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Current Opinion in Colloid & Interface Science 19 (2014) 561574

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Current Opinion in Colloid & Interface Science


journal homepage: www.elsevier.com/locate/cocis

Tunable rheology of dense soft deformable colloids


Dimitris Vlassopoulos a,b, Michel Cloitre c
a
b
c

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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D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

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

center-to-center distances and logarithmic repulsion at short distances


(Fig. 1) [41]. The amplitude of the potential and its range of repulsion
depend on the number of arms. The logarithmic repulsion accounts
for the microscopic interactions which develop when the arms come
into contact, interpenetrate, and deform at short distances. The number
of arms, f, is the unique control parameter for tuning the starstar interaction from hard-sphere-like to polymer-like (Fig. 1), the potential scaling with f 3/2 as the normalized elastic free energy [41]. This potential
has been very successful in describing the structure of stars and starlike micelles, including the crystallization and glass transition, as conrmed experimentally [5,27,30,4144]. On the other hand, particles
without dangling chains like microgels or emulsion droplets can be
thought of as effective hard spheres up to the point of contact, and as
elastically deformable spheres at shorter distances. When the particles
come into contact they develop facets through which they exert normal
repulsive forces which are well modeled using Hertz theory [4547].
The resulting potential is accurate up to particle deformation of about
15% but extensions have been proposed to account for the large particle
overlaps that take place under ow [48]. These potentials successfully
apply to dense microgel suspensions or concentrated emulsions
[4550]. Hence, the key features of soft interactions that distinguish
them from their hard-sphere counterparts are their wide-ranging and
the less-steep potential at contact and beyond, which explain the
tunability of soft interactions.
1.4. Particle volume fraction
In relation to particle elasticity, a consequence of softness is the ability of the particles to deform/compress in contrast to hard spheres.
Emulsion droplets adapt their shape to steric constraints by forming
facets at contact at constant volume. Hairy particles (like star polymers,
block copolymer micelles or grafted particles) and microgels can adjust
both their shape and volume in response to external stimuli like pressure, ow, pH, and temperature, which makes their properties tunable
[4]. Moreover, the hairy structure of star-like particles allows for interdigitation in addition to deformability. The above features profoundly
affect the denition of the volume fraction of soft particles and their
behavior at high concentrations.
The volume fraction of a hard sphere colloidal suspension is usually
determined in reference to the onset of crystallization at c = 0.494 or
the maximum packing fraction at HCP = 0.74. Hard particles subjected
to a centrifugal force eld will eventually reach the latter limit so that
desired volume fractions can be subsequently prepared by dilution
[10,51,52]. This procedure does not apply to soft deformable particles

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).

D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

which de-swell osmotically at large volume fraction [5356]. The


volume fraction of concentrated soft particle suspensions thus remains
an ambiguous quantity [52]. Generally, the effective volume fraction
based on the single particle hydrodynamic size is agreed upon as a universal parameter, albeit different from the actual volume fraction [51,
52,57,58]. The determination of the latter is extremely challenging
and, apart from a few studies for microgels and star polymers, few results are available [53,56,59]. The effective volume fraction has been
shown to work well in terms of scaling the properties (such as zeroshear viscosity or self-diffusion) for different soft particles over a
range of sizes and concentrations [57,58,60,61]. Hereafter we shall call
it volume fraction unless otherwise specied.

2. State diagram: crystallization, vitrication and jamming


Particle interactions are reected in the form of the potential and
eventually in the phase behavior. Since some phases are metastable,
we prefer to call the respective morphological diagrams of athermal
(i.e., possessing only entropic interactions) soft colloids as state diagrams. Before studying the state diagrams of soft colloids, it is useful
to revisit the reference case of hard spheres. Fig. 2a shows the behavior
of monodisperse and non-interacting colloidal spheres suspended in
Newtonian uids [62,63]. With increasing volume fraction there is a
transition from the disordered uid phase to a crystal phase (at volume
fraction c) through an intermediate uidcrystal coexistence regime
where crystals are in equilibrium with the uid phase. Above volume
fraction g, the crystalline order is lost and a disordered amorphous
glass, where the positions of the particles are uncorrelated, appears instead. The upper limit of the glassy region is the maximum fraction of
randomly packed spheres, J, where the particles are forced into contact
in a jammed state [64]. Above J, samples must have domains of crystalline structure or be entirely crystallized. Polydispersity inuences the
state diagram through the values of the glass and jamming transition,
which are larger for polydisperse samples, and more notably suppresses
crystallization [65].

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The state diagram of non-interacting soft microgels is shown in


Fig. 2b for comparison. It exhibits apparent similarities with that of
hard-sphere suspensions: microgel suspensions undergo the same
sequence of transitions from uid to crystal to amorphous solid with
increasing volume fraction. However several major quantitative differences signal the role of softness. First, particles can be compressed
well above the jamming transition where they come into contact,
because they can accommodate the increased osmotic pressure by
adjusting their volume and shape as discussed in Section 1.4 [4]. Secondly, crystallization and melting seem to occur at higher volume fractions and exhibit a narrower phase coexistence region compared to
hard sphere suspensions [66]. Sometimes, it may happen that crystallization is suppressed, whereas the glass and jamming transition are
shifted to higher volume fractions [58]. Finally, the presence of soft interactions combined with the development of appropriate annealing
protocols (rapid heating and subsequent cooling after certain rest
time) [67] and variations in synthesis (for instance changing the degree
of crosslinking) [13] offers unique possibilities to manipulate the morphology of soft microgel suspensions to get ordered crystalline phases
over a wide range of volume fractions. Note that the state diagram in
Fig. 2b is based on the behavior of microgel suspensions which are not
purely athermal: poly(methylmethacrylate) (PMMA) spheres swollen
in benzyl alcohol [68] and thermosensitive poly(N-isopropylacrylamide)
(PNIPAm) particles in water [39,50,66]. The state diagrams of ionic
microgels with varying softness qualitatively also conform to that
in Fig. 2b [69], which supports the generality of the trends we have
identied so far.
The softer star-like systems are characterized by a large uid region,
practically up to the overlap concentration (c*), a very small crystal region which may be completely masked by the glass, and a relatively
large glass-jamming region (Fig. 2c). The suppression of crystallization
in hairy suspensions is related to the fact that the dangling chains interpenetrate above c* and uctuate beyond the limit allowed by the
Lindeman criterion [5,35,70,71]. At sufciently long times, star glasses
eventually crystallize (in fact, this has been reported for hard spheres
as well) [43,72,73]. It appears that a large core contributes to damping

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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D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

the uctuations, hence promoting crystallization. This explain in part


why in general block copolymer micelles and densely grafted hard
nanoparticles can crystallize easily whereas star polymers cannot [5,
30,74,75]. When the dangling chains are short, the dynamical nature
of the micelles allows for appropriate adjustment of the number of
arms to promote crystallization [76,77].
From the above discussion we can draw some general conclusions
about the impact of softness on the state diagram of colloidal suspensions. A general and important trend is that the uid phase tends to expand when the softness increases. This observation can be connected to
the behavior of polymer coil solutions which remain uid throughout
the whole range of volume fractions (Fig. 2d). For monodisperse systems, the same sequence of phases and states leading from uid phase
to glassy states through crystalline phases is qualitatively observed.
However, the actual values of the effective volume fraction marking
the transitions depend on softness. External stimuli, such as shear [78]
or thermal annealing [43,72,73], can promote local rearrangement and
even lead to crystallization.
Polydispersity systematically inhibits crystallization so that in polydisperse soft colloids we are left with the glassy and jammed regimes
only, which are often, but not always, the states of principal interest
for rheology. The glass transition can be described to a rst approach
by the cage model originally proposed for hard spheres where colloidal
particles are topologically constrained by their neighbors in virtual
cages [9,62,79,80]. In the jammed state, soft particles are still arranged
in a disordered amorphous way but they form polyhedral facets at contact [4]. Interpenetration of star-like particles introduces an additional
complexity, which has not been investigated in detail yet [81,82].
Today there is growing evidence suggesting that solidication of polydisperse soft particle suspensions does not obey a universal description,
and different scenarios have been proposed as particle softness is varied.
Emulsions, which are relatively rigid particles ( 106), exhibit a glass
transition at g = 0.58 and a jamming transition around J = 0.64
[8385]. Star polymer solutions ( 103) exhibit a liquid to solid transition at a relatively well-dened concentration, but the glass or
jammed nature of the solid phase is unclear [86]. These experimental
observations qualitatively conform to the predictions of a recent
model which combines the contributions of Brownian motion and harmonic interactions [87,88]. Observations for microgels are somewhat
contradictory. The approach of the glass transition from the liquid
phase seems to become more gradual for softer microgels [89]. Aqueous
suspensions of submicron thermosensitive PNIPAm microgel or core
shell particles have been shown to exhibit a well-dened glass regime.
They represent an exquisite model system for studying the rheology
of entropic glasses in relation with Mode Coupling Theory (MCT) [90].
However, it is interesting to note that the rheology of very similar
PNIPAm suspensions near the liquid-solid transition has been
interpreted in terms of jamming [91] of a mixed glass-jamming state
[92]. Understanding the details of particle microstructure is important
in order to further advance the eld in this direction.
3. Mixtures and osmotic interactions
3.1. Colloidpolymer mixtures
Athermal mixtures of colloidal hard spheres with non-adsorbing
linear polymers constitute an archetypical situation where osmotic
forces induce new morphologies and original rheological behavior
(Fig. 3a) [10,93104]. For example, in the colloidal gas domain (i.e.
uid phase, F), the addition of linear polymers to hard spheres is responsible for attractive depletion interactions which induce the aggregation
of particles [93104]. At low volume fraction phase separation (PS) is
observed whereas at larger volume fractions colloidal aggregates ultimately ll all the available space leading to gel formation (Gel). The interplay between strength and range of particle interactions (both
repulsive and attractive), and gravity remains a subject of debate

[105108]. There are reports pointing to arrested phase separation as


the ultimate equilibrium state in the system (with short-range attractions) and others suggesting that percolation prevails [106112]. The
most intriguing phenomena occur in the high-volume fraction glass regime. When linear polymers are added at increasing concentrations to
hard spheres at a size ratio of about 1/10, the initial repulsive glass
(RG) melts due to depletion interactions and eventually a re-entrant
attractive glass (AG) forms [99,100,103,113].
A natural question concerns the role of softness. Long-range soft potentials are expected to impart not only quantitative but also qualitative
differences in the behavior of soft colloidlinear polymer mixtures [71,
114]. Let us rst discuss the case of three-component mixtures made
of solvent (background), soft colloids and linear chains. Earlier work
with highly crosslinked microgel systems, which behave very much
like hard spheres, conrmed the repulsive glass to liquid to re-entrant
attractive glass or depletion occulation scenario [115118]. Slightly
crosslinked microgels, which respond to external elds by both volume
and shape adjustments (Section 1.4), were found to de-swell in the
presence of small linear polymers [118121]. More systematic studies
have dealt with hairy particles and in particular star polymers
(Fig. 3b) [55,122129]. Due to the osmotic pressure of the linear polymers, star polymers are expected to shrink (de-swell), causing a change
of volume fraction, and eventually experience depletion interactions.
This has been studied in reasonable detail both theoretically and experimentally [55,125,128,129]. Whereas the main physics associated with
osmotic pressure effects is the same as for polymer/hard sphere mixtures, the state diagrams are different (Fig. 3b). More importantly, the
re-entrant solid state is not an attractive glass (or at least not necessarily) but a gel instead (Gel) [128,129]. For given attraction strength,
phase separation is observed [55]. Due to the range of the potential,
the liquid pocket (F) which exists at intermediate volume fractions of
linear chains and stars is larger than in the hard sphere case. Moreover,
polydispersity of the hard spheres may reduce or even eliminate the ergodic phase, but not the glass-to-glass transition [113]. These conclusions are based on systematic rheological measurements supported by
Small Angle Neutron and Dynamic Light Scattering (SANS, DLS), simulations and theoretical models in terms of effective interactions and Mode
Coupling Theory [55,122129]. Nonlinear rheology and in particular
Large Amplitude Oscillatory Shear (LAOS) is an exquisite tool to detect
the softening and eventual melting of the repulsive glass (RG) upon addition of linear chains through the reduction of the yield stress, yield
strain and cage modulus [128130]. It also supports the conjecture
that yielding in these metastable colloidal systems is a gradual process
involving multiple cooperative breakage events [131135]. For large
enough fractions of linear polymers, the ergodic pocket (F) disappears
and the colloidal mixture undergoes a transition from a repulsive glass
(RG) to a gel (Gel). This is unambiguously probed by linear and nonlinear rheology since the LissajousBowditch stressstrain signatures of
gels and glasses measured in LAOS experiments are distinct, the former
being a nearly square curve characteristic of viscoplastic behavior and
the latter a tilted ellipse as is the case for viscoelastic materials
[132135].
The star polymer paradigm has motivated or put into perspective
studies involving hairy particles, and in particular the structure and
dynamics of mixtures of polymer grafted nanoparticles and linear
polymers in good solvents [136] or block copolymers and linear
homopolymers in selective solvents [26,31,137]. In the latter case
in particular, the homopolymers not only melt the crystalline phases
formed by the block copolymer micelles but can also inuence their
aggregation number, hence providing a control parameter for selfassembly [31,137].
Recently, the role of linear polymers in inducing liquid-like behavior
in concentrated microgel suspensions via depletion was exploited [33,
138,139]. Adding polymers to microgel glasses induced melting and
eventual re-entrance attractive glass formation, with the extension of
the ergodic region depending on the microstructure of the particles

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565

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

D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

solutions [45,86,197]. At high angular frequency, the loss modulus of


many soft systems like emulsions and microgels increases like G ~ 0.5,
which is the sign of anomalous dissipation [83,174,178,198,199].
A recent comprehensive study combines particle scale simulations
and a microscopic mean-eld theory [200]. The particles are treated
like elastic non-Brownian spheres dispersed in a solvent (viscosity: s)
at high volume fraction, which interact through Hertz-like potential
and elastohydrodynamic lubrication forces [48]. The theory gives predictions for the pair correlation function of the suspensions, the high
frequency moduli, and the osmotic modulus [200]. Simulations also
allow computing the frequency dependence of the viscoelastic moduli
including the high frequency regime and the variations of the lowfrequency plateau modulus with volume fraction [45,135]. The predictions compare well with experiments without adjustable parameters
when the moduli are scaled by the contact modulus E* of the particles
and the frequency by the characteristic time = s/E*. Other models
have been proposed to take into account the complex interfacial structure of emulsions and the non-homogeneity of coreshell particles
[201,202]. Similar investigations for star-like particles are still missing
but are highly desirable.

4.2. Zero-shear viscosity and self-diffusion


The most striking manifestation of the difference in softness (hence
interaction potential) among colloidal particles appears in the terminal
viscoelastic regime, and a relevant macroscopic quantity is the zeroshear viscosity of the suspensions. It turns out that it is possible to
build a generic plot where the zero-shear viscosity of various systems
scaled with the solvent viscosity is represented versus the effective hydrodynamic volume fraction [57,203]. This is depicted in Fig. 4 which for
clarity only includes one data set from each particle type: hard spheres
[204], high functionality stars [86], block copolymer micelles [32] and
microgels [53]. Interestingly, the limited long-time self-diffusion data
available for hard spheres and stars (not shown here) are in excellent
agreement with the viscosity data when plotted accordingly, hence
conrming the validity of the StokesEinsteinSutherland relation
even at large volume fractions [81,205207]. Data for colloidal particles
of any softness (e.g., stars, grafted particles, block copolymer micelles,
microgels) could be included in such a plot, which reveals the role of
softness in reducing the relative viscosity and increasing the effective
maximum packing fraction [27,61,170,208]. However, it is important

567

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

Fig. 4. Dependence of the zero-shear viscosity (normalized to the solvent viscosity) of


various colloidal systems on the effective volume fraction. Selected data are shown for
suspensions of hard spheres [204], microgels [53], block copolymer micelles [32], and
high functionality star polymers [86]. The dashed line is the best t of hard sphere data
to the Quemada model [53]. The low-shear viscosity data of star polymer data are well
represented by a double exponential function (dotted line) [86].

