscosities B 1.19. The grey line in (b) corresponds to the t of eqn (2) with the expression of the viscoelastic modulus given by eqn (7). The surface energy and plateau modulus are s 20 mN m1 and G0 1.9 105 Pa. The corresponding real and imaginary parts of the viscoelastic modulus are displayed in Fig. 4.

is therefore fully described without the inclusion of any adjustable parameter. The uctuation spectrum of Fig. 3b, measured at the free surface of a cross-linked PDMS, has a shape utterly different from the one of dodecane. The complex viscoelastic modulus of PDMS possesses both a real and an imaginary part, and its modulus |G*| is indeed much larger than the one of dodecane. The variations of the PDMS modulus therefore correspond to the upper region of the |G*| vs. u diagram: region III, for which |G*| > c1/2s/R. In that case, the propagation of surface thermal waves is driven by elastic effects: at the rst order, the spectrum does not depend on surface energy, but only on the real and imaginary parts of |G*| or, equivalently, to the imaginary part of the compliance. The grey line of Fig. 3b corresponds to a t
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performed to determine the elastic and loss moduli of the PDMS, we detail that point in the following section. Linear viscoelastic properties of cross linked PDMS from surface uctuation measurements In order to retrieve the viscoelastic complex modulus of crosslinked PDMS from the uctuation spectrum, we have developed a tting procedure that uses the theoretical expression for the signal given by eqn (2). In that expression, all parameters are known but the complex viscoelastic modulus G*. We describe the frequency variations of G* with a series of discrete relaxation times, such that:
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G G0

N X Hk iusk 1 iusk k1

(7)

Where the Hk are constants to be determined, and the relaxation times sk are xed such that their range encompasses the range of experimental time scales. They are chosen such that sk s1pk1 where p is a chosen integer. In practice, for PDMS, 14 relaxation times are needed to describe the uctuation spectrum, with 3 relaxation times per decade (s1 0.5 ms and p 3). Eqn (7) is well adapted to viscoelastic solids, for which the real part of G* is a non zero constant at vanishing frequency. Implicitly, the principle of determination of G* lies on the fact that the real and imaginary part of G*, on which the uctuation spectrum depends, are not independent functions but obey KramersKronig relations.21 The uctuation spectrum is tted according to eqn (2) (which is numerically integrated) and using eqn (7) as the expression for G*(u): the relaxation times are xed and the parameters Hk are the tting parameters, which are determined by a least squares method. The prefactor of expression (3) being unknown in the case of a solid, the value of the zero frequency elastic modulus G0 is needed to perform the t. It can easily be measured using conventional rheometry. For the PDMS sample considered herein, G0 1.9 105 Pa. The obtained t of S(u) for the cross-linked PDMS sample is reported in Fig. 3b; it accurately describes the experimental spectrum. Fig. 4 shows the variations of the elastic and loss moduli of the sample of PDMS as a function of frequency. The data deduced from the tting procedure, and corresponding to the real and imaginary parts of eqn (7), is displayed together with the rheometric data obtained on the same PDMS sample. There is a good agreement between the two sets of data, considering the uncertainty of rheometric measurements. In conclusion, we have measured the uctuations of the free surface of a soft polymeric solid whose rheological properties are known over a wide frequency range using rheometric data, and applying the timetemperature superposition principle. We have shown that, provided the zero elastic modulus is known, the elastic and loss moduli of the soft solid can be inferred from the surface uctuation data, in good agreement with the rheometric data. These results demonstrate that SFSR constitutes a new accurate technique to characterize frequency dependent rheological properties. In the following section, we show that SFSR is also well suited for the determination of the linear viscoelastic properties of a complex uid: a supramolecular polymer solution.
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Fig. 4 Frequency dependent elastic and loss moduli of the cross-linked PDMS determined by rheometry (squares for G0 and circles for G00 ) and by the tting procedure of the SFSR spectrum of Fig. 3b (solid line for G0 and dotted line for G00 ). For the sake of readability, only one error bar (corresponding to an uncertainty of 20%) is shown for the rheometric data.

Linear viscoelastic properties of supramolecular polymer solutions The supramolecular polymers we consider are long chains formed by hydrogen bonding between EHUT molecules. At low frequencies, the rheological behaviour of their solutions has been shown to be similar to the one of wormlike giant micelles, which are supramolecular polymers formed by surfactant molecules.26 The common property of all supramolecular polymers is that the formed chains can break and recombine. When the characteristic time sbreak associated with that process is much shorter than the reptation time of the chains, it has been shown that the relaxation is characterized by a single time, which is the geometric average of the breaking and reptation time.23 Thus, supramolecular polymer solutions exhibit a Maxwellian behaviour at low frequencies, i.e. generally smaller than 10 Hz.12,22 At larger frequencies, the rheological behaviour of EHUT solutions has never been characterized to date; as in polymer and wormlike micelle solutions, the relaxations are then expected to result from intrachain processes. The wormlike micelle chains have a large persistence length and have been shown, using micro-rheological techniques, to behave as semiexible polymers at high frequencies.24 At those timescales, relaxation results from RouseZimm modes, and by bending modes of Kuhn segments at even larger frequencies. The crossover between the two regimes corresponds to a change in the exponent of the power law describing the frequency dependence of G00 : G00 f u5/9 in the RouseZimm regime, whereas G00 f u3/4 in the regime dominated by the relaxation of Kuhn segments.24,25 The persistence length of the EHUT chains is also largeeven larger than the one of wormlike micelles26a semiexible polymer-like behaviour can therefore also be expected for EHUT. The uctuation spectrum of the free surface of the EHUT solution is shown in Fig. 5. Since the viscoelastic modulus is smaller than c1/2s/R z 1100 Pa, it is the lower part of the |G*| vs.
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u diagram that is described when the frequency varies; regions I, II and IV are therefore crossed. At low frequencies, corresponding to region I, the decreasing part of the spectrum reects the frequency dependence of G00 (u)/u; at high frequencies, the strong decrease of the signal is the one expected in region IV, with an asymptotic term varying as G00 /u5. The inuence on the uctuation spectrum of the elastic modulus is contained in second order terms, and does therefore not appear in the rst order terms given in the diagram. To determine the viscoelastic complex modulus of the EHUT solutions, we have used the same tting procedure as for crosslinked PDMS. The only difference is that, in order to describe the zero modulus at vanishing frequencies expected for a liquid, eqn (7) is used with G0 0. In practice, for the EHUT solution, 25 relaxation times are needed, with 3 relaxation times per decade (s1 0.05 ms and p 3). In order to compute the uctuation spectrum, the surface tension has been xed at the value of the one for the solvent, i.e. dodecane, since EHUT molecules are not expected to adsorb at the interface with air.27 Preliminary tting processes of the EHUT solution spectrum with varying surface tension have shown that the best tting results are obtained with the value for dodecane alone, which conrms the fact that EHUT molecules do not signicantly adsorb at the interface with air. Unlike cross-linked PDMS, the elastic modulus of the EHUT solution is expected to vanish at zero frequency, the retrieval of the rheological data from the uctuation spectrum does therefore not rst require the determination of the zero-frequency modulus. The prefactor of the weighting function given by eqn (3) is the one determined from the uctuation spectrum of dodecane (which is the same as the prefactor for a set of silicon oils), and, as pointed out in the preceding paragraph, the surface tension is the same as that of dodecane. Therefore, in the case of

the EHUT solution, the viscoelastic complex modulus can be entirely determined from the uctuation spectrum. The elastic and loss moduli resulting from the tting procedure are shown in Fig. 6a together with their rheometric measurements. In the common frequency range of rheometry and SFSR, the agreement between the data is very good, considering the uncertainty in rheometric measurements. At low frequencies, which cannot be reached with SFSR, the behaviour is

Fig. 5 SFSR spectrum of the EHUT solution. The grey line corresponds to the t of eqn (2) with the expression of the viscoelastic modulus given by eqn (7) with G0 0. The surface tension is the one of dodecane s 24.8 mN m1 and the prefactor B in eqn (3) is the same as for dodecane. The corresponding real and imaginary parts of the viscoelastic modulus are displayed in Fig. 6.

Fig. 6 (a) Frequency dependent elastic and loss moduli of the EHUT solution determined by rheometry (squares for G0 and circles for G00 ) and by the tting procedure of the SFSR spectrum of Fig. 5 (black line for G0 and grey line for G00 ). For the sake of readability, only one error bar (corresponding to an uncertainty of 20%) is shown for the rheometric data. (b) High frequency variations of the loss modulus without the solvent contribution, G00 uhs as determined by the tting procedure of the SFSR spectrum (open circles). Between about 100 Hz and 1.3 kHz, G00 uhs grows as a power law with an exponent 5/9 (grey line), whereas at frequencies larger than 1.3 kHz, a power law with an exponent 3/4 (black line) better describes the variations. The crossover frequency between the two behaviours is up z 1.3 kHz.

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Maxwellian, as detailed in other works for EHUT solutions,12 with a relaxation time close to 150 s. In the range encompassed by the SFSR measurements, another Maxwell-like behaviour is exhibited, with a relaxation time close to 0.2 s. The elastic and loss moduli further increase with frequency, following power-law behaviours. Fig. 6b shows the variations of the loss modulus without the solvent contribution, i.e. G00 uhs, in the frequency range 100104 Hz. A power law with an exponent 5/9 well describes the variations of G00 uhs from about 100 Hz to 1.3 kHz. Above the latter value, the increase of G00 uhs with frequency is better described with an exponent 3/4. Such high frequency behaviour is similar to that of wormlike micelle solutions; it has been interpreted as a crossover between Rouse Zimm relaxation modes of the supramolecular chains, to the bending relaxation modes of Kuhn segments.24 The crossover is expected to occur at a frequency that depends on the persistence length of the chains: up z kT/8hsl3. For the EHUT solution, the p persistence length inferred from the crossover frequency is close to 40 nm, which is smaller the value found in the literature (about 100 nm),26 but is of the same order of magnitude. A more detailed study of the rheological behaviour of EHUT solutions will be the object of a forthcoming study since it is out of the scope of the present work. In conclusion, we have shown that the rheological properties of a supramolecular polymer solution can be characterized over a wide frequency range using SFSR measurements. Provided surface tension is known, both elastic and loss moduli can be fully determined from a single uctuation spectrum. The SFSR technique is therefore very promising for the successful characterization of the high frequency linear viscoelasticity of complex uids.

inherent to those measurements. The results we present in this paper indicate that SFSR should provide successful characterization of complex uid interfaces in a wide frequency range.

Acknowledgements
We thank L. Bouteiller for providing the EHUT and for fruitful discussions, and A. Papon for her help in the rheometric measurements of PDMS. L.T. gratefully acknowledges the support of CNRS for her full time research years. This work is part of the thesis of B.P., funded by French Research Ministry.

