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FORTH, Institute of Electronic Structure & Laser, Heraklion 70013, Crete, Greece
University of Crete, Department of Materials Science & Technology, Heraklion 71003, Crete, Greece
Matire Molle et Chimie (UMR 7167, ESPCI-CNRS), ESPCI ParisTech, 10 Rue Vauquelin, 75005 Paris, France
a r t i c l e
i n f o
Article history:
Received 24 August 2014
Received in revised form 26 September 2014
Accepted 29 September 2014
Available online 7 October 2014
Keywords:
Soft colloids
Viscoelasticity
Microgels
Star polymers
Glass/Jamming
Depletion
Particle elasticity
Viscosity
Yield stress/strain
Flow curves
a b s t r a c t
In the last two decades, advances in synthetic, experimental and modeling/simulation methodologies have
considerably enhanced our understanding of colloidal suspension rheology and put the eld at the forefront of
soft matter research. Recent accomplishments include the ability to tailor the ow of colloidal materials via
controlled changes of particle microstructure and interactions. Whereas hard sphere suspensions have been
the most widely studied colloidal system, there is no richer type of particles than soft colloids in this respect.
Yet, despite the remarkable progress in the eld, many outstanding challenges remain in our quest to link particle
microstructure to macroscopic properties and eventually design appropriate soft composites. Addressing
them will provide the route towards novel responsive systems with hierarchical structures and multiple
functionalities. Here we discuss the key structural and rheological parameters which determine the tunable
rheology of dense soft deformable colloids. We restrict our discussion to non-crystallizing suspensions of
spherical particles without electrostatic or enthalpic interactions.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
1.1. Classication of soft colloids
Looking at the rich landscape of soft matter systems it is a prime
challenge to identify and classify the different types of nanoparticles
which have been investigated in reasonable depth and at the same
time are representatives of basic features in terms of phase behavior
and macroscopic properties. A reasonably comprehensive, albeit nonexhaustive list of soft colloids includes emulsions and nanoemulsions,
surfactant onions and liposomes, microgels, grafted coreshell particles,
block copolymer micelles, dendrimers, and star polymers [18]. Softness can be appreciated from different perspectives: particle elasticity,
diversity of soft interactions, and particle volume fraction.
1.2. Particle elasticity
The importance of the elasticity of Brownian object can be quantied
by the non-dimensional parameter = F/kT which represents the
ratio of the elastic free energy, F, to the thermal energy kT [911]. Polymer coils have a free energy of entropic origin with F kT indicating
that 1; they are the most deformable objects available. On the
E-mail addresses: dvlasso@iesl.forth.gr (D. Vlassopoulos), michel.cloitre@espci.fr
(M. Cloitre).
http://dx.doi.org/10.1016/j.cocis.2014.09.007
1359-0294/ 2014 Elsevier Ltd. All rights reserved.
other hand, spherical elastic particles with modulus E and radius R are
characterized by F = ER3 and = ER3/kT. Thus, innitely rigid hard
spheres correspond to the limit . Besides hard spheres, colloidal
star polymers and microgels are archetypical representatives of two
important classes of soft particles. Star polymers are made of a large
number of arms, f, each with the degree of polymerization Na,
which are attached to a central core. Following the DaoudCotton
model [12], each arm can be viewed as a succession of blobs whose volume V(r) r3f3/2 increases with distance r from the core. Due to the topological stretching of the arms, the elastic modulus at distance r scales
as: E kT/V(r). At the periphery of the star, we have EkTR-3f 3/2 so that
f 3/2. For stars with a few hundreds of arms, is of the order of a few
thousands. Microgel particles are crosslinked polymeric networks swollen by solvent [4,13,14]. Their modulus depends on many parameters
such as the crosslink density, the solvent quality, the presence of ions,
and the network architecture. For neutral microgels, a reasonable estimate is E kT/V, where V NxV0 (Nx: number of statistical units between crosslinks; V0: volume of a statistical unit). For submicron
microgels (typically, R = 100 nm; V0 = 1 nm3; Nx = 100), we estimate
= 104. Nanoemulsion and emulsion droplets are soft colloidal objects
used in many applications. Here the elastic energy is associated with the
surface energy of the interface (typically oil/water) which resists deformation [15]: F = R2 (with the interfacial tension). For R = 100 nm
and = 103 N/m, we estimate 106. For completeness, let us briey
mention multilamellar vesicles which exhibit strong analogies with
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emulsion droplets, the effective surface elasticity resulting from a combination of the bending and compressive elasticity of the smectic layers
constituting the particles [4,16]. In the context of this discussion, recent
efforts to characterize the elasticity of individual particles using various
techniques like micropipette aspiration, AFM, and microuidic ow appear very promising [1723].
Fig. 1 summarizes the classication of soft colloids based on the
above approach. Clearly, colloidal particles span the softness parameter
space from ultrasoft polymer coils and star polymers to quasi-hard
spheres, indicating that softness can be tuned at will during synthesis
or preparation to meet the requirements of various applications. Naturally, our classication is somewhat simplied and does not account
for the variations in parameters like star functionality, crosslink density,
and interfacial tension (always in the absence of charges or enthalpic effects). For example, star polymers are the simplest representatives of a
wider class of particles with heterogeneous internal microstructure. It
includes dendrimers [8,24,25], block copolymer micelles resulting
from the dissolution of diblock or multiblock copolymers in a selective
solvent [2633], and polymer-grafted (or polymer-adsorbed) particles
[11,3436]. The latter nd many applications as they provide an exquisite way to stabilize colloidal particles and tailor their rheology. Further
complications to our classication arise from more complex structures,
such as for example coreshell microgels consisting of a solid core covered with a network-like shell [3740] and block copolymer micelles
with a multi-compartmented coreshell microstructure [29,32]. Despite
these issues, the classication of Fig. 1 offers a comprehensive description of the important features governing the behavior of soft colloids.
A useful, albeit rough parameter for coreshell particle's softness is
the fraction of the shell layer [34]: s = L/(L + rc), where L is its thickness
and rc is the core radius; for hard spheres, stars (for f = 100 arms and
Na = 100 statistical units per arm) and polymers, s is about 0, 0.95
and 1, respectively. In all these systems it is possible to de-swell the
outer soft layer by adjusting the physicochemical conditions (pH, temperature, solvent quality, addition of small non-adsorbing polymers)
so that the system switches from soft-like to hard-like behavior.
1.3. Particle interactions
The softness of particles is linked to the softness of interactions
which can be characterized by the form of the repulsive pair potential
between two particles. For instance, star polymers or, equivalently, particles covered with long end-grafted polymer chains (such as block
copolymer micelles) are characterized by coarse-grained ultrasoft potentials which exhibit long-ranged Yukawa-like repulsion at large
Fig. 1. Cartoons of different nanoparticles with the arrow pointing to the direction of enhanced elasticity and transition from soft to hard repulsive pair interaction potential: polymeric
coil, star polymer, microgel, emulsion, and hard sphere. Dashed and dotted lines illustrate the variability of the repulsive potentials upon changes in molecular characteristics, which affect
particle elasticity. Particles with grafted or adsorbed polymers (not shown here) are typically positioned between stars and emulsions (see text).
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Fig. 2. Schematic one-dimensional state diagrams of nearly-monodisperse athermal soft colloidal suspensions, as function of their effective volume fraction (see Section 2). The numbers
are values for volume fractions of hard spheres; values above 0.74 are relevant only for soft systems. From bottom to top the diagrams of a): hard spheres, b): microgels, c): star polymers
and d): polymeric coils are shown. Letters refer to different regions: uid (F, the blue-shaded regions), crystal (C, at c = 0.545 for hard spheres), coexistence (F + C, above volume fraction
0.494 for hard spheres), glass (G, at g = 0.58 for hard spheres), and jammed (J). RCP and HCP are the random close packing and hexagonal close packing volume fractions, which for hard
spheres are determined to be 0.64 and 0.74, respectively. The solid black vertical lines represent established transitions (even if occurring at different volume fractions for different
systems) whereas red dashed lines represent transitions whose universality is still debatable. The values of the volume fraction in the horizontal scale are indicative and do not respect
the actual scale.
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Fig. 3. Schematic state diagrams of (from top to bottom): a) linear polymerhard sphere mixture at Rpolymer/RHS b 0.2; b) linear polymercolloidal star mixture at Rpolymer/Rstar b 0.5;
c) binary hard sphere mixture at Rsmall/Rlarge b 0.2; d) binary star mixture at Rsmall/Rlarge = 0.3; and e) hard spherestar mixture at RHS/Rstar = 0.25. Notation: F = uid, PS = phase
separation, RG = repulsive glass, AG = attractive glass, SG = single glass, DG = double glass, C = crystal, F + C = uidcrystal coexistence, APS = arrested phase separation,
AsG = asymmetric glass.
(e.g., density of crosslinks), the size ratio and the potentially changing
solvent quality for the polymer. Furthermore, the role of depletion in
the aggregation and phase separation of food protein systems, which
are also dominated by softness and exhibit qualitatively similar features
to those reported here, was recently reviewed [140].
Interesting phenomena also occur in the melt, i.e. in the absence of
solvent background, where grafted nanoparticles or star polymers can
be thought as solvent-free colloids [141144], with signicance for
nanocomposite systems. Although we do not review the eld of nanocomposites here, it is worth mentioning that recent work suggested
that adding linear homopolymers to polymer-grafted nanoparticles
originally in the uid state can result in the formation of anisotropic domains comprising trapped particles [145147]. This brings analogies to
the asymmetric caging of binary star mixtures [148] which will be
discussed below. A further worthy example is the systematic investigations of grafted particles in polymer melts (say polystyrene-grafted
polyorganosiloxane in linear polystyrene matrices) where by increasing
the size ratio between the radius of gyration of the polymer and the
particle radius it is possible to reduce the strength of depletion and promote dispersion of the particles, with important consequences on their
dynamic response [144,149153]. More recently, blends of crosslinked
PMMA microgels with linear PMMA of much smaller size were investigated [154]. In the case of slightly crosslinked microgels the linear
chains penetrate and swell the microgels and homogeneous dispersions
are obtained. However, highly crosslinked microgels behave like impenetrable hard spheres and aggregate due to the depletion effects induced
by linear chains.
3.2. Binary colloidal mixtures
The consequences of strong entropic effects discussed in Section 3.1
can be extended to more complex, yet interesting from the standpoint
of applications, systems, by replacing the linear polymer by another colloidal particle. For instance the morphology of binary asymmetric
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mixtures of hard spheres was explored with emphasis given to the existence of freezing transitions and the formation of superlattice structures, driven by the maximization of entropy as the system adopts its
most efcient packing arrangement. Fig. 3c shows that, for a give size
ratio and depending on the relative volume fraction, hard sphere mixtures exhibit both crystalline (C) and glassy regions (SG, DG). Single
glasses (SG) and double glass (DG) form when either the small (here)
particles or both small and large particles become kinetically trapped
in amorphous structures [155,156]. Mixtures of small star polymers of
low-functionality (up to 32) and large hard colloids were found to
phase separate for size ratios not exceeding 0.5 and colloid volume fractions below 0.5 [157]. Microgel particles were used as depletants (instead of polymers) to hard spheres and it was found that gels were
formed more easily and eventually demixed [158].
A much richer behavior is observed and actually predicted in star
mixtures (with functionalities exceeding 64), placing them in the soft
colloidal domain [71,159], where the softness leads to the formation
of different types of arrested states: not only those with one or both particle populations trapped as in hard sphere mixtures, but also a novel
asymmetric glass (AsG) where the effective large particle cages become
anisotropic due to the osmotic pressure of the small particles (Fig. 3d)
[148,160162]. Recently, mixtures involving block copolymer micelles
with frozen and living cores and short arms were studied, and it was
found that a balance between crystallization and vitrication results
from an optimum adjustment of the number of arms [163].
Combining soft and hard interactions opens another route for exploring and tuning macroscopic properties. A mixture of small hard
spheres and large star polymers represents such a situation, where repulsive pair potentials which have different ranges are coupled
[164166]. As depicted schematically in Fig. 3e, at low polymer star volume fractions the colloidal liquid phase separates upon adding hard
spheres. At higher volume fractions in the star glass regime, there is a
small domain where the glass melts due to depletion and further addition of hard spheres results in APS. Rheology was again used in order to
identify the different transitions and the strength of the moduli for different mixture compositions, whereas the gradual nature of the yielding
process under shear was conrmed [166].
This plethora of morphologies has important consequences on the
macroscopic properties of mixtures. The various stable and metastable
states discussed above in the context of colloidal mixtures possess different rheological properties so that both linear and nonlinear viscoelastic characterizations can very sensitively diagnose their differences. At
the same time this richness of behavior allows tailoring the ow of
soft colloidal composites at wish [4,5,167].
4. Linear viscoelasticity, diffusion and zero-shear viscosity
4.1. Viscoelastic relaxation spectrum and plateau modulus
The viscoelastic properties of soft particle suspensions are exquisitely reected in the dependence of the storage and loss moduli on frequency. As the volume fraction increases, the rheological response
alters from viscoelastic liquid behavior where terminal regime is observed over the experimental frequency window, to solid-like behavior
where the storage modulus dominates. The evolution of the viscoelastic
spectra leading to solidication has been studied in detail for soft particles
in the colloidal regime like emulsions and nanoemulsions [83,168,169],
coreshell particles [3739,90,170172], and microgel particles [40,92,
173175], which have softness parameters N 104. The approach of the
glass transition is signaled by the superposition of G and G at higher frequencies before a plateau in G and a shallow minimum in G appears. The
onset of terminal relaxation shifts to lower frequencies as the volume
fraction increases up to the point where it falls outside the experimental
frequency window. These viscoelastic properties can be qualitatively
understood in the framework of the cage model where a colloidal
particle is topologically constrained by its neighbors in a hypothetical
cage [9,79,80]. It moves locally within the cage (beta relaxation) but
will escape only if the environment of the cage can renew at long
times (alpha relaxation). The minimum of G expresses the transition
from in-cage motion to out-of-cage motion, and it can be also probed
in creep recovery experiments [176,177].
The shape of the viscoelastic spectra remains qualitatively the same
as the suspensions cross over the jamming transition although there are
some important quantitative differences that will be discussed later on
in this section. The solidication scenario is not well-known yet for
softer particles with 10104 although it is denitely more gradual
[86]. Inside the solid state, the viscoelastic spectra of star-like particle
suspensions also exhibit a plateau in G and a minimum in G but new
features are observed at low frequencies where the relaxation of the
interdigitated arms apparently contributes to an additional relaxation
process [81]. Before alpha relaxation is activated, the arms can disengage from their neighbors and deform the cage. As a result, star-like
colloidal glasses with many dangling arms often have an experimentally
accessible alpha relaxation, marking a clear departure for other systems
[178,179]. This may not necessarily be the case for colloidal block
copolymer micelles which have a larger core and smaller dangling
ends than stars and usually exhibit slightly larger particle elasticity
[180182].
In view of the huge diversity of soft particles in terms of effective
elasticity and architecture, a real challenge is to draw a one to one
comparison of their viscoelastic properties. This is a formidable task,
which in general seems inaccessible, because of the difculty to determine the glass and jamming transitions (Section 2) and the actual volume fraction of the suspensions (Section 1.4). Even for a given class of
particles such as star polymers, manifestations of softness like osmotic
shrinking and interdigitation depend on functionality, and there are
no systematic experimental studies [81,183]. An additional difculty
comes from the fact that, unlike for polymers, mean-eld theories of
colloids are in general not possible since the coordination number
does not exceed a value of 12. The rationalization of experimental results often relies on semi-phenomenological approaches or simulations.
However, recent progress in the eld allows us to identify some important trends.
Mode Coupling Theory (MCT) [184] has proven highly successful in
predicting the linear rheology of hard colloids on approaching the glass
transition by accounting for density correlations from the static structure factor and then calculating the viscoelastic moduli [185]. It also
works well for soft glassy colloids with the same t parameters [84,
186188]. Recent extensions of MCT [189191] have been developed
to predict the frequency-dependent moduli of coreshell particles and
star polymer suspensions well-within the glassy regime, which is beyond the expected range of validity (up to and at the glass transition)
of the initial theory [39,192]. However, MCT is unable to capture the
low frequency relaxation which occurs in addition to alpha relaxation
as already mentioned. For the sake of comparison with predictions,
the experimental viscoelastic moduli have to be scaled with the entropic elasticity of individual particles, kT/R3, while the angular frequency
is converted into the Peclet number: Pe = (6R3)/kT. These scaling
forms are expected to be valid in the thermal glass regime g b b J
due to the entropic nature of the suspension dynamics [134]. Note
that a successful alternative, albeit similar in spirit, statistical mechanical theory exists, which describes glassy dynamics based on a nonequilibrium free energy that incorporates local cage correlations and
activated barrier hopping processes [193196].
The properties of jammed suspensions exhibit several quantitative
differences from those of entropic glasses because of the presence of
repulsive elastic interactions which exceed thermal forces. The plateau
modulus scales with the contact modulus E* of the particles (E* = E/
(1 2); E and are the Young modulus and the Poisson ratio, respectively) and exhibits a rapid linear increase with the distance to the jamming transition: G0/E* ( J). This has been observed for
concentrated emulsions, microgel suspensions and even star polymer
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to emphasize that the transition to a weaker viscosity at higher fractions, and eventually to divergence, also signals osmotic de-swelling
or shrinking. This phenomenon, which can also be triggered externally
by temperature of ionic strength variation, fully reects particle softness
and reduces the actual volume fraction and stiffness as discussed above
[54,61,120,209,210]. For polyelectrolyte particles it has been shown that
the divergence of the viscosity exhibits little departure from the hard
sphere case once the volume fraction is appropriately corrected for
particle shrinkage [53].
The type of representation shown in Fig. 4 emphasizes the fact that
softness affects only the high volume fraction regime, where particle interactions come into play. At low volume fractions reduced viscosities
for all particles collapse to the EinsteinSutherland and Batchelor curves
[57]. But on increasing volume fraction the data depart according to
their softness. Recent extensive mesoscale simulation studies, accounting
for the effects of hydrodynamics as well, successfully predict the volume
fraction dependent viscosity of linear and star polymers shown in Fig. 4
[211213]. Several empirical models have been proposed to describe
the viscosity departure and divergence at the glass transition. The
KriegerDougherty and Quemada models are very successful for a wide
range of systems [11,203]. The approach to glass transition is a subtle
issue because in reality there do not exist true hard sphere experimental
systems due to stabilization needs [214]. In this case even models used in
molecular glasses were invoked to capture the steep viscosity increase
[215]. To further characterize the variations of the viscosity before solidication, the concept of fragility was used [47,89]. It was proposed to build
Angell-type fragility plots by dening a glass transition volume fraction
and plotting the normalized viscosity of the suspension against its distance from this glass transition [89]. The outcome of this analysis is that
softer colloids make stronger glasses and indeed, a closer look at the
trend of the data in Fig. 4 conrms this conclusion and suggests that polymer coils are potentially the strongest glasses.
4.3. Aging
A comment on aging is in order to close this section. Disordered
crowded materials, such as glassy and jammed colloids exhibit a slow
time evolution of their dynamic and structural properties, also termed
aging. There are several features of aging which are shared by many colloidal glasses, such as a certain time regime characterized by a logarithmic increase of storage modulus and slowing-down of dynamics. On the
other hand, the dependence or not of macroscopic properties on the age
and the exact form of the respective scaling, as well as the presence of
different aging regimes for different systems, represent distinct signatures of softness [134,179,199,216,217]. We shall not discuss aging further, as this has been the subject of other reviews [218,219]. However
we emphasize that irrespectively of its study, aging must be properly
accounted for when analyzing properties of glassy and jammed materials. In this respect, an appropriate preparation protocol is necessary
to place the material in a reproducible state. It consists of shearmelting the glass or jammed state in analogy to thermal annealing of
molecular or polymeric glasses, and following the dynamics over time
until a quasi-steady state is reached. This is not necessary a trivial task
since internal stresses may affect the dynamics, hence proper denition
of a protocol and careful implementation are important for obtaining
consistent data [179,220222]. The properties discussed above such as
the volume fraction dependence of the moduli or the frequency spectrum of viscoelastic moduli, all refer to aged systems.
5. Nonlinear rheological phenomena
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Fig. 5. Master ow curves representing normalized shear stress vs. normalized shear rate
relationship for microgels (, ) and star solutions (, ; ) at high effective volume
fractions eff, with f: star functionality and Ma: arm molar mass. The dotted line is a t of
the data for microgels to the HerschelBulkley model [48]. The dashed line is a t of the
data for star polymers with f = 390 and Ma = 24 kg/mol to the modied HerschelBulkley
model (see text) [86]. The data for star polymers with f = 122 and Ma = 72 kg/mol collapse onto the data for the other star polymers and the microgels at high shear rates;
the plateau observed at low-shear rates is indicative of shear-banding (continuous straight
line) [178].
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