5.1. Yielding behavior


Concentrated suspensions of soft particles exhibit solid-like properties at rest but ow at large stresses. When the applied stress is decreased, the material is progressively slowed-down and eventually

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immobilized at a nite value of the stress, called dynamic yield stress,


which for the present discussion will be simply called yield stress, y.
Note that the static yield stress represents the stress needed to apply
in order to induce macroscopic ow from rest. In general, the yield
stress can be viewed as a viscosity bifurcation: the application of a stress
is followed by ow stoppage ( b y) or steady deformation ( N y)
depending on the stress value [216,223225]. There are many other
ways of determining the yield stress [226], the most straightforward
and frequently used being the strain amplitude sweep tests [131,174,
188,199,227,228]. Recently, the application and analysis of Large
Amplitude Oscillatory Shear (LAOS) has emerged as a powerful tool
for probing the yielding and ow properties of glasses and jammed suspensions [133,135,227,229232].
Referring to the old dilemma whether glasses ow or not, there is
consensus that yielding exists, i.e. an external eld can drastically alter
the structure of a material, hence its macroscopic properties [233,234].
However, there is still a debate as to whether yield stress is a true material parameter or not. A useful distinction has been made between true
yield stress materials and thixotropic materials exhibiting apparent
yield stress [11,235238].
Densely packed systems such as glassy and jammed particle suspensions (sometimes termed pastes) made of soft repulsive colloids, which
are the focus in this review, are true yield stress materials. Yielding occurs through a continuous break and reformation of the cages which
keep the particles motionless at rest. In this context, LAOS is a unique
tool due to the possibility to reproduce within a cycle the sequence of
events that characterize ow and yielding [133,229,239,240]. One interesting outcome is the effective cage modulus, which is dened as the
slope of the stress vs. strain amplitude plot at zero stress and appears
to match the value of the bulk (plateau) modulus G0 and remains insensitive to the strain or stress amplitude [130,133]. A natural question at
this point is how do yield stress and strain compare for different soft
jammed colloids and depend on volume fraction [131,134]. Due to the
prominence of elastic effects, y is often proportional to G0 with the coefcient of proportionality being the yield strain y: y = G0y. As
discussed in Section 4.1, the storage modulus of soft particle suspensions scales with kT/R3 in the entropic glass regime, and the particle contact modulus E* in the jammed regime. In the literature not much
attention has been paid to the yield strain [199,227,228]. Simulations
and theoretical modeling have predicted that the yield strain of soft
elastic spheres in the jammed regime should increase exponentially
with the distance to the jamming transition (it varies from low values
of about 0.02 near J to about 0.08 for = 0.9) [49]. This prediction is
relatively well obeyed by emulsions [48,49,85,168] and microgel particles [48,134]. Note that entropic hard-sphere glasses have a nonmonotonic yield strain with a maximum value of about 0.15 at a volume
fraction between the glass and close-packing volume fractions [176,227,
241]. Combining the scaling expected for G0 and y provides the variations of the yield stress. Due to their long-hairy conformation, star-like
colloids exhibit distinct yielding properties [86,130,134,199,228]. Since
terminal alpha relaxation is accessible in these systems even at very
high concentrations, as explained in Section 4.1, yielding exists only in
a limited range of frequencies or time scales. Moreover, the yield strain
depends very weakly on concentration. These ndings call for more
detailed investigations.
Colloidal gels of occulated dispersions with attractive interactions
mostly belong to the class of thixotropic materials [11,242,243]. The
microstructure responsible for solid-like properties at b y is
destroyed by the ow, which induces a sudden drop of viscosity and
substantial structural changes. The disruption of the structure under
ow is reversible but typically characterized by a large hysteresis as
the structural timescale is usually longer than the inverse shear rate
[243,244]. Due to their microstructure, stars in the weak glassy regime
in temperature-sensitive solvents exhibit thixotropic-like response
[245]. Although there is some confusion in the terms, the slow evolution
of thixotropic materials is distinct from the aging and rejuvenation

