Advances in Colloid and Interface Science 206 (2014) 79–91

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Advances in Colloid and Interface Science

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

Three-phase interactions and interfacial transport phenomena in

coacervate/oil/water systems
Gregory Dardelle, Philipp Erni
Firmenich SA, Corporate Research Division, Materials Science Department, 1217 Meyrin, Geneva, Switzerland

a r t i c l e i n f o a b s t r a c t

Available online 30 October 2013 Complex coacervation is an associative liquid/liquid phase separation resulting in the formation of two liquid
phases: a polymer-rich coacervate phase and a dilute continuous solvent phase. In the presence of a third liquid
Keywords: phase in the form of disperse oil droplets, the coacervate phase tends to wet the oil/water interface. This affinity
Interfaces has long been known and used for the formation of core/shell capsules. However, while encapsulation by simple
Encapsulation or complex coacervation has been used empirically for decades, there is a lack of a thorough understanding of
Emulsions
the three-phase wetting phenomena that control the formation of encapsulated, compound droplets and the role
Wetting
Rheology
of the viscoelasticity of the biopolymers involved. In this contribution, we review and discuss the interplay of wet-
ting phenomena and fluid viscoelasticity in coacervate/oil/water systems from the perspective of colloid chemistry
and fluid dynamics, focusing on aspects of rheology, interfacial tension measurements at the coacervate/solvent in-
terface, and on the formation and fragmentation of three-phase compound drops.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
1.1. Top-down vs bottom-up formation of compound drops and core/shell capsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
1.2. Complex coacervates in nature and in encapsulation technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2. Rheology of complex coacervates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.1. Measurements of the rheological material functions of coacervates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2. Interplay of rheology and structure of coacervate droplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3. Hydrodynamics and interfacial tensions of coacervate droplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4. From wetting to core/shell formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.1. Apparent contact angles in coacervate/oil/water systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.2. Interfacial energy balance in three-phase compound drops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5. Fluid dynamics of compound drops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.1. Partial coverage — drops with ‘caps’ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.2. Fluid dynamics of fully encapsulated compound drops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.3. Deformation and fragmentation of compound drops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

1. Introduction food products, perfume formulation, pharmaceuticals, or inks [1–5]. To

1.1. Top-down vs bottom-up formation of compound drops and core/shell
capsules
Core/shell capsules are important for controlled delivery and release
of active ingredients in applications such as the flavoring of beverages or
E-mail address: philipp.erni@firmenich.com (P. Erni).
obtain particles with a core/shell structure, wherein a barrier layer sur-
rounds the liquid or solid core, two essential fluid processing operations
are necessary: (i) the core material must be dispersed in the continuous
phase in the form of an emulsion (for liquid active ingredients) or sus-
pension (for solids); and (ii) the shell material must be formed, brought
to the active/solvent interface, and stabilized by physical and/or cova-
lent cross-linking.
A vast amount of recent literature describes simultaneous, ‘top-down’
dispensing and shell formation via coaxial flow channels or flow focusing

0001-8686/$ – see front matter © 2013 Elsevier B.V. All rights reserved. 自上而下和自下而上的壳核结构制备，显然通过coacervation的方法是后者
http://dx.doi.org/10.1016/j.cis.2013.10.001
80 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91

geometries in microfabricated channels [3,6–8]. Similar flow geometries
have been described [9] and commercialized previously with larger
capillary or channel dimensions; in the area of encapsulation technology,
the methods are often called ‘prilling’ (i.e. the continuous ejection of
gel-forming droplets via dripping from a capillary into continuous fluid
for rapid gelation [10]) or ‘laminar jet breakup’. Typically, the capillary
is vibrated at a controlled frequency via accoustic actuation. Interestingly,
the attention that the microfluidic approach to capsule formation has
received in academics since the first articles on droplet formation using
microporous membranes are not mirrored in actual usage of the technol-
ogy in industrial applications [11,12]. This lack of industrial implementa-
tion is somewhat surprising, since the average article on microfluidic or
membrane-based droplet formation typically starts or ends with claims
to industrial relevance.
Here, our objective is to review a bottom-up route for the formation
of core/shell capsules that does not rely on microfluidics and discuss
the formation of core/shell capsules via complex coacervation, i.e. the
bottom-up formation of capsules by coating of an ensemble of oil drop-
lets or solid particles with a polymeric layer material in a large-volume,
three phase flow, from the perspective of fluid dynamics and interfacial
transport phenomena (Fig. 1).
1.2. Complex coacervates in nature and in encapsulation technology
For applications in foods, consumer products, or for pharmaceutics the
choice of capsule wall materials is naturally restricted to ingredients in
line with legislation constraints [5,13–15]; self-assembled, biopolymer-
based capsules are among the most important delivery systems in this
field [1,2,16,17].
More recently, coacervates have also been used as scaffolds to form
interpenetrating silica/biopolymer materials. Classical precipitated silica
has been used as a carrier for such molecules for decades [18], but the pro-
tection of the entrapped volatiles is typically poor. In contrast, coacervate-
templated silica/biopolymer hybrid capsules have recently been shown
to dramatically improve retention of volatile encapulated oils [2].
Complex coacervation is a liquid/liquid phase separation occurring in
colloidal systems, resulting in the formation of two liquid phases [19–21]:
a hydrocolloid-rich phase (coacervate phase) and a dilute continuous
phase. The coacervate appears as amorphous liquid droplets exhibiting
表现为液
affinity for oil/water or solid/liquid interfaces. Formation of microcap- 滴
sules by complex coacervation typically involves the steps of (i) phase
separation and formation of coacervate nodules; (ii) emulsification/
dispersion of the active ingredient; (iii) deposition and coalescence
of coacervate nodules onto the active/continuous phase interface, 乳化过程
(iv) physical gelation and, optionally, (v) covalent crosslinking of the
wall. Whereas step (i) has been covered in much detail in the literature
over the last decades [22–26], there is far less quantitative knowledge
available regarding the engineering/processing of the (micro)capsule 然而很少
描述
genesis described in the steps (ii)–(v). Lemetter et al. [16] studied 后面上界
microcapsule formation by complex coacervation from a process engi- 面的过程
neering perspective and specifically focused on the role of different
processing parameters, such as the Reynolds number in the reactor,
cooling rate profiles, and the type of emulsification. These authors
emphasized the different microcapsule morphologies that arise in co-
acervate capsule formation, including (a) mononucleated capsules
(one core, surrounded by a shell), (b) polynucleated capsules (several
cores contained within one shell, and (c) ‘grape’ type, aggregated
capsules.

solvent
100%
b

50% 50%
weak polyanion protein

Fig. 1. Overview of the core/shell capsule formation process by complex coacervation. (a) Schematic of a core/shell encapsulation process by complex coacervation, starting with
oil-in-water emulsification, coacervate formation by protein/polyanion phase separation, coacervate deposition at the substrate/water interface, and subsequent physical gelation of the
protein followed by covalent cross-linking. (b) Typical coacervate capsules obtained with different processing conditions and compositions (left); gelatin/Acacia gum coacervate phase
immediately after phase-separation (middle left) and after gelation (middle right); typical ternary phase diagram [2,5,19] for coacervates formed by a protein (such as gelatin) and a
weakly anionic polysaccharide (such as Acacia gum) (right).
 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91
Formation of capsule walls from phase-separated, polymer-rich drop-
lets dispersed in their own solvent relies on the interfacial energy balance
between the three phases (oil/solvent/polymer-rich phase). The relation
between the interfacial energies must be such that the polymer-rich
phase wets the oil/solution interface at least partially. This coating process
results in a compound suspension of oil or solid cores contained within
larger drops of phase-separated polymer.
Recently, coacervation has also received attention for its role in bio-
logical adhesion [27], studied for example for the case of coacervates
formed by hyaluronic acid and recombinant mussel adhesive proteins
[28,29]. On the other hand, coacervates also form between synthetic
polyelectrolytes such as poly(acrylic acid) (PAA) and poly(allylamine
hydrochloride) (PAH) [30].
Despite its relevance for the formation of core/shell capsules and for
biological adhesion, the interplay between surface thermodynamics,
背景介绍
rheology of the coacervate phase, and multiphase flow has not been
studied in much detail. Moreover, while the mechanisms underlying
the formation of core/shell capsules with shells formed by phase-
separated biopolymer gels have been known for decades, there appears
to remain some confusion about the sequences of physical processes
leading to capsule formation. Even for many scientists familiar with
polyelectrolyte complex formation, the particular mechanisms of cap-
sule formation remain unclear, and the interested reader trying to get
an overview of the subject is treated to descriptions as varied ‘complex
formation at the interface’, ‘precipitation of a coacervate at the inter-
face’, ‘coacervation at the oil/water interface’, ‘layer formation by coac-
ervation’ or ‘deposition of polyelectrolyte complexes at the oil/water
interface’ for one and the same process.
Why is there such confusion on a topic that, in principle, has been
known in the scientific and patent literature for over 60 years? Part of
it might be due to the interdisciplinary nature of this topic: coacervation
is largely discussed in the colloid science community. Conversely, the
physical principles for the formation of composite droplets, double
emulsions and core/shell capsules have traditionally been discussed in
the context of chemical engineering or multiphase fluid dynamics.
Therefore, in this article we start from the view that coacervate core/
shell capsule formation is a three-phase, free-interface flow problem,
流动 where one of the three phases has been formed by associative phase
三相润湿 separation, and we investigate the interplay between the flow, three-
凝聚性流变学
phase-wetting, and the rheology of coacervate phases.
Since the physicochemical aspects of complex coacervate forma-
tion have been summarized in several excellent overview articles
[22–24,31–35], we will discuss only the key results and insights rele-
vant for the three-phase wetting process in core/shell capsule forma-
tion with coacervates.
Coacervates can be formed between a variety of biopolymers. Typi-
cally, the polyanion is a weakly anionic polyampholyte; strongly anionic
polysaccharides, such as the carrageenans, cause precipitation rather
than coacervation. An overview of the most important polymer pairs
for complex coacervation is provided in an overview article by de
Kruif et al. [22]. Some prominent examples are β-lactoglobulin/Acacia
gum [36–38], β-lactoglobulin/pectin [39], gelatin/Acacia gum, or
chitosan/Acacia gum [40,41]. For reference, we also point out the case
of simple coacervation, wherein a single polymer phase-separates by a
change in solvent conditions, i.e. gelatin in water/ethanol mixtures
[42]; their structure, rheology and physicochemical properties appear
to be more closely related to precipitates formed by strongly charged
polyampholytes rather than being an actual phase-separated liquid
phase.
2. Rheology of complex coacervates
2.1. Measurements of the rheological material functions of coacervates
Given their relevance for biological or bioinspired adhesion and for
industrial encapsulation processes, the rheology of complex coacervates
81
has surprisingly received little attention. Those studies that have
addressed their rheology tend to focus on the viscosity as a function of
parameters such as the ionic strength, pH, polymer concentration or
the mass or molar ratios of the constituent polymers.
Spruijt et al. [43] described the role of the electrolyte concentration
for the rheology of electrostatic complexes using two equally long and
oppositely charged polyelectrolytes and found that the small amplitude
oscillatory shear rheology can be condensed shifted onto a master-curve
by a time/salt superposition (similar to time/temperature or time/
concentration superposition, and not accounting for swelling). The
same authors also discussed interfacial tension measurements of coac-
ervate phases against their polymer-depleted solvent using an atomic
force microscopy technique.
The rheology of coacervates formed by whey proteins and Acacia
gum was investigated by Weinbreck et al. [44]; they measured the
steady shear viscosities and the dynamic moduli at varying shear rates
and frequencies. Varying the polymer concentration, pH value and the
protein-to-polysaccharide ratios, they found that the averaged viscosity
values of the coacervate phase as a function of pH follow a trend parallel
to the polymer content in the coacervate phase, with a pronounced
maximum around pH 4.0. For the coacervates with the highest viscosi-
ty, coinciding with what the authors described as the point of the stron-
gest electrostatic interactions, they found that the flow curves showed a
hysteresis effect between the up- and down curves. While we prefer not
to use hysteresis curves for the data shown later in this work (mostly
because they blur the line between the separate effects of shear history,
shear thinning and time-dependence), they do indeed suggest that
significant structure formation takes place in the coacervate, as is typi-
cally the case for weakly aggregated suspensions or gels. However,
Weinbreck et al. also found clear evidence that in their whey protein/
Acacia gum coacervates at room temperature the elastic modulus G′
was only very weak and the viscous modulus G″ was dominant. Their
data for G″ at 25°C and at different pH values suggest a predominantly
viscous scaling law of the shear modulus with frequency. From a differ-
ent perspective, Thomasin et al. [45] discussed the role of viscosity for
coacervate-based encapsulation but did not mention the effects of
fluid elasticity.
As we will show below, elastic stresses need to be taken into account
especially for coacervates wherein one of the polymers is a gel-forming
protein. Gelatin/Acacia gum complex coacervates for rheometry and
for all experiments described in the following were formed as described
in more detail elsewhere [2] with a 1:1 mass ratio of the polymers at
pH 4.5 and ionic strength 5 mM. Phase separation was induced by di-
lution with water to yield final polymer concentrations of 1.7% w/w
each.
With the data shown in Figs. 2 and 3 the rheological response of
complex coacervates formed from gelatin and a weak polyanion can be
decomposed into a contribution stemming mostly from the protein (per-
colation related to the concentration of collagen triple helices) [46] and
reflected in the temperature profile of the loss tangent G″/G′(T), and
into a contribution of the polyanion, reflected merely in the increase in
the overall level of the modulus. To a minor extent, the presence of the
polyanion slightly softens the percolation threshold of the gelatin, indi-
cated by a less abrupt change in the slope of dG′/dT.
2.2. Interplay of rheology and structure of coacervate droplets
In a few studies the role of coacervate rheology for the encapsulation
process is mentioned [47–49], as previously summarized by Weinbreck
et al. [17,44]. In particular, high coacervate viscosity was mentioned as a
reason for improved coalescence stability of the capsules by Burgess
[48]. Later, Liberatore et al. [50] studied the role of shear flow for the
formation of polyelectrolyte/mixed micelle coacervates.
Hwang et al. [29] investigated the viscosity and friction properties of
mussel-inspired coacervates formed between recombinant proteins
and hyaluronic acid using the surface force apparatus (SFA).
82 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91