References
1 R. G. Larson, The structure and rheology of complex uids, Oxford University Press, New York, 1999. 2 D. T. N. Chen, Q. Wen, P. A. Janmey, J. C. Crocker and A. G. Yodh, Annu. Rev. Condens. Matter Phys., 2010, 1, 301322. 3 F. C. MacKintosh and C. F. Schmidt, Curr. Opin. Colloid Interface Sci., 1999, 4, 300307. 4 T. A. Waigh, Rep. Prog. Phys., 2005, 68, 685742. 5 F. Gittes, B. Schnurr, P. D. Olmsted, F. C. MacKintosh and C. F. Schmidt, Phys. Rev. Lett., 1997, 79, 32863289. 6 T. G. Mason and D. A. Weitz, Phys. Rev. Lett., 1995, 74, 12501253. 7 E. K. Hobbie, S. Lin-Gibson and S. Kumar, Phys. Rev. Lett., 2008, 100, 076001. 8 Q. Lu and M. J. Solomon, Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top., 2002, 66, 061504. 9 I. Y. Wong, M. L. Gardel, D. R. Reichman, E. R. Weeks, M. T. Valentine, A. R. Bausch and D. A. Weitz, Phys. Rev. Lett., 2004, 92, 178101. 10 A. Tay, C. Thibierge, D. Fournier, C. Fretigny, F. Lequeux, C. Monteux, J. P. Roger and L. Talini, Rev. Sci. Instrum., 2008, 79, 103107. 11 F. Lortie, S. Boileau, L. Bouteiller, C. Chassenieux, B. Deme, G. Ducouret, M. Jalabert, F. Laupretre and P. Terech, Langmuir, 2002, 18, 72187222. 12 G. Ducouret, C. Chassenieux, S. Martins, F. Lequeux and L. Bouteiller, J. Colloid Interface Sci., 2007, 310, 624629. 13 J. D. Ferry, Viscoelastic properties of polymers, Wiley, New York, 1980. 14 D. Langevin, Light Scattering by Liquid Surfaces and Complementary Techniques, Marcel Dekker, New York, 1992. 15 C. H. Sohl, K. Miyano and J. B. Keterson, Rev. Sci. Instrum., 1978, 49, 1464. 16 F. Raynal, S. Kumar and S. Fauve, Eur. Phys. J. B, 1999, 9, 175178. 17 C. Pichard and L. Davoust, Rheol. Acta, 2006, 45, 497504. 18 M. A. Bouchiat and J. Meunier, J. Phys., 1971, 32, 561571. 19 J. L. Harden, H. Pleiner and P. A. Pincus, J. Chem. Phys., 1991, 94, 52085221. 20 S. R. de Groot and P. Masur, Non-equilibrium thermodynamics, Dover, New York, 1984. 21 B. N. J. Persson, Eur. Phys. J. E, 2010, 33, 327333. 22 M. E. Cates and S. M. Fielding, Adv. Phys., 2006, 55, 799879. 23 M. E. Cates, Macromolecules, 1987, 20, 22892296. 24 N. Willenbacher, C. Oelschlaeger, M. Schopferer, P. Fischer, F. Cardinaux and F. Scheffold, Phys. Rev. Lett., 2007, 99, 068302. 25 D. C. Morse, Macromolecules, 1998, 31, 70447067. 26 J. van der Gucht, N. A. M. Besseling, W. Knoben, L. Bouteiller and M. A. C. Stuart, Phys. Rev. E, 2003, 67, 051106. 27 L. Bouteiller, private communication. 28 P. Cicuta and I. Hopkinson, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2004, 233, 97107.

Conclusion
In conclusion, we have developed a new optical method to measure the linear viscoelastic properties of materialseither solid or liquidin a wide frequency range. The SFSR technique is based on the measurement of the surface uctuations of the materials, it is therefore non invasive and of peculiar interest for soft viscoelastic media, such as complex uids that cannot be fully characterized with conventional rheometry. The material properties are probed at a mesoscopic spatial scale, which is set by the laser beam size, typically a few tens of microns. We have demonstrated herein that, for materials that do not exhibit surface viscoelasticity, the frequency dependent bulk properties could be inferred from the uctuation spectrum, in very good agreement with rheometric measurements. Indeed, for systems such as monolayers that possess a surface viscoelasticity, the SFSR signal is expected to result from both surface and volume properties; the characterization of surface properties only therefore requires separating the different contributions to the SFSR signal. This has been successfully done in the past with surface light scattering measurements28 but with the limitations

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This journal is The Royal Society of Chemistry 2011