phenomena which are known to occur in purely repulsive systems


[246249]. On the other hand, the yield stress reects in part the
strength of bonds and/or cages. Its determination from the ow curves
poses serious problems because homogeneous ow ends-up over a
limiting range of low shear rates [250]. We will not review the eld of
thixotropy here [11,251]. However, it is worth emphasizing that some
features of thixotropic materials like non-homogeneous ow at low
shear rates are also found in repulsive star-like colloids [178,249]. This
shows that the distinction between true and apparent yield stress
materials is not as denite as often believed, and that some materials
share properties of different classes.
5.2. Flow properties
An important question concerns the establishment of steady-state
ow conditions in the form of stressshear rate relationships or ow
curves. In most experiments, measurements start at high shear rates
(associated with the so-called rejuvenated state) where steady state is
reached rapidly, and the shear rate is progressively decreased down to
the yield point. Applying a stress larger but close to the yield stress is
followed by extremely long transient phenomena, after which steady
state is eventually reached [249,252254]. In practice, the shape of the
steady state ow curves constitutes a remarkable ngerprint of the
system under investigation. In many soft colloidal suspensions like
microgels, emulsions, polystyrenePNIPAm coreshell particles, and
star polymers, the onset of the glass transition is signaled by ow curves
exhibiting two branches at low and large shear rates, separated by a
slowly increasing plateau at intermediate rates (in double logarithmic
coordinates) [86,90,168]. The low-shear rate branch corresponds to terminal behavior, and the high shear-rate branch reects shear-thinning.
As the volume fraction increases, terminal behavior shifts to very low
shear rates due to the huge increase of the -relaxation time, up to
the point where it falls outside the experimental window; meanwhile
the intermediate plateau widens and attens. In the entropic glass regime, the ow curves are conveniently

 represented in dimensionless
coordinates as: kT=R3 f R2 =D0 . Here, kT/R3 represents the characteristic scale of the yield stress while R2 =D0 is a characteristic time
scale associated with the self-diffusion of individual particles (D0 is
the self-diffusion coefcient at innite dilution). In this regime, MCT
provides remarkable quantitative predictions of the ow curves, suggesting that the effects of softness and deformability can be effectively
lumped into the structure factor at least at low shear-rates [90,189,
190,255]. Other nonlinear features like creep behavior [256], stress
overshoots during shear ow start-up [257,258] and the built up of
residual stress [222,259] are also predicted by MCT [260].
At higher volume fractions corresponding to the regime of jammed
suspensions, the ow curves (again in double-logarithmic representation) of a wide range of viscoplastic uids with yielding properties are
characterized by a stress plateau at low-shear rates and a shearthinning behavior at high shear rates [217,246,261,262]. Empirically,
they are very well represented by the HerschelBulkley phenomenologn
ical equation: y k with an exponent n which for different materials has been found to be close to 0.5. The value of the yield stress is in
good agreement with independent measurements based on other techniques. The consistency parameter k depends on material properties. It
has been shown [262] that normalizing the stress and shear rate with
yield stress y and time scale S/G0 (S being the solvent viscosity), respectively, collapses the data obtained for different jammed materials
onto a master curve (Fig. 5). A recent micromechanical model quantitatively accounts for these results and provides a physical understanding
of yielding and ow in soft colloidal particles [49]. The suspensions are
modeled as three-dimensional packings of non-Brownian elastic
spheres which are subject to repulsive central forces and
elastohydrodynamic (EHD) drag forces analogous to those at the origin
of slip near solid surfaces [263,264]. This EHD model provides quantitative predictions for the ow curves [49], the microscopic dynamics and


D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

569

excluded, effects like the cooperative local particle rearrangement,


which for stars and long hairy particles is manifested via interpenetration [5,81,82,205] can contribute to slow relaxations visible at low
shear rates. A phenomenological description of such behavior is possible
m
n
using a modied HerschelBulkley model where A B [86].
In some cases a stress plateau exists but it is associated instead to inhomogeneous ow structure where the ow splits into two bands of
different viscosities, one that is essentially uid (N y), whereas the
other remains solid (b y), separated along the ow gradient direction
and coexisting at the same shear stress. Such a situation has been mainly
reported in thixotropic suspensions [225,236,237] but it also exists in
some star polymer suspensions [178,249,271] where depending on volume fraction and softness (which can be tuned via functionality as
discussed above) a plateau or weak power-law in stress can be observed
(Fig. 5). Interested readers are referred to different reviews on the topic
[272276]. A number of colloidal systems have been shown experimentally to exhibit gradient banding in addition to star polymers: surfactant
solutions [277], hard sphere suspensions [278], block copolymer micelles [275,279281], and carbopol microgels [282]. Presently there is
no consensus on the origin of shear-banding in soft colloidal material
and many different explanations have been proposed: coupling between ow and concentration eld [278], mechanical instability and
mobileimmobile phase coexistence in the low-shear region [178,
283], slow relaxation due to transient bonding [44,284], competition between aging and rejuvenation [271,285], competition between microstructural time and the characteristic ow time scale [286]. Returning
to Fig. 5, it is remarkable that one can tune the ow properties of soft
colloids (such as stars) at a molecular level, and in particular induce or
avoid shear banding. Note that for stars with short arms, mesoscopic
simulations did not produce any shear banding for functionalities
f 50 [212,213]. The fundamental question, which is still under debate
and needs further investigations, is whether there are generic features
of banding in colloids and what is the exact role of softness. For the
star case in particular, the exact role of molecular parameters (number
and size of arms) remains elusive [212,213,271,284]. In general, the interplay of shear banding, yielding, slip and aging in dense soft colloids is
subtle. Clearly, there are ample opportunities for further exploring the
nonlinear shear rheology of colloidal materials including mixtures and
understanding the possible connection of banding to shear-induced
transitions in soft matter.
A nal aspect of signicance in this topic is the role of particle
surface interactions in the macroscopic rheological response of jammed
materials. In a recent investigation of the ow and velocity proles of
microgel suspensions with purely repulsive interactions it was found
that surface roughness and surface chemistry have a strong effect on
ow properties [287]. Below the yield stress, wall slip is of hydrodynamic origin when the surfaces are smooth and the particlesurface interactions repulsive. Slip can be suppressed or reduced by attractive surfaces
[288]. When attractive interactions are weak, slip can occur as a result of
EHD lubrication. Moreover, yielding depends on the surfaces again: it is
uniform near rough or smooth repulsive surfaces and, hence, the bulk
ow properties are recovered. It is non-uniform near smooth attractive
surfaces, suggesting that different dynamical states coexist, forming a
macroscopic boundary layer (and not an immobile band). This marks
a clear difference from bulk properties and from the behavior of nonthixotropic materials discussed above. This important development,
which was recently extended to account for slip heterogeneities in
microchannel ows with different particlesurface interactions [289],
demonstrates another possibility to tailor the ow properties of soft
colloids [290].


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].

macroscopic rheology in LAOS [135], as well as the internal stress that


persists upon ow cessation [221].
In an attempt to propose a unied description, computer simulations
of concentrated suspensions of soft repulsive particles involving thermal uctuations and viscous dissipation were performed [87,88]. They
predicted a transition in ow curves from power-law to plateau stress
vs. rate at jamming, and an empirical model of the form Glass
Jammed s was proposed to describe the entire rheology. Scaling
relations extracted from simulations were used to model the glassy
and jamming contributions to the stress.
As discussed above, the distinction between the entropic glass regime and jammed regime is not always clear. Recent work with PNIPAm
microgel particles at volume fractions close to the jamming transition
suggests that the stress plateau occurs only above the jamming transition whereas a non-Newtonian behavior is observed below [91,92,
265]. These results conrm that the stress plateau is a robust signature
of jamming. However, here the system jumps directly from the liquid
state to the jammed state without crossing the entropic glass regime.
The ow curves measured above and below the yield point collapse
onto two branches exhibiting power-law scalings of shear stress and
shear rates with the distance to the jamming transition. The same
type of critical scaling collapse was reported using numerical simulations and simple models of soft particles interacting through repulsive
interactions, but the exact values of the exponents are largely modeldependent [266269]. These results are qualitatively consistent with
the EHD micromechanical model, albeit again with different exponents,
leaving the issue partially unsettled. Two parameters seem to be important: the distance to the jamming point (EHD model results are for
suspensions well inside the jammed regime) and the exact form of the
viscous drag force between particles [270].
Despite the link between the existence of a stress plateau at low
shear rates and jamming that has been mentioned in the previous
paragraph, there are situations where the plateau is not indicative of
true yielding behavior or does not even exist. A deviation of the lowrate stress from a true plateau may also reect the particle's internal microstructure, even when aging is carefully accounted for. A powerful
manifestation of these effects for systems where a yield stress is dened
from dynamic strain sweep experiments was reported for star polymers
[86]. An interpretation of this remains elusive, but with slip being


5.3. Mesoscopic modeling of soft colloidal rheology


Besides MCT and micromechanical models discussed above, the rich
behavior of soft colloids at high volume fractions has stimulated a
wealth of phenomenological modeling activities. While these models

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D. Vlassopoulos, M. Cloitre / Current Opinion in Colloid & Interface Science 19 (2014) 561574

involve many parameters not directly accessible in experiments, they


enjoy reasonable success in reproducing several features of the rheology
of dense suspensions. For example, the Soft Rheology Model (SGR) uses
trap dynamics for local mesoscopic non-ergodic events, with the effective noise temperature parameter x characterizing the jump rate out
of local traps [291,292]. Appropriate variation of x allows to reproduce
macroscopic yield and ow dynamics observed in steady, oscillatory
and transient ows as well as viscosity bifurcation and thixotropy
[285]. Historically the SGR model has opened the route for many phenomenological models, which are impossible to review in depth here.
In the following we mention briey a few of them and we refer the interested reader to more specialized articles [293,294]. The starting
point of all these models is a coarse-grained representation of the material divided into mesoscopic cells, where the stress evolves according to
a prescribed law. In the uidity model, the local state of the system is
expressed by a Maxwell equation which involves the local relaxation
frequency of the stress, called the uidity [172,217,295]. The time evolution of the uidity results from the competition between aging, which
decreases the uidity as time passes, and ow-induced rearrangements,
which increases uidity. Further developments of the uidity model
take into account the spatial variation of the uidity, which can be
used to reproduce the occurrence of various spatial heterogeneities
like shear banding [249,271]. An approach bearing similarities with
the uidity model is the non-local cooperative model which accounts
for the cooperative nature of rearrangements by relating the spatial
stress response in each cell to the global stress uctuations occurring
over the entire system [294,296298]. A characteristic cooperative
length was proposed to exist and be intrinsic material property, something that is not totally supported by existing experiments. This cooperative model has been used to explain deviations observed in concentrated
emulsions from bulk rheology in conned geometries [299301].
6. Conclusions and perspectives
This partial presentation of the views of the community on the
rheology of soft colloids demonstrates the unprecedented richness
imparted by softness on the properties of colloidal suspensions. It is evident that the eld of soft colloids is picking-up. We believe that the
major advantage of these systems is their tunability which allows tailoring their ow properties at molecular level. This indicates that understanding the ne details of internal microstructure of the particles is
often of crucial importance [4,5,128,302]. The two most important distinct features are their change of shape/size (e.g., microgels) and their
interdigitation (e.g., stars) in the dense state. It is evident from the
above discussion that several outstanding challenges remain. We list
them below.
The existence and the nature of the glass and jamming transitions in
soft dispersions pose several important questions. Does a glass to jamming transition exist for all types of soft colloids (say microgels and
stars)? Is there universality in scaling the viscoelastic properties with
the actual volume fraction? In relation to this, aging and the related
role of internal stresses need further elaboration for the different soft
colloidal archetypes.
Osmotic effects due to additives are shown to yield new dynamically
arrested states. New types of mixtures and other combinations of size
ratio and volume fractions must be investigated to deeply understand
the state diagrams. The rheology of these states and the possible owinduced transitions remain largely unexplored.
In the eld of nonlinear rheology, linking the scaling of ow curves
in the glassy and jammed regions represents a grand challenge. Along
the same lines, the high-shear and extensional rheology of soft colloids
in these states are entirely unexplored territories and their possible
combinations with rheo-physical observations of particle/structure deformation will advance the eld and also contribute to our understanding of the relations among various types of shear-banding, yielding, and
slip with respect to particle architecture and the nature of the conning

surfaces. Moreover, the effects of softness and volume fraction on the


remarkable shear thickening phenomenon associated with colloidal
dispersions have received very little attention so far [303,304]. Recently,
discontinuous shear thickening was discussed in friction-dominated
large hard sphere suspensions (somehow equivalent to jammed particles) and the principal role of contact friction was identied [305,306].
To go beyond entropic spherical systems, variations of temperature
or pressure can change the quality of the background solvent and
hence introduce attractions. Likewise, the presence of functional endgroups can lead to clustering and hierarchical order with the possibility
of obtaining well-characterized patchy supramolecular structures [307]
whose rheology is unknown. Finally, departure from spherical shape
combined with softness is expected to change the packing of colloids
and hence their structure and rheology. These are promising new directions. The eld remains as exciting as ever!
Acknowledgments
This review was written when D.V. was visiting ESPCI ParisTech
with the support of the Michelin Chair. We thank Jan Mewis for helpful
comments on the manuscript ESPCI ParisTech is member of PSL Research University.
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