a 104
b
G' (Pa) 101
G'' (Pa) 25 °C
30 °C
103 105
37.5 °C
104 45 °C

Apparent viscosity (Pa·s)

55 °C
103 65 °C

102 102
G', G'' (Pa) 101 100
10–1 100 101 102 103
(rad/s)
101

100
10–1

10–1
20 40 60 100 101 102 103
T(oC) Shear stress (Pa)

Fig. 2. Rheology of the coacervate phase forming the shell of the core/shell structure. (a) Temperature sweep experiment for complex coacervates formed from gelatin and Acacia gum,
showing the transition from the liquid coacervate to physical gel. Inset: frequency sweep experiment performed after gelation. (b) Steady shear viscosity, plotted as a function of the
shear stress at various temperatures. The coacervate phase transitions from a weakly shear-thinning viscous fluid behavior at temperatures above 37 °C to strong shear thinning in an
intermediate regime, followed by the onset of an apparent yield stress for temperatures below 30 °C.

研究粒径
Priftis et al. [51] also studied the rheological properties of complex breakup or coalescence of coacervate droplets has been studied by
coacervates formed by (ethylene-imine)/poly(D,L-glutamic acid) and Sanchez and coworkers [52].
observed the typical reduction in the viscosity with salt concentration Interestingly, the connection of the vast literature on the thor-
[22] also found for biopolymers. Depending on the acid:base ratio, oughly studied field of morphology development in immiscible poly-
these authors also found weakly shear-thinning behavior in steady mer blends [53] seems to be rarely made in studies of coacervates
shear flow, and demonstrated that for the dynamic oscillatory rheology [54], even though the underlying competition between interfacial
the frequency sweep data form a master-curve via a superposition of forces, shear forces, droplet breakup and (re-)coalescence is identi-
frequency and salt concentration. cal. In contrast, these similarities are discussed more explicitly in
Coacervates formed by bovine serum albumin (BSA) and poly the literature on water-in-water biopolymer blends formed by seg-
(diallyldimethylammonium chloride) were investigated by Bohidar regative phase separation [55–61].
et al. [25] in dynamic oscillatory shear flow and observed mostly Recent measurements by Priftis et al. [62] on coacervates formed
liquid-like rheological responses with dominant viscous moduli between the synthetic polypeptides poly(L-lysine hydrochloride) and
G″ N G′ and typical Newtonian scaling G″∝ω and G′∝ω2 at high oscilla- poly(L-glutamic acid sodium salt) with a capillary adhesion technique
tion frequencies ω. At the lower end of the frequency range, a slow re- using the surface force apparatus (SFA) reveal that the interfacial ten-
laxation shoulder with increased G′(ω) occurred. This onset of weak sions are consistently below 1 mN/m. These authors discussed the
elasticity at low frequencies suggests that despite the predominantly role of operational parameters (such as compression force and separa-
viscous response a very weak network is present, a view supported tion speed), solution conditions and total polymer chain length for the
by the reduction in these elastic effects with increasing strain ampli- interfacial tension. As in the work of Spruijt et al. [63], increasing salt
tude. Similar frequency sweep data were also presented for coacer- concentrations decrease the interfacial tension. The possible role of
vates formed from Acacia gum and chitosan by Espinosa-Andrews non-Newtonian fluid rheology for the force balance used in the interfa-
et al. [41]. 这些流变学数据能说明什么信息 cial tension measurements remains an interesting topic for further
Kizilay et al. [34] pointed out the effect of shear rate on the size of studies. We expect that these effects are also relevant for coacervates
coacervate droplets; the effect of different levels of shear rate on the formed with globular proteins [17,31,33] although in that case gel

102 102
gelatin only
10 1
10 1 coacervate
* (Pa s)
G''/G' (-)

100 100

gelatin only
10-1 10-1
coacervate
10-2 10-2
20 30 40 20 30 40
T (oC) T (oC)

Fig. 3. Comparison of the rheology of a coacervate phase (protein: gelatin, polyanion: Acacia gum) and with the corresponding protein-only system at comparable protein concentration,
ionic strength and pH value. Both the temperature dependence and the dynamic behavior of the coacervate phase directly reflect that of the protein component, but in the coacervate the
gel transition is softened and the overall level of the shear stress is increased. In contrast, the polyanion merely increases the level of the viscosity above the gel temperature, but does not
alter the elasticity due to gelation of the protein component.
 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91
formation will proceed by different mechanisms [64] as compared to
gelatin. The latter form thermoreversible gels upon cooling, essentially
determined by the recombination of disordered gelatin chains to re-
form portions of the original collagen triple helix [65]. Coacervates
formed with globular protein will therefore not melt upon heating,
and the relatively simple rheological behavior found for gelatin-based
coacervates above the gel point does not exist in those cases.
11s加热后形成microgel,跟明胶比有着更复杂的流变行为
3. Hydrodynamics and interfacial tensions of coacervate droplets
The interfacial tension between complex coacervates and their
coexisting aqueous solvent σcoa/w is important for the hydrodynamics
and formation of core/shell droplets and capsule. However, there is
surprisingly little experimental or theoretical work available on actual
values, experimental measurements, or theoretical predictions for in-
terfacial tensions in coacervate/solvent systems. The main experimental
challenge is the low level of σcoa/w. Since common methods, such as
pendant drop or drop volume tensiometry, rely on the presence of a
pendant drop
不能直接测 well-defined droplet and on a balance between interfacial tension and
gravity, they are difficult to apply, and it is challenging to even form
droplets that can be analyzed quantitatively by these (quasi-)static
methods. In an early study, De Ruiter and Bungenberg de Jong [66]
describe tensiometry measurements using a capillary method and
found very small interfacial tensions of the order of ≈1 μN/m. More re-
cently Spruijt et al. [63] used atomic force microscopy (AFM) to record
force–distance curves for liquid bridges formed by coacervates adhering
to solid surfaces. They obtained values for the coacervate/solvent inter-
facial tension of the order of tens to hundreds of μN/m. Similar values
were found using the surface force apparatus [62].
Like coacervates, phase-separated polymer mixtures formed by
segregative phase-separation have similarly low interfacial tensions
[54,60,61,67–69]; interfacial tensions in those systems have been stud-
ied in more detail using rheo-optics, microscopic droplet deformation or
retraction methods, or spinning drop tensiometry. 测表面张力的方法
Antonov and coworkers [54] investigated associative phase sepa-
ration and flow-induced structures in gelatin/Acacia gum systems
using rheo-SALS and used droplet deformation and breakup models to
estimate the interfacial tension; they obtained values of the order of
tens of μN/m. Hydrodynamics has also been shown to influence the for-
mation of coacervates: Liberatore et al. [50] studied shear-induced
phase-separation for polyelectrolyte/mixed micelle coacervates using
rheo-small angle light scattering (SALS) experiments. Those coacervate
systems possess a critical temperature or shear rate and tend to undergo
a transition from Newtonian to shear thinning as the temperature in-
creases, and the corresponding SALS patterns [70] reveal flow-induced
deformation of the coacervate droplets. Although the authors did not
make this comparison, those phenomena appear to be rather similar to
the flow-induced morphologies of uncompatibilized, immiscible two-
phase polymer blends. Seen from this perspective and applied to the co-
acervate systems of interest here, 'shear-induced phase separation' is
likely an initial phase separation (quiescent or under shear) followed
by shear-induced coalescence of non-compatibilized coacervate droplets.
The shape of liquid filaments immersed in a second fluid evolves
under the action of the capillary pressure, which acts as a driving force
in the capillary thinning dynamics of the filament [9,71–75]. This flow
occurs spontaneously if the configuration of a liquid bridge is brought
beyond its static Rayleigh–Plateau stability limit [76] and is driven by
the surface tension. It is slowed down by a combination of viscous and
elastic stresses in the fluid [77–80]. Therefore, the material properties
of the filament can be extracted from its thinning dynamics. They are
typically measured as the change in the radius at the neck of the liquid
bridge over time R(t). If boundary conditions are properly chosen and
adapted to the material, capillary thinning can be used as a rheometric
flow [76–78,81–83].
A necessary condition for microfilament rheometry is that the
viscocapillary time scale tvc = η0R0/σ be sufficiently long that a
83
well-defined capillary-driven flow can be established and fluid iner-
tia should be negligible [76,83] (σ is the interfacial tension, R0 is the
radius of the filament, and η0 is the zero shear viscosity). From the
definition of tvc it is clear that this can be achieved either via high
viscosity levels or low interfacial tensions. This corresponds
pffiffiffiffiffiffiffiffiffiffiffiffi to high
values of the Ohnesorge number Oh ¼ t vc =t r ¼ η0 = ρR0 σ N1 , a di-
mensionless group comparing tvc with the Rayleigh time scale
tr = (R30ρ/σ)1/2 [84–87]. Interestingly, although the zero shear vis-
cosity and the interfacial tension both appear in tvc, it seems that
the capillary thinning technique is mostly used to extract apparent
viscosities of complex fluids whereas the interfacial (or surface) tension
is measured (or assumed) independently and used as a constant to
calculate the rheological properties from appropriate fluid models. Con-
versely, capillary thinning dynamics in principle also allows to proceed
the other way around and estimate the interfacial tension if the rheo-
logical properties are known [60,61,73,88]. This approach is particularly
interesting if a sample is Newtonian, its viscosity is known, and the
capillary thinning dynamics occur on a time scale that is experimentally
accessible and within the boundary conditions needed for the model
calculations to be applicable — all of which happens to be the case for
an aqueous coacervate thread immersed in its coexisting, polymer-
depleted solvent. We therefore suggest that the dynamics of microfila-
ments are very useful to estimate the interfacial properties of phase-
separated polymer solutions and other low-interfacial-tension systems.
It is crucial to ensure that viscoplastic behavior is absent — if the fluid
thread possesses even a weak yield stress (i.e. due to gel formation of
the protein or peptide component), or if it tends to form a gel under
the conditions of the measurement, standard viscous or viscoelastic
fluid models will underpredict the interfacial tension. If those proper-
ties cannot be neglected, quasi-static experiments wherein the liquid
thread slowly expands step by step, are preferable: postulating a stress
balance between the yield stress (conserves the filament) and the cap-
illary pressure (tends to break up the filament) at the precise radius at
which the filament breaks provides at least an estimate of the apparent
interfacial tension.
In Fig. 5, a capillary thinning experiment performed with a complex
coacervate filament floating in its coexisting aqueous solvent is shown.
The polymer-rich phase was formed by coacervation with gelatin and
Acacia gum, separated by sedimentation and reinjected into the
polymer-depleted water phase. The temperature is T = 60 °C, which
is above the gelation temperature of the protein. In first approximation,
the rate of thinning of the coacervate filament is controlled by the radius
of curvature, the coacervate/water interfacial tension, and the viscosi-
ties. The floating coacervate thread immersed in the coexisting solvent
thins down and breaks with the radius decreasing linearly with time,
as predicted for Newtonian fluids [89]. Due to the low interfacial ten-
sion, the critical time scale for filament thinning and breakup is of the
order of seconds, tc ≈ 2.2 s; the numerical front factor f follows from
Papageorgiou's similarity solution for capillary thinning of Newtonian
fluid filaments [76,89] (a typical approximation is f = 0.0709):
R σ
¼f ðt −t Þ: ð1Þ
R0 η0 c
The linear decrease of the radius of the coacervate filament with
time suggests that a Newtonian fluid model can be used to describe
the behavior [89]; with the zero shear viscosity η0 known from inde-
pendent rheology measurements, the data shown here can be used
to extract an estimate for the coacervate/solvent interfacial tension
σ ≈ 87 ± 5 μN/m.
These experiments were performed far above the gelling tempera-
ture of the protein component in the coacervate. Using the zero shear
viscosity to approximate the fluid rheology to first order is a simplifica-
tion; for systematic studies on compositional effects on the interfacial
tension, more detailed fluid models (e.g. weakly shear thinning) are
needed. On the other hand, the advantage of this liquid filament method
84 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91
to estimate interfacial tension is that the role of fluid rheology is more
directly visible in the experiments — indeed, non-Newtonian rheology
or even fluid elasticity or a yield stress remains more obscure and diffi-
cult to differentiate in AFM or SFA-based methods [63]. If these fluid
rheology effects play a role in coacervates, they most likely lead to an
over-prediction of the interfacial tension. For simply shear thinning,
the effect might be weak or negligible; in contrast, if even a very weak
yield stress is present, the effect on the measured apparent interfacial
tension might be quite dramatic. Our view is that interfacial tension
measurements on coacervates always must be accompanied by rheolo-
gy measurements. Additionally, for measuring techniques between
solid surfaces it is vital to account for the effect of confinement on
fluid rheology. Confining a complex fluid to the length scale of its struc-
tural elements can lead to drastic changes in the rheological material
functions [90,91]. Depending on the polymer chemistries used, these ef-
fects are likely to occur at several length scales in coacervates.
4. From wetting to core/shell formation
4.1. Apparent contact angles in coacervate/oil/water systems
Complex coacervates are traditionally used to encapsulate hydro-
phobic core materials. This process is indeed a combination of a ‘top-
down’ emulsification or dispersing process for the core material (here:
oil droplets) with a ‘bottom-up’ coacervate formation process. The re-
sult is a three-phase emulsion consisting of (i) oil droplets, (ii) aqueous
coacervate droplets rich in polymer, and (iii) a continuous, polymer-
depleted continuous aqueous phase.
To form core/shell drops, the polymer-rich phase needs to coat the
core oil droplets or solid particles, resulting in a composite emulsion
of oil droplets contained within larger coacervate drops. Knowing that
the liquid coacervate droplets are pre-formed and are available in the
vicinity of the oil or solid core, this coating could, in principle, occur
via different routes: (i) the polymer-rich phase spreads at the oil/
water interface, thereby forming a primary thin coacervate film, and a
shell forms by further growth via coalescence of additional coacervate
droplets; (ii) individual coacervate droplets wet the oil core, without
spreading spontaneously, and the shell is formed by simultaneous or se-
quential wetting with additional coacervate droplets until a contiguous
shell is obtained. At first sight, the question seems to be whether the co-
acervate ‘spontaneously’ spreads at the oil/solvent interface to form a
shell around to oil core, and the feasibility of encapsulation would simply
be predicted by the capacity of the coacervate to spread at the interface.
However, Fig. 4 shows that this is clearly not the case: a droplet of oil –
here: eugenol (2-Methoxy-4-(2-propenyl)phenol, a fragrance oil with a
relative density higher than that of water) – is dispensed onto a gelled
coacervate surface immersed in the aqueous coexisting solvent consis-
tently assumes a contact angle far greater than 90°. In combination
with the aqueous coexisting solvent, no spontaneous spreading occurs.
Fig. 4 also shows the events observed for the inverted configuration:
a spherical, gelled bead of a coacervate phase formed by gelatin as the
protein and Acacia gum as the polyanion, is placed on a hydrophobic
substrate (PTFE surface) immersed in the coexisting aqueous solvent
at 25°C. Initially, the apparent ‘contact angle’ of the spherical coacervate
bead is θapp = 180°, a value which is of course fully determined by the
gel elasticity and integrity of the bead. As the temperature rises (at a
rate of 1°C per minute), the bead melts, and the apparent advancing
contact angles are now determined by a balance of viscoelasticity in
the bead and surface energy. Gravitational sagging of the coacervate
bead pushes the liquid front in the outward direction, and the contact
angle attains a minimum value at θapp ≈110° at a temperature of 31°C.
Notice that even at this point, θapp N 90°. Increasing the temperature
further again increases the angle to θapp ≈ 135–140° above T = 31 °C;
the rheology data shown above strongly suggest that elastic stresses no
longer play a significant role in this regime, and that wetting is now con-
trolled entirely by interfacial energy. Indeed, the values of the contact
angles above the melting point of the protein gel are similar to those
found above for the inverse, oil drop-on-gel configuration, where the
wetting drop was purely Newtonian.
4.2. Interfacial energy balance in three-phase compound drops
Generally, two immiscible liquid drops surrounded by a third im-
miscible liquid can form a range of equilibrium configurations deter-
mined by the relative interfacial tensions σij and spreading coefficients
Si = σjk − (σij + aik). This topic has been addressed in 1970 in a sem-
inal article by Torza and Mason. Following their definitions, coacervate
compound drops with complete encapsulation of the oil drops corre-
spond to 2-singlet (2 s) structures (shown in the right-hand side in
Fig. 7). Torza and Mason's work is based entirely on equilibrium interfa-
cial energy considerations (Fig. 8). They already pointed out that in
many cases additional factors arise, and specifically mention increased
viscosities as one of them. However, in view of our discussion of the
role of non-Newtonian fluid rheology for three-phase wetting, high vis-
cosity alone is not expected to be the sole reason for non-engulfment: a
high shear viscosity alone merely slows down a process. In contract, the
presence of shear elasticity in the shell material will actually resist the
spreading flow.
Waters [92] and van Zyl et al. [93] described the role of surface
thermodynamics for the synthesis of polymer particles with a variety
of wetting/dewetting-controlled morphologies. This same approach
was more recently also used for microfluidic particle generation
[7,94,95].
Torza and Mason's study is the basis for the understanding of the ad-
ditional effects of fluid flow, interparticle forces and the actual volumes
of the two droplets (or the shell and the core droplet). These effects
were later discussed in several articles in the 1980s by Johnson, Sadhal,
and coworkers [96]. These authors additionally discussed the role of the
volumes present for each phase (shell and core drop).
In additional to fluid rheology effects, the role of the actual flow pro-
cess also influences the formation of compound drops. To illustrate this
effect, Fig. 6 shows two different flow configurations, with experiments
performed using identical fluids (fluids: (i) an oil drop, (+)-carvene,
rising from a stainless steel capillary, (ii) a complex coacervate phase
as shown in the previous figures formed from gelatin and Acacia gum,
and (iii) the aqueous coexisting solvent that has been kept in equilibri-
um with the coacervate phase; in all experiments shown in Fig. 6, the
optical setup is placed in a transparent thermostated glass cell kept at
T = 50°C (cell inner diameter 9.5 mm). In the first experiment (top
row of images), the oil drop is retained at the rising steel capillary and
is in contact with the solvent. The coacervate phase, also kept at 50 °C,
is injected from the top at varying flow rates.
If the flow rate of the coacervate thread is increased above a critical
volumetric flow rate, the flowing coacervate thread begins to fold, rath-
er than to increase its thread diameter. The folding patterns [97,98] are
similar to some of those observed with fluid threads formed in miscible,
but highly viscous fluid pairs by Cubaud and coworkers [99–102]. Due
to the low viscosity of the continuous phase the timescales are shorter
and folded morphologies only last for times of the order of a few tenths
of a second. Folding of the coacervate thread flowing downwards onto
the oil drop is favored over wetting/coating of the coacervate phase.
This behavior is determined by the overall balance of interfacial energy
between the three fluids, the viscosities of the coacervate phase and the
solvent, and the flow rate of the coacervate thread. No core/shell struc-
ture is formed at any of the flow rates. Although the coacervate estab-
lishes contact and wets the oil drop, it simply flows downwards and
easily de-wets the oil/solvent interface.
In the second set of experiments, shown in the bottom row of images
in Fig. 6, the optical cell is filled with the molten coacervate phase to a
level just above the oil drop. In this experiment, the (+)-carvene oil is
injected and made to detach from the capillary. As shown in the figure,
the detached oil rises upwards through the molten coacervate phase,
 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91 85

a b

c
180
θapp (o)

135

intermediate regime:
90 - fluid viscoelasticity
gel elasticity - interfacial energy interfacial energy
dominates - flow (e.g. gravitational sagging) dominates
25 30 35 40
T (oC)

Fig. 4. Three-phase wetting behavior in coacervate/water/oil systems. (a) Typical macroscopic appearance of a liquid oil drop in contact with the interface between a coacervate substrate
below its gelation temperature and the aqueous coexisting phase. Apparent contact angles are typically far above 90° (here: 135°). The oil used here (eugenol) has a higher specific density
than the aqueous phase and forms a sessile drop. (b) Evolution of the apparent contact angle of an initially spherical, gelled bead of coacervate resting on a PTFE support immersed in the
aqueous coexisting solvent during a slow change in temperature. (c) Apparent contact angle θapp obtained from the same images. The evolution of θapp with increasing T is in parallel to the
disappearance of elasticity revealed by the rheology experiments. Scale bar: 1 mm.

4.10–4 d
d (tc - t)· / 0

3.10–4
d (m)

2.10–4

1.10–4

0
0.0 0.5 1.0 1.5 2.0
t (s)

Fig. 5. Capillary thinning dynamics of a coacervate thread in contact with its coexisting aqueous solvent; the polymer-rich phase has previously been formed by complex coacervation with
gelatin and Acacia gum, separated by sedimentation and reinjected into the polymer-depleted water phase. The temperature is T = 60 °C, which is above the gelation temperature of the
protein. In first approximation, the rate of thinning of the coacervate filament is controlled by the radius of curvature, the coacervate/water interfacial tension, and the viscosities. The linear
decrease of the radius of the coacervate filament with time suggests that a Newtonian fluid model can be used to describe the behavior [89]; since an apparent shear viscosity η0 can easily
be obtained from independent measurements, the data shown here can be used to extract an estimate for the coacervate/solvent interfacial tension σ from the viscocapillary time scale
tvc = η0R0/σ. Image width for each frame: 8 mm. Scale bar: 0.5 mm, time step between images shown: 0.25 s.
86 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91

c
Fig. 6. Hydrodynamics in three-phase coacervate/oil/water systems. Oil drop brought into forced contact with a liquid coacervate phase. The images show a drop of limonene oil rising
from a steel capillary immersed into a salt solution. The heated coacervate phase is injected from a second capillary on top of the measuring cell. (a) An initial large drop of liquid coacervate
phase is formed. The large coacervate drop sediments, widens, and comes into contact with the oil drop, rolls past the oil drop, leaving behind an extended thread of the coacervate phase.
(b) As the flow rate of the coacervate phase is increased, the stream does not spontaneously coat the oil/water interface but flows past the oil drop. A coacervate stream flowing at a faster
rate starts to fold but still does not spread on the oil. (c) Oil drop pinching off from a capillary into a heated coacervate phase, penetrating the coacervate/solvent interface, dragging behind
a coacervate stream in its wake. Coacervate phase in all examples: gelatin/Acacia gum.

and pushes through the coacervate/solvent interface while retaining a
gradually thinning coacervate film at its front. After penetration of the
coacervate/solvent interface, a compound drop remains, leaving behind
a thinning coacervate thread in its wake. The comparison of these two
examples demonstrates that three-phase wetting in coacervate com-
pound drops strongly depends not only on interfacial thermodynamics,
but also on the character of the flow process. We note that this second
type of flow has also been described in the literature for encapsulation
[103].
5. Fluid dynamics of compound drops
The core/shell structures of coacervate/oil or coacervate/solid drops
have already been discussed since the first half of the 20th century from
the technological [104], colloidal [19,20,66], and biophysical [105] per-
spectives. In contrast, interest in the fluid dynamical aspects of core/
shell liquid drops has only developed later; an initial wave of studies
was initiated by Mason and coworkers in the late 1960s and 1970s.
They investigated equilibrium configurations, as well as spreading, de-
formation and coalescence of immiscible compound drops [106–110].
Only later on, in the 1980s, full fluid mechanical analyses were pub-
lished by Johnson, Sadhal and coworkers [96,111–113]. In the vein of
historic analyses on translating simple drops [114–116], these studies
first focused on spherical geometries. Stone and Leal [117] presented
an analytical solution using a perturbation method [118] for the small
deformation behavior of core/shell drops, and applied the boundary in-
tegral method to larger deformations. More recent studies have mostly
focused on computational approaches [119–121].

Fig. 7. Scheme and examples of interacting three-phase systems droplet 1/droplet 2/solvent, following the classical paper by Torza & Mason [110].
 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91 87

Fig. 8. Theoretical wetting state diagrams for a coacervate/oil/water system. Each subplot shows the feasibility of encapsulation based on interfacial equilibrium thermodynamics as a func-
tion of the interfacial tensions oil/coacervate and oil/water (σoil/coa,σoil/w, shown on the axes of the plots) for a given value of the coacervate/water interfacial tension (σcoa/w, constant for
each subplot). Boundaries between the different colored regions are made to appear diffuse to emphasize experimental uncertainty in measuring ultralow interfacial tensions. Note that
realistic values of coacervate/water interfacial tensions are below 1 mN/m.

5.1. Partial coverage — drops with ‘caps’ 5.2. Fluid dynamics of fully encapsulated compound drops

Sadhal and Johnson [112] provided an exact solution for Stokes flow
past bubbles and drops that are partially coated with a thin, stagnant
film in the limit of spherical drop configurations. In particular, those au-
thors provided results for the drag force as a function of the size of the
stagnant cap of immobile film and of the capillary number. Additionally,
the authors extended their study to the corresponding problem of drops
covered with larger fluid caps with internal circulation [96,111]. One
interesting result in the context of encapsulation processes is that the
thickness of a macroscopic fluid cap on a primary drop under flow
depends on the viscosity of the surrounding medium, rather than on
the viscosity of the primary drop.
To describe the flow of ‘capped droplets’ (assuming the shell is still
liquid-like and not yet a gel), the Navier–Stokes equations need to be
solved for each of the three phases i = o,w,c, and appropriate boundary
conditions at the interfaces oil/coacervate, coacervate/water, and – in
case not all the oil droplets are covered with coacervate – oil/water
must be specified.
Since the structure is axisymmetric, the drag force follows directly
from the stream function [122]. For the full expressions of the stream
functions for the different drop geometries we refer to the literature
for the cases of clean drops [114,115,118], drops with a rigid cap
Sadhal and Johnson [112], or fully encapsulated compound drops
[113,123,124]. Curves for the normalized drag force Fd on compound
drops with a rigid cap are shown in Fig. 10. Fd is shown for a range of
drop-to-continuous phase viscosity ratios ηd/ηc and for varying angles of
coverage with the cap φ, measured in radians in the forward apex direc-
tion of the drop. Two limiting values found: at small coverage angles, the
drag force approaches that of a clean drop, identical to the Hadamard–
Rybczynski solution [114,115]. For fully covered drops (φ → π), or for
extremely high relative drop viscosities, Fd approaches the Stokes solu-
tion for the drag force on a solid sphere.
We now move from the ‘capped droplet’ geometry to fully encap-
sulated core/shell droplets. Although this geometry appears simpler
at first sight, a different coordinate system is necessary to solve the
Stokes equations: following the classical approach used for two
interacting spheres in creeping flow by Stimson and Jeffery [125] in
1926, Sadhal and Oguz [113] showed that the flow field in and around
compound droplets can be described analytically using a bipolar coordi-
nate system.
The translation of spherical core/shell drops under creeping flow
conditions was studied by Rushton and Davies [124], motivated by
applications in membrane separation processes, where the selective ex-
traction of one liquid into a second immiscible liquid is of interest.
Sadhal and Oguz [113] found analytical solutions for the flow field of
core/shell drops in the limit of spherical shapes at small capillary num-
bers. They provided a parametrization of the geometry using bipolar co-
ordinates following the classic study by Stimson and Jeffery [125] on the
flow of two interacting spheres, and gave expressions for the stream
functions, translational velocity and the drag force on the compound
drop. In particular, these authors studied the effect of the eccentricity
of the core liquid on the flow behavior, including the streamlines of
the flow in all three phases, and also provided a stability analysis.
We note that in the examples discussed herein, the shell of the liquid
capsules is relatively thick; for thin shells in combination with relatively
large core diameters, hydrodynamic instability of thin films becomes
important [126,127].
When the oil/water interface is coated with the polymer-rich phase,
it is typically already covered with a rigid polymer adsorption layer
[128,129]. Such interfaces behave differently from those stabilized
with small-molecular weight surfactants because the bulk stresses are
no longer balanced by the interfacial tension alone, but interfacial
shear and dilatational stresses [70,130–135].
88 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91

5.3. Deformation and fragmentation of compound drops
Most analytical solutions for the flow of compound drops require the
drop shape(s) to be spherical. In addition to the analytical solutions
summarized above, most studies on the flow of core/shell drops now
involve one of the available methods of computational fluid dynamics
for free surface flows, typically focusing on the low Reynolds number re-
gime (Stokes flow). Numerical simulation has become popular because
the analytical treatment and interface parametrization of two concen-
tric liquid interfaces that move and deform simultaneously are quite
challenging already at small deformations (Fig. 9).
From the analytical side, description of the small-deformation be-
havior has been achieved using perturbation methods [117,136].
Stone and Leal [117] provided analytical solutions for the behavior
of core/shell droplets in linear flows for the limiting case of small
deformations; for finite interface deformations, they performed nu-
merical simulations using the boundary integral method.
A combined Eulerian–Lagrangian technique was used in a computa-
tional study by Kan et al. [137] focusing on the deformation and recovery
of a core/shell droplet in an extensional flow field. These authors used the
ratio of the two time scales defined from the ratio of viscosity and capil-
lary pressure both for the inner core and the outer drop to assess the de-
formation behavior of the drop. They found that sufficiently deformed
core/shell drops behave like simple, homogeneous drops if these two
time scales are comparable, but found different relaxation stages defined
by the core and the shell if the two time scales are different.
Toose et al. [138] simulated the deformation of non-Newtonian
compound drops in axisymmetric flow fields using a 2D boundary inte-
gral method; an Oldroyd-B fluid model was used and the effect of the
non-Newtonian character of the outer membrane layer of the drop on
the breakup behavior as studied.
Further extending the range of capillary numbers to include the
breakup regime, Smith et al. [119] numerically solved the equations of
motion for core/shell drops in shear flow with a level set method
[139] to describe the interface trajectories. These authors assembled a
phase diagram for the different resulting droplet morphologies follow-
ing breakup using the Capillary number and the ratio σi/σo, where σi
and σo are the interfacial tensions of the inner and outer interfaces.
The breakup of compound liquid threads (which ultimately results in
the formation of core/shell droplets) was investigated in a comprehen-
sive study by Craster et al. [140] using asymptotic analysis, linear stabil-
ity analysis and numerical simulation.
Feng's group uses a two phase, diffuse-interface approach
[120,121,141] with a variational framework to model droplet flows
(in this two-phase model, the core and the outer phase are the same
fluid). In it, the classical, ‘sharp’ interfacial stress boundary condition
is replaced by a diffuse interface term G∇ϕ, where G is the chemical
potential expressed as a function of the three parameters (i) interfacial
energy density, (ii) capillary width, and (iii) the phase field parameter
ϕ. These authors successfully applied the finite element method
with adaptive meshing to simulate the deformation of core/shell drops
flowing through a contraction geometry [142]. Using this approach,

Analytical:

Zero Deformation (Spherical Compound Drops) Small Deformation (First Order)

Stream function Shape of

interfaces

Drag force
Kinematic
condition
Rushton & Davies [124]
Johnson et al. [111-113, 123] Stone & Leal [117]

Numerical:

Boundary Integral Method (BIM) Level Set Methods Cahn-Hilliard/Diffuse Interface Approach

BIM solution to quasi-steady Stokes equation: Momentum balance Momentum balance incl. diffuse interface term

Kinematic condition Equation for level set function L Phase field (or: concentration field c)

Stone & Leal [117] Smith et al. [119] Chemical potential

Toose et al. [138] Chang et al. [139]

Park & Anderson [144]

Feng & coworkers [120, 141-143]

Fig. 9. Overview of the main methods used in the literature to investigate the fluid dynamics of core/shell drops, organized into analytical (top row) and numerical (bottom row) ap-
proaches along with key references. All methods start with the continuity equation ∇ ⋅ v = 0 and momentum balance; for the analytical approaches the Stokes equation is shown, where-
as for the numerical methods we show the full Navier–Stokes equations as in the original publications, but with slightly modified notation for consistency of presentation. Zero
deformation theories [111,112,124] provide information on streamlines, translation velocity, and drag force. Ψi is an exemplary stream function [124] in phase i, A–D are coefficients de-
termined from the boundary conditions. Asymptotic analysis for small deformations involves solution of the shape for the interfaces along with the kinematic condition dxs/dt. The drop
shape coefficients A12 and A23 for the inner and outer interfaces are a result of the analysis [117]. The Boundary Integral Method (BIM) allows to solve the Stokes equation numerically for
larger deformation via a set of coupled integral equations [117,138]. The Level Set [119,139] and Diffuse Interface methods [144–146] both allow to predict deformation and breakup of
compound drops in significant detail. Symbols used: v: velocity, v∞: far field velocity, p: pressure; η: viscosity, x, y: position vectors, n: interface unit normal vector, r: radial coordinate, κ:
ratio inner/outer undeformed drop radius, E: rate-of-strain tensor, Ti: shear stress in phase i, J, K: BIM kernels [117], Re: Reynolds number, F: body force, Li: level set function, ϕ: phase field
variable [142], μ: chemical potential, M: mobility parameter [144], f: specific free energy, ϵ: gradient energy parameter [144], c: concentration, N: number of fluids (here: 3). The index i
identifies one of the three fluid phases (i = 1,2,3).
 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91 89

a b

1.4

Fd / (4 v R)
d/ c

1.2 d/ c = 10
d/ c =1
d/ c = 0.1
d/ c = 0.001
1.0

0 1 2 3
(-)
c d
2.2

Ca (-)

0.4
0 0.5

core/shell
/ shell/continuous
(-)

Fig. 10. (a) Illustration of flow patterns in the absence of deformation (shape is postulated to be spherical); from ‘clean’ drops to core/shell drops in a homogeneous flow field. Left and
middle: drop with a sta\gnant interfacial region; right: fully enclosed compound drop surrounded by a macroscopic fluid layer. Streamlines plotted following the analytical work by
Johnson and Sadhal [96] for spherical drops covered with a cap and compound drops. Flow direction of outer fluid is upwards. (b) Drag force Fd on a compound drop [112] as a function
of the cap angle for varying drop/continuous phase viscosity ratios ηd/ηc. v∞: far field velocity, R: drop radius, φ: cap angle (in radians). (c,d) Sample results from the literature for the sim-
ulation of deformation and breakup of compound drops, as investigated by Smith et al. [119] (data replotted, with permission). Ca: capillary number; σi: interfacial tensions.

Zhou et al. [142,143] also performed detailed numerical studies on the
formation of compound drops formed from concentric channels in
flow-focusing type geometries. In particular, these authors used the
adaptive meshing/diffuse interface technique to construct a morphology
diagram for compound droplet formation, predicting morphologies as a
function of the Capillary number, flow rate ratio and viscosity ratios.
Full three-phase simulations with a diffuse interface model were
used by Anderson's group [144] to predict the formation of core/shell
drops in axisymmetric flow-focussing geometries. They solved the
Navier–Stokes/Cahn–Hilliard model [145,146] for three immiscible,
Newtonian fluids using a finite element method. The four governing
equations are the mass and momentum balances, a composition
equation, and a difference equation for the chemical potential. For the
finite element solution using a velocity/pressure formulation, the latter
two equations are first solved at each time step and are then used to
solve the flow problem. For the Cahn–Hilliard approach, the interfacial
thermodynamics as described above for coacervates follows from the
model's free energy parameters; these derive (in principle) from the
phase diagrams of the systems studied, but for simulations they are
typically postulated such that core/shell configurations ensue.
6. Summary and conclusions
The core/shell structure of complex coacervate compound drops
or capsules is not formed by direct, spontaneous spreading of the
coacervate phase on the oil drops, but rather by successive buildup of
a shell layer by deposition and fusion of individual coacervate nodules.
Complex coacervation forms two liquid phases: a polymer-rich coacer-
vate phase and a dilute continuous solvent phase. If a third liquid or
solid phase in the form of disperse oil droplets is present, the coacervate
phase tends to wet the oil/water interface. Here, we discussed the con-
nection between wetting phenomena and fluid viscoelasticity in coacer-
vate/oil/water systems from the perspective of both colloid chemistry
and fluid engineering. An important point to take into account is the
non-Newtonian rheology of typical protein-based coacervates used in
practically relevant delivery systems. It influences not only the fluid dy-
namics of the encapsulation process, but also the physicochemical mea-
surements that depend on the viscosity. In particular, the interfacial
tension between coacervate phases and their coexisting solvent is
known to be orders of magnitude lower than typical oil/water gas/liquid
interfacial tensions. Recent new methods for nanomechanical capillary
force measurements have led to new insight on the interfacial tension
of coacervates. In this article, we also outlined how quantitative analysis
of the capillary thinning dynamics of liquid threads can potentially be
used to estimate the interfacial tension in coacervate/water systems.
For the capillary thinning method, the fluid rheology must be known.
This point is also a conceptual advantage: it forces the user to directly
address the question of coacervate viscoelasticity and gel formation,
whereas in nanomechanical methods (AFM, surface force apparatus)
these important effects are obscured since they are not included in
the force balance used for data analysis. For typical coacervates formed
by gelatin as the protein and Acacia gum as the weak polyanion, the
temperature-dependent rheology appears to be dominated by the pro-
tein component above, around, and below the gel point. A wetting state
90 G. Dardelle, P. Erni / Advances in Colloid and Interface Science 206 (2014) 79–91
analysis for compound drops based on equilibrium surface thermody-
namics is the basis to understand wetting and coating of coacervate/
oil/water systems, but those approaches do not yet account for rheology
and fluid dynamical effects. Deformation and breakup of core/shell
compound drops are governed by the three viscosities and their ratios,
the two interfacial tensions, and the relative and absolute sizes. In the
simplest approach for experiments and analytical or computational
modeling, these properties can be written as a Capillary number for ei-
ther the inner or outer interface (i.e. for one fluid pair) and a ratio of in-
terfacial tensions or viscosities, while keeping the ratios of the other
fluid pair constant. Predictions of the deformation and breakup behav-
ior using analytical approaches (asymptotic analysis and perturbation
methods) are more challenging for compound drops than for simple
drops (geometrical parametrization of the two concentric or eccen-
tric interfaces can become tedious even for the seemingly simply
case of near-spherical drops). Therefore, recent work on the multi-
phase fluid dynamics of compound drops has focused on computa-
tional methods, including boundary integral or diffuse interface
approaches.
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