J.

of Supercritical Fluids 47 (2009) 523–530

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

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

Review

Colloids in supercritical fluids over the last 20 years and future directions
Keith P. Johnston a,∗ , Sandro R.P. da Rocha b
a
Department of Chemical Engineering, Center for Nano and Molecular Science and Texas Materials Institute, University of Texas, Austin, TX 78712, United States
b
Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI 48202, United States

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

Article history: In this work, the history of colloids in supercritical fluids in the last two decades and future directions
Received 18 August 2008 in several promising areas are discussed. The primary focus of this article is on microemulsions and
Received in revised form 14 October 2008 emulsions, although new developments are described involving protein colloids, electrostatic stabilization
Accepted 15 October 2008
of inorganic particles and the use of CO2 as an antisolvent for separation of metal colloids. The focus on
the CO2 –water interface is related to the fact that, historically, the studies of colloids in supercritical
Keywords:
fluids began with microemulsions and emulsions, and then evolved to polymer latexes and inorganic
Compressible fluids
dispersions. Moreover, many of the same types of stabilizers have been used for the various types of
Supercritical CO2
Colloids
colloids.
Interfaces
© 2008 Published by Elsevier B.V.
Dispersions

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
2. Interfacial properties and surfactant design for microemulsions and emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
3. W/C and C/W microemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
4. W/C macroemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
5. Future directions in colloid science in supercritical fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
5.1. C/W emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
5.2. Protein colloids in CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
5.3. Electrostatic stabilization in low dielectric CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
5.4. CO2 as an antisolvent for processing of colloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
5.5. Particle stabilized emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529

1. Introduction
continuous phases. These emulsions may be phase separated eas-
Many nonvolatile solutes are insoluble in CO2 because of the ily for product recovery simply by depressurization, unlike the case
weak van der Waals forces and lack of a dipole moment. Thus, for conventional emulsions.
many recent advancements in supercritical fluid science and tech- The environmentally benign, non-toxic and non-flammable
nology starting in the late 1980s have utilized colloids in carbon fluids water and CO2 are the two most abundant and inexpen-
dioxide (CO2 ) to take advantage of insoluble phases such as water, sive solvents on earth. W/C or C/W dispersions in the form of
polymer latexes, metals and semiconductors. Whereas the solvent microemulsions and emulsions offer new possibilities in waste
strength of CO2 is limited, water-in-CO2 (W/C) and CO2 -in-water minimization for the replacement of organic solvents in fields
(C/W) microemulsions and emulsions have the ability to function including chemical processing, pharmaceuticals, microlectronics,
as a ‘universal’ solvent medium by solubilizing high concentrations for solubilization and separations (e.g., proteins, ions and heavy
of polar, ionic and nonpolar molecules within the dispersed and metals), particle formation, organometallic catalysis and synthesis
of polymer colloids and inorganic nanoparticles [1–4]. Additional
applications include photoresist drying [5,6] and cleaning of low k
∗ Corresponding author. dielectrics in microelectronics [7,8], emulsion-templating in poly-
E-mail address: [email protected] (K.P. Johnston). merisation [9], drug delivery [10], and enzymatic catalysis [11].

0896-8446/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.supflu.2008.10.024
524 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530

Table 1
Classes of colloids and stabilizers in low and high temperature supercritical fluids.

Colloid and supercritical fluid Stabilizing group

Water-in-alkane microemulsion Alkane [83]

(1988)
Water-in-CO2 microemulsion a. Alkane/fluoroalkane hybrid
(1994) [29,30]
b. Perfluoropolypropylene oxide
(<1000 molar mass) [12,84]

Polymer latex in CO2 (1994) Polymeric flouroacrylates and

siloxanes (high molar mass) [85]

Metal and semiconductor a. Perfluoropolypropylene oxide

nanocrystals in water/CO2 and alkane [31]
microemulsion (1999)
b. Perfluoropolypropylene oxide
[32]

Metal nanoparticle dispersion in a. Without stabilizer [86]

water (2000) Fig. 1. Schematic representation of the effect of formulation variables (x-axis) on
b. Alkane thiols [87] microemulsion and macroemulsion phase behavior and interfacial tension () of a
ternary water–CO2 –nonionic surfactant system. Cs stands for surfactant concentra-
Metal nanocrystal dispersion in Fluoroalkane thiol [33] tion.
CO2 (2000)
Gold nanocrystal seeds for Si Alkane thiol [88]
nanowires in alkanes and octanol surfactant tails in CO2 often leads to low solubilities [23,27] of the
at high temperature (2000) surfactants in the CO2 phase and weak steric stabilization [28].
Si nanocrystal dispersion in Octanol [89] Historically, the studies of colloids in supercritical fluids began
alkanes and octanol (high T) (2001)
with microemulsions and then evolved to polymer latexes and inor-
ganic dispersions. Many of the same types of stabilizers have been
Colloids including microemulsions, emulsions, polymer latexes, used for the various types of colloids. A variety of metal and semi-
proteins, and metal and metal oxide nanoparticles may be sta- conducting colloids have been stabilized in SCF CO2 and in both low
bilized in supercