Current Opinion in Colloid & Interface Science 13 (2008) 206 – 216

www.elsevier.com/locate/cocis

Controlled production of emulsions and particles by milli- and

microfluidic techniques ☆
W. Engl a , R. Backov b,1 , P. Panizza c,⁎
a
Department of Chemical Engineering, Yale University, P.O. Box 208284 New-Haven Connecticut 06520, USA
b
Centre de Recherche Paul Pascal, UPR CNRS 8641, 115 Avenue A. Schweitzer, 33600, Pessac, France
c
Groupe Matière Condensée et Matériaux, UMR CNRS 6626, Université Rennes 1, Campus Beaulieu, 35000, Rennes, France
Received 14 July 2007; received in revised form 10 September 2007; accepted 19 September 2007
Available online 26 September 2007

Abstract

The recent developments of soft lithography and microfluidic techniques now permit the manipulation of small quantities of fluids with very
good control and reproducibility. These advances open a new “bottom-up” route to emulsification that paves the way to the fabrication of
calibrated hierarchically organized emulsions and particles. In this article, we describe the microfluidic techniques elaborated for engineering
emulsions and new dispersed materials and discuss their advantages over “top-down” approaches. We review and comment the high potentialities
these techniques offer to emulsion and colloid science, to the development of high-throughput set-ups for chemistry, physics and biology. We
illustrate them through a few examples taken from the current literature.
© 2007 Elsevier Ltd. All rights reserved.

1. Introduction necessity. From a practical point of view, monodispersity also

Emulsions are metastable dispersions of one fluid in another
immiscible. They are ubiquitous to our daily life since they con-
cern many areas, as different as the food, paints, pharmaceutical,
polymers, colloids or oil industry, where they occur either as end
products or during the processing of products [1,2]. As end
products, emulsions enable to avoid using organic solvents when
processing hydrophobic coatings for paints, to vehicle viscous
dispersed phases or to encapsulate, transport and vectorize active
molecules. In product processing, emulsion droplets can also be
used as reactors to engineer hierarchically organized dispersed
materials such as for instance mesoporous silica capsules, polymer
and ceramic spherical particles. Since most physical properties of
these materials are size dependent, controlling their monodisper-
sity as well as their uniformity in shapes and composition is a
☆
Major recent advances: Microchannel technology is a new “bottom-up”
approach for emulsification and colloid science. Recent advances in scaling up
droplet production and dimensions of microdevices yield promising prospects
for transposing this technique into Industry.
⁎ Corresponding author. Tel.: +33 223235700; fax: +33 223236717.
E-mail addresses: will.engl@yale.edu (W. Engl),
backov@crpp-bordeaux.cnrs.fr (R. Backov), pascal.panizza@univ-rennes1.fr
(P. Panizza).
1
Tel.: +33 556845630; fax: +33 556845000.
1359-0294/$ - see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2007.09.003
enhances emulsion stability. As a result of many years of research,
several emulsification techniques that produce emulsions with
narrow droplet size distributions now exist. The proper choice of
the process conditions is dictated by the value of the droplet mean
size to reach. Thus, well calibrated fine (50 nm to 1 μm) emulsions
are industrially produced by high-pressure microfluidic injection
[3], whereas droplets of intermediate sizes (1 to several μm) are
obtained using narrow gap shear devices [4]. All these “top-down”
techniques handle huge quantity of droplets at the same time. In
contrast, the recent advents made in microtechnologies and in
microfluidics [5] these last few years, now open a new “bottom-
up” approach to emulsification. The goal of this review is to
1) describe and understand the numerous advantages such a
methodology presents, and 2) discuss the numerous prospects it
opens for material science and science. We first describe the
various microfluidic devices and their flow configurations used to
produce calibrated droplets.
2. Microfluidics: a new “bottom-up” approach
to emulsification
The high potentialities of the microfluidic fabrication ap-
proach stem from the possibility to generate highly monodisperse
 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216
droplets, one at a time with an incomparable degree of control
over size. This method leads to extremely narrow-sized dis-
tribution since no stabilization over coalescence is needed as
collisions between droplets are suppressed during the droplet
formation process and the transport in the channels.
2.1. Droplet production
Several microchannel techniques exist to generate calibrated
droplets depending on the type of technology used for the
fabrication of the microfluidic devices. They are depicted in
Fig. 1. With planar chips, designed using soft lithography or
laser etching fabrication methods, two main configurations
are now commonly used. Periodic trains of monodisperse
droplets can form by colliding two immiscible fluids streams at
a T-shaped junction (Fig. 1a) [6,7] or by using a flow focusing
microdevice (FFD) where a 2D planar co-axial stream is forced
to flow through a small orifice (Fig. 1b) [8]. With both con-
figurations, experiments can be performed either by imposing
the flow rates or the pressure drop of the various streams. In
each case, the mechanism of droplet formation which results
from a subtle interplay between confinement, viscous and
capillary stresses leads to the production of periodic trains made
of monodisperse droplets with extremely narrow size distribu-
tion. The mean droplet size can be fine-tuned by adjusting the
flow parameters of the various streams from 10 μm, typically
the lateral size of the channels used for the experiment, up to a
few hundreds of microns. It decreases with the flow rate and
Fig. 1. Shown are different strategies used to generate monodisperse emulsions droplets one by one and images of the droplets obtained with these techniques: a) T
junction in planar microfluidic devices, b) flow focusing microfluidic device and c) double capillary millifluidic set-up.
207
viscosity of the continuous phase and increases with the flow
rate of the dispersed phase [9–11]. The dispersion in droplet
size is extremely low as the coefficient of variation (CV) de-
fined as the ratio of the standard deviation of the droplet size
over the mean size is typically lower than 5%. To decrease the
droplet size, one may break the drops into controlled daughter
droplets at a simple T junction [12] or at a junction of any
arbitrary angle [13]. This passive method of break-up is very
powerful since the size ratio of daughter droplets can be ad-
justed by modifying the hydrodynamic resistances of the two
junction's outlets. It can be carried out in succession without
increasing the polydispersity of the droplets until their dimen-
sions are larger than the channel dimensions.
A drawback of planar devices is that prior to droplet for-
mation, both the to-be-dispersed and the continuous phases are
in contact with the channel walls. It follows that the wetting
properties of the materials constituting the channels play a key
role since they control the nature and stability of the droplets
with respect to phase inversion [14,15]. Thus, when oil pref-
erentially wets the channels, as for instance with polydimethyl-
siloxane (PDMS) based microdevices, stable O/W droplets
cannot be prepared. To avoid this problem, it is necessary to
modify the wetting properties of the channels at the location
where droplet are formed for instance by applying a specific
surface treatment [16,17].
Droplets with comparable narrow size distribution can also be
generated with non-planar microfluidic devices which do not
necessitate any expensive technologies such as soft lithography
208 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216

or laser etching techniques for their design. One may thus extend
the flow focusing method to 3D, by injecting the disperse fluid
with a syringe pump through a capillary tube with an inner
diameter of typically a hundred microns, inside a chamber
pressurized by a continuous supply of another immiscible fluid
[18,19]. When the tip of the feeding capillary tube faces the
small exit orifice of the chambers, the outer fluid stream focuses
and forces the injected disperse fluid to exit the chamber through
the orifice producing a microjet. As a result of a capillary
instability, the microjet then breaks up into a chain of nearly
monodisperse droplets, much smaller than the exit orifice.
Monodisperse drops in larger sizes can also be generated
using double capillary devices, by injecting the disperse phase
through the co-flowing matrix fluid (Fig. 1c) [20–23]. The set-
up consists of a blunt calibrated needle with a diameter φ of
typically a few hundreds of micrometers, centred to a cylindrical
glass capillary with a diameter of D ≥ φ.Using independent
syringe pumps, two immiscible fluids are respectively infused
through both the needle and the annular gap between it and the
internal capillary wall. The flow rates are independently con-
trolled and adjusted in order to form monodisperse droplets of
the dispersed phase in the continuous one. Both W/O and O/W
droplets can be prepared provided that the wetting properties of
the internal capillary wall are compatible with the continuous
phase. With glass surfaces, this can easily be done. Such devices
then allow the extension of the preparation of well calibrated
emulsions up to sizes of a few millimeters. Emulsions with
smaller sizes (typically a few tens micrometers) can be generated
by using a double capillary device which consists of a cylindrical
capillary tubes co-axially nested within a square glass [24••].
2.2. Fabrication of double emulsions
Microfluidic emulsification techniques offer a promising
route to the fabrication of monodisperse double emulsions and to
the tailoring of complex architecture. It is the only technique
which enables to encapsulate 100% of an active product in a
single step and to control the nature of the encapsulated objects.
To illustrate this, let us consider the fabrication of double emul-
sions, which consists of emulsion drops containing smaller
droplets inside. In batches, the fabrication process usually re-
quires two step processes: an emulsification of the inner droplets
in the middle fluid followed by a second emulsification for
dispersion [2]. In microfluidic planar devices, calibrated double
emulsions can be generated with a mere succession of two T
junctions as depicted in Fig. 2a [25••]. Aqueous droplets of
uniform size are formed at a T junction by colliding water and
oily flows. The resulting periodic train of W/O droplets is then
directed towards another T junction placed downstream, to form
monodisperse organic drops containing aqueous droplets within

Fig. 2. Shown are illustrations of the different microfluidic techniques used to produce double emulsions and corresponding images of emulsion droplets. I, M and O
stand respectively for the inner, middle and outer fluids. a) The two steps drop break-up method using a planar device. Photograph of the droplet formation mechanism
are reprinted from “Production of monodisperse double emulsions by two steps drop break-up in microfluidic devices”, Okushima S., Langmuir, 2004, 20:9905–9908.
with permission from ACS. b) 3D equivalent of the double step drop break-up technique using double capillary devices. Images of the droplets are reprinted from
“Controlled production of hierarchically organized large emulsions and particles using assemblies on line of co-axial flow devices”, Panizza P. et al., Colloids Surf. A:
Physicochem. Eg. Aspects (2007), doi:10.1016/j.colsurfa.2007.06.026 with permission from Elsevier and c) microcapillary device used to break-up concentric streams
and form monodisperse double emulsions or core-shells (images are reprinted from “Monodisperse double emulsions generated from a microcapillarydevice”, Utada
A.S. et al., Science, 2005, 308:537–541 with permission from AAS.
 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216
an external aqueous phase. The sizes of drops and inner droplets
can be fine-tuned independently by adjusting the flow rate
values of the various streams. Moreover, the number of en-
capsulated droplets can also be monitored independently
from their size and that of the drops. This can be achieved
by performing an additional injection or withdrawing of the
continuous phase between the two T junctions using another T
junction. This enables to dilute or concentrate the initial W/O
droplet train before its encapsulation without altering the droplet
size. From a practical point of view, double W/O/W emulsions
can only be prepared provided that the upstream and
downstream T junctions, used to form droplets and drops are
respectively hydrophobic and hydrophilic. O/W/O emulsions
are prepared by inverting the wetting properties of these two
junctions. This method is very versatile. It can successfully be
transposed to 3D as shown in Fig. 2b and extended to more
than two steps [26••]. W/O/W/O macroemulsions can then be
prepared using an assembly of glass double capillary devices
connected to each other by means of Plexiglas home-made
modules. A promising feature of this multiple steps emulsifica-
tion technique is the possibility to encapsulate in a same drop,
droplets of various compositions and to control their sizes and
respective ratio (Fig. 2a). When two droplet trains having the
same continuous phase but droplets of different composition
meet at a T junction, they form a periodic alternated train [27].
Monodisperse drops containing droplets of different composi-
tion are generated by injecting this droplet train through the
needle of another double capillary device placed downstream.
The size of the internal droplets, their respective number as well
as the size of the drops can be tuned continuously and in-
dependently by changing the flow conditions [25••, 26••].
Double emulsions can also be generated in a single step
process using a different strategy. The idea consists of desta-
bilizing a liquid thread of two or more parallel co-flowing
streams in order to form monodisperse drops containing
droplets (Fig. 2c). This can be achieved for instance in planar
microfluidic devices by forcing this liquid thread through the
small orifice of a flow focusing geometry [28 •• ]. A similar
approach has successfully been transposed to 3D by Utada et
al. Their device consists of two cylindrical glass capillary
tubes co-axially nested within an outer square glass tube and
tapered at their facing ends as depicted in Fig. 2c [24 •• ]
Three different fluids are simultaneously injected in the sys-
tem at controlled flow rates. The innermost fluid is pumped
through one of the inner tube, whereas the middle fluid is
injected through the outer square capillary region, in the same
direction. Since the outermost fluid is pumped through the
outer co-axial region of the opposite direction, all fluids are
forced through the exit orifice formed by the other inner
cylindrical tube. The thread breaks up to produce double
emulsion in the collecting tube. The size of the inner and
outer droplets as well as the number of inner droplets can be
monitored and varied with a very good degree of control.
This technique offers an incomparable step forward for the
production of core-shell droplets with a control over both
droplet size and shell thickness [29]. For instance, core-shell
droplets with a ratio of shell over size as low as 3% have been
209
prepared. By photopolymerizing a polymer in the interme-
diate fluid, these structures can be used to form capsules.
They can also be transformed into polymer vesicles by using
for the middle phase a volatile fluid where diblock co-poly-
mers are dissolved [30].
2.3. Towards the tailoring of complex dispersed materials
Synthesis of solid particles in planar microfluidic reactors is
an excellent route to particles with unconventional shape and
morphologies. In batches, dispersed materials obtained by using
droplets as microreactors are generally spherical systems since
the minimization of interfacial energy leads to spherical shapes
during most syntheses, whether they are polymer latexes formed
through emulsion polymerization or droplets formed using shear
flows in microfluidic devices. This inherent difficulty can
however be circumvented by using a microfluidic scheme which
permits good controls of the droplets geometrical and concen-
tration environments. In 2004–2005, several papers have thus
demonstrated the possibility to generate non-spherical particles,
such as disks, ellipsoids or rods by photopolymerizing monomer
droplets on the “fly” while flowing in constrained geometries as
illustrated in Fig. 3 [31–33]. Monodisperse monomer droplets
with different volume are first produced using a flow focusing
device by varying the flow rates of the continuous and droplet
phases. These droplets are then forced to flow through a narrow
channel in which polymerization takes place. Because of
confinement, droplets adopt a non-spherical shape, dictated by
a relationship between w and h, the two lateral dimensions of the
channel and d, the diameter of an undeformed droplet. At low
capillary numbers, for w N d and h N d, the droplets minimize
their surface energy by taking a spherical shape whereas for
h N d N w, and for situations where d N w and d N h, confinement
suppresses the relaxation of their shape into spheres, and the
droplets respectively deform into discoid or rod shapes. With
this approach, the aspect ratio of the non-spherical droplets can
be conveniently monitored by changing the ratio between the
droplet volume and the dimensions of the microchannels.
The fabrication of solid particles using continuous micro-
fluidic reactors exhibit many features that distinguish it from
batch polymerization of monodisperse emulsions produced by
“top-down” emulsification methods [2–4]. The polydispersity
of the solid particles obtained using microfluidic tools is com-
parable to that of the droplets prior to hardening, typically below
3%. This value is therefore much narrower than in the batch
methods, where coalescence and Oswald ripening occur. In
microfluidic reactors, no stabilization against coalescence of
monomer droplets is necessary since their collisions are
suppressed. Furthermore, polymerization in a confined geom-
etry allows for the production of non-spherical shapes such as
disks, rods or tubes with an independent and very good control
over volume, shapes and aspect ratio. The ability to generate and
to control composition gradients with microfluidic devices
offers a unique route to synthesize colloids with complex archi-
tectures. A good illustrative example of this concept concerns
the production of Janus particles obtained by breaking up a
liquid thread of two parallel co-flowing streams of monomer
210 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216

Fig. 3. Schematic (a–c) and optical microscopy (a′–c′) images of particles obtained from with polymerization of deformed monomer droplets with different shapes:
microspheres (a, a′), disks (b, b′) and rods (c, c′). Reprinted from “Continuous microfluidic reactors for polymer particles”, Seo M. et al., Langmuir, 2005, 11614–11622
with permission from ACS.

of two immiscible polymer solutions that is forced through a
narrow orifice (Fig. 4). The resulting droplets present a Janus-
like structure, with an approximate flat interface between the
adjacent polymer phases that can be solidified with an UV
exposition, performed downstream [34•]. This synthesis method
gives a precise control over the volume ratio of the constituent of
the particles as well as their size. It can also be extended to
generate ternary particles by breaking up a three parallel co-
flowing monomer streams.
The possibility to perform independent operations on indi-
vidual dispersed objects and to integrate them opens incom-
parable broad prospects for engineering new materials. Complex
architectures prepared along these lines are now flourishing in
literature. They include the fabrication of colloid-filled hydrogel
Janus granules of tunable size, geometry and composition, the
encapsulation of solid particles in liquid drops or the production
of non-spherical objects with liquid compartments. Consider for
instance, the fabrication of colloid-filled non-spherical Janus
granules reported by Shepherd et al. [35]. It necessitates several
operations. To start, monodisperse colloid-filled hydrogel Janus
droplets are produced with a flow focusing device according to
the method previously described, the two hemispheres of the
droplets differing by their composition in colloids. These spher-
ical droplets are then deformed, by flowing through a con-
strained geometry, while being photopolymerized.
2.4. Turning microfluidic emulsion technology into an industrial
tool
Microfluidic technology paves the way to a bottom-up ap-
proach to emulsion science that offers numerous prospects
compared to the “top-down” techniques that handle large pop-
ulations of droplets at each step of an industrial process.
However, its impact in industry relies on the ability to generate
high throughput. So far, it is limited because of the extremely
small flow rates involved (typically of the order of 0.1 ml/h) in
such devices. The formation rate of monodisperse droplets in a
single FFD is only a few tens of droplets/s. The necessity to
parallelize droplets generators such as FFD or T junctions is
therefore the central issue for potential industrial applications.
From a practical point of view, this issue turns out to be a real
difficult task which raises numerous theoretical questions. By
parallelizing devices with multiple nodes, branches and cross-
flows, one couples non-linear fluidic oscillators. At low Reynold
numbers, monophasic flows of Newtonian fluids in a network
made of channels are governed by linear equations since the flow
rate of a fluid flowing through a channel is proportional to the
pressure drop applied to the extremities of this channel. Such
interconnected flows can be solved using an analogy with
resistors electrical circuits and do not present any difficulty. In
contrast, multiphase flows of immiscible fluids are highly non-
 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216 211

Fig. 4. (a) Sheath-flow microfluidic device used to produce monodisperse colloid-filled hydrogel granules. b) Schematic representation of the granules shapes and
composition. c) View of the parallel two streams prior to their dispersion in droplets. d) Formation of Janus droplets. Reprinted from “Microfluidic assembly of
homogeneous and Janus colloid-filled hydrogel granules”, Shepherd R.F., Langmuir 2006, 22:8618–8622 with permission from ACS.

linear. Understanding such flows in hydrodynamic networks is a
challenging problem in the field of hydrodynamics and non-
linear physics. Take for instance, a situation where a train of
droplets or bubbles is directed towards a T junction and ask how
the droplets and carrier phase divide between the two outlets
[23]. When a droplet reaches the junction, two directions are
possible if it does not break. The selection is triggered by the
dominant stream so that the droplet flows into the outlet
characterized by the lower hydrodynamic resistance. Since the
presence of droplets in conducts increase the resistance to flow,
there is a hydrodynamic feedback between choices of successive
droplets. The outcome turns out to be a complex non-linear
dynamical problem which may lead to chaos or quasiperiodicity.
With such effects, producing droplets in parallel microfluidic
devices yields to emulsions with large polydispersity [36].
A possible way to circumvent this difficulty of paralleliza-
tion is to generate droplets without applying cross-flows. In the
last two years, large efforts have been undertaken along this
line by Nakajima's group in Japan [37•• ,38]. They have
conceived and developed two different microchannel array
devices able to generate monodisperse droplets with a pro-
duction rate increased by a factor 100 and more with respect to
single channel devices. The first device is a silicon micro-
channel (MC) array plate with a multilevel structure. The
method consists of forcing the to-be-dispersed phase through
an array made of several hundreds of parallel channels into a
shallow well, filled with the continuous phase as depicted in
Fig. 5 [37•• ]. This MC array plate is capable of generating
monodisperse discoid droplets of O/W or W/O types without
applying a forced cross-flow of the continuous phase, up to a
thousand droplets per second. The other device consists of a
silicon array of about 10 4 asymmetric straight through-holes
vertically microfabricated on a plate surface of a liquid cham-
ber to supply the to-be dispersed phase [38]. Each asymmetric
through-hole is composed of a slit (with typical length, width
and depth values of respectively 100, 10 and 20 μm) and a
cylindrical channel (typically 10 μm in diameter and 5 μm in
depth). These through-holes are uniformly arranged with in-
tervals of typically 100 μm across the asymmetric straight-
through MC. The phase to disperse is injected through the
array of vertical channels into the horizontal module filled with
the continuous phase. This device can be applied to the
preparation of monodisperse emulsions as well as micropar-
ticles and microcapsules. Since the formation rate of droplets
from each active through-hole is typically a few tens of
droplets/s, this apparatus can produce up to 10 5 droplets per
second.
2.5. Scaling up microfluidics
Scaling up these microdevices into millimetric ones presents
some considerable advantages. Recently, a continuous co-axial
flow scheme to engineer and industrially produce at low cost
hierarchically organized structures of larger sizes with an in-
comparable degree of control over their size, shape and internal
structure has been developed (Fig. 6) [26••]. The method con-
sists of using an assembly of capillaries or flexible tubes (with
diameters ranging from 50 μm to a few mm) put together with
elementary home-made modules. This synthesis method is
based on the association of three different elements able to
achieve the basic following four functions used in microfluidic
devices: (1) form periodic trains of monodisperse droplets
with very good control over their size, (2) dilute–concentrate
these trains while keeping the volume of droplets unchanged,
212 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216

Fig. 5. Schematic illustrations of the two techniques based on microchannel arrays developed by M. Nakajima's group to scale up production of monodisperse droplets
and photographs of produced emulsions. a) The two level structures conceived to scale up droplet production is made of an array of several hundreds of parallel
channels. The to-be-dispersed phase is injected through the microchannels into the shallow well filled with the continuous phase. (Left) Images of successfully
generated O/W discoid droplets. Reprinted from “Controlled generation of monodisperse discoid droplets using microchannel arrays”, Kobayashi I. et al., Langmuir,
2006, 22:10893–10897 with permission from ACS. b) Mechanism of droplet formation using an asymmetric straight through-holes MC plate. (Right) An microscopic
photographs of the resultant droplets. Reprinted from “Novel asymmetric through-hole array microfabricated on a silicon plate for formulating monodisperse
emulsions”, Kobayashi I. et al., Langmuir, 2005, 21:7629–7632 with permission from ACS.

(3) generate periodic trains made of alternated droplets and
(4) deform droplets in a controlled manner. Modular millifluidic
set-ups can then be designed to produce newly controlled in-
tegrated architectures limited only by the number of combina-
tions possible and one's creativity. The great versatility of this
method is already illustrated through the encapsulation of drop-
lets or solid particles of various shapes, composition and size, in
liquid or solidified drops, the formation of large organic or
inorganic cylindrical particles as well as the generation of double
and triple emulsions. This strategy presents several advantages
over microfluidic synthesis while keeping its specificities. Since
no lithography, glass etching techniques or specific equipment
are necessary for the design of the devices, their fabrication costs
are low. The connecting capillary tubes and the various modules
can assemble and disassemble easily so that modular set-ups can
be designed on demand in a short time. This modularity is also
considerable advantage from a practical point of view since
modifying a hydrodynamic circuit on a planar microfluidic chip
demands starting over at the lithography or glass etching level.
Combined with the ability to modify very simply the wetting
properties of the glass capillary tubes used for connection
it offers the opportunity to fabricate multiple emulsions of
different nature with a same device. The use of such devices pave
the way to an industrial integrative formulation of dispersed
materials with very large characteristic sizes ranging from
typically 100 μm to several mm and new complex architectures
[39]. This should lead to the rapid emergence of new products in
cosmetics or food where the texture and visual aspect plays a key
role for sale.
3. Miniaturizing the laboratory using droplet-based
microfluidic devices
Monodisperse droplets generated by microfluidic devices
can serve as microreactors to compartmentalize reactions and
control the reaction time precisely [40]. One of the key
properties of droplet-based high-throughput microfluidic
devices stems from the uniform constant speed motion of
droplets in the channel allowing equivalence between distance
and reaction so that one can perform a stationary measurement
of a kinetic process along the flow. Using this property,
microfluidic platforms to perform kinetic measurements of
fast and very fast reactions with better than millisecond
resolution using very small volumes of reagents have recently
 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216 213

Fig. 6. (a) Sketches of the different elementary tubular millifluidic modules and their corresponding basic functions. b) Shown are schematic representations of the
different modular set-ups used to fabricate triple and double emulsions and images of emulsions produced with different number of internal droplets reprinted from
“Controlled production of hierarchically organized large emulsions and particles using assemblies on line of co-axial flow devices”, Panizza P. et al., Colloids Surf. A:
Physicochem. Eng. Aspects (2007), doi:10.1016/j.colsurfa.2007.06.026 with permission from Elsevier.
214 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216
been developed [40]. This microreactor technology is a very
efficient alternative to batch chemical procedure, because of the
rapidity of analysis and the low consumption of reagents.
Furthermore, other advantages results from the high heat and
mass transfer rates provided by microfluidic reactors which
induce safe and fast syntheses and therefore may open new
chemical reactions [41]. Briefly, the droplets are usually formed
at a T junction by using the to-be-disperse phase, streams of the
various reagents separated from each other by buffer streams in
order to avoid premixing. Rapid mixing of the reagent inside the
droplet is necessary since it determines the starting time of the
reaction. This is achieved by chaotic advection when the
droplets flow through a winding channel [42]. The composition
of the reaction mixture at the reaction time, t, is then determined
with spectroscopic techniques (UV–vis, Raman or Flurores-
cence) by analyzing the composition inside the droplets at the
distance d = tU (where U is the velocity of the droplet) within
the channel. Since the composition of reagents within each
droplet carrier can be changed by simply varying the flow rates
of the reagent streams, this technique can be used for screening
of a target. Using droplets as microreactors is not limited to
chemical reactions, but can apply to other fields such as for
instance enzyme kinetics, DNA analysis, synthesis of nano-
particles or protein crystallization. We advise the reader to refer
to the reviews written by R.F. Ismagilov to get more information
and precision on the use of droplets in these various fields
[43••].
Another interesting specificity of droplet-based microfluidic
devices is the possibility to rapidly carry out many experiments
(typically a few hundred per second) under the same
controllable conditions. These features are well suited to
study stochastic processes where many experiments are
necessary to accurately measure the probability of a single
event. A good example of this approach concerns, a droplet-
based set-up recently developed by Laval et al. to investigate
crystal nucleation kinetics [44•]. Monodisperse droplets of a
solution are produced, convected along a channel and then
rapidly submitted to a temperature quench so that nucleation
may occur. The nucleation rate is then determined by measuring
the probability that a droplet contains a nucleus at different
positions along the channel on a large number of droplets. This
technique presents numerous advantages over the classical
droplet methods using emulsions. They include the production
of monodisperse droplets of tunable size with no surfactant
molecule which may induce heterogeneous nucleation, the
rapidity of the temperature quench, the possibility to eliminate
interactions between multiple nuclei by choosing small enough
droplets and a fast and direct measurement of the proportion
of crystallized droplets. This continuous method yields to
rapid and reliable statistical measurements of the nucleation
kinetics, and offers the opportunity to carry out high-throughput
crystallization conditions [45].
The ability of microfluidic technology to produce, handle
and manipulate single droplet in a very controlled way opens
new prospects to study the physical properties and stability
of emulsions, at the scale of an individual or two droplets.
Along this line, a microfluidic interfacial tensiometer has been
conceived [46]. The method is based on quantitative real time
observation and analysis of drop shape dynamics in micro-
channels. Drops of controlled diameter and spacing are
produced at a T junction of two immiscible fluids and injected
in a wider downstream channel where they become spherical.
They are then deformed by flow constrictions. Measurements
are performed at the exit or entrance of a constriction where the
flow is respectively accelerating or decelerating, producing an
extensional flow that deform the drops. This tensiometer gives
very accurate and precise results, with very low reagent
consumption and rapidity. Because of the equivalence between
time and position along the channel, the age of the interface is
known, so that information on the dynamic surface tension and
kinetics of adsorption surfactant at the interface can be gained
by using multiple constrictions along the channel. With no
doubt, in the near future, microfluidic tools will be used to
investigate the coalescence between two droplets. Such a study
could for instance be performed by forming in a capillary tube
an alternating train of small and large droplets using a T
junction. Since in the downstream channel, the small droplets
are convected faster than the large ones, coalescence events
could therefore be observed and quantified.
An important research field now deals with developing
active techniques and new tools to handle droplets in
microfluidic devices.
4. Conclusion and prospects
Microfluidic technology offers a new “bottom-up” approach
to emulsification which shows much promise in the emulsion
field. By contrast to the “top-down” approach of other
emulsification techniques, which operate on a very large
number of droplets at each step, microfluidic generates one
single droplet at a time with incomparable results in terms of
size control. Its abilities to create chemical gradient and to
handle each produced droplet individually lay the foundation of
a new concept in colloidal science, that of Continuous
Integrative Chemistry. The novelty and originality of this
approach consists of using monodisperse droplet as individual
chemical reactor and operating “on line” on each reactor to
successively add a chemical or physical function at each step of
a process. This integrative approach is based on several
elementary functions that microfluidic tools can accomplish.
These basic operations include formation of parallel streams
with different composition, generation of monodisperse droplet
trains, dilution and concentration of these trains, formation of
alternated trains with droplet of different compositions,
asymmetric droplet breaking-up, fusion of two droplets,
controlled deformation of the droplets, and encapsulation. By
combining and integrating these various functions with
polymerization, solidification or any other chemical process,
it then becomes possible to synthesize new dispersed materials
with complex architecture. This methodology yields to a very
good control of the size, shape, and internal structure of the
manipulated objects, at each step of the process. It is for instance
the only technique that can ensure encapsulation of an active
product at 100% in a single step. Illustrative examples of the
 W. Engl et al. / Current Opinion in Colloid & Interface Science 13 (2008) 206–216
high potentialities of this approach are now numerous in
literature. They concern for instance double emulsions with
internal droplets of different composition, triple emulsions, non-
spherical particles, Janus or ternary particles and core-shells.
With no doubt, the further step to make is to combine
microfluidic and millifluidic formulation methods to generate
multiscale structured materials. By integrating these tools with
classical emulsification techniques, the fabrication of multiple
emulsions with four or five degrees of multiplicity and
hierarchical sizes ranging from the micrometer for the
innermost droplets up to typically a millimeter for the size of
the outer drops should in principle be feasible. However, despite
its numerous advantages, the microfluidic technology is not yet
suitable as a production tool for industry because of the very
small flow rate involved (typically of the order of a few
hundreds of microliters per hours) in this type of devices.
Consequently, a very important and active research work must
now be devoted to overcome this limitation since both industrial
and financial stakes are tremendous.
Generating monodisperse droplets with controllable sizes and
shapes and being able to manipulate them individually and
reproductively in networks of small channels give the oppor-
tunity to miniaturize a laboratory down to a few inches per
square [47, 48•]. This is the lab-on chip concept. Using droplets
as individual microcarriers and reactors in such devices is very
promising for developing high-throughput applications since
reaction conditions can easily be compartmentalized and ad-
dressable [44•]. This approach enables to considerably increase
and accelerate the number of tests up to a few tens per seconds,
using very small amounts of materials. The prospects are nu-
merous for many scientific fields where one target must be tested
against a large number of reaction conditions. In chemical
engineering, this continuous screening approach permits for
instance to explore the conditions of a reaction, to optimize it and
consequently to orientate the synthesis of new materials. For
biology, it permits to efficiently and rapidly test the effect of a
drug on viruses.
The possibility with droplet-based microdevices to rapidly
perform many experiments (typically a few hundred per second)
under the same controllable conditions also opens many op-
portunities to address fundamental issues. These tools are thus
well suited to study stochastic processes which necessitate a
statistical analysis such as for instance coalescence phenomena
or crystallization nucleation. In biology, such a digital high-
throughput technique may give access to the statistical dis-
tribution of a population as a function of a stress [49]. Finally, on
another level, flows of droplets occurring in microfluidic devices
raise challenging questions in the field of hydrodynamics and
non-linear physics [23,50].
To conclude, the recent progresses made in the production
of droplets of controllable size and in their individual manipula-
tion lead to novel approaches of emulsification and synthesis
of complex materials, and the foundation of new scientific
methods and applications in many different fields. Recent
advances in scaling up droplet production and the dimensions
of microdevices now allow to transpose these promising tech-
niques into industry.
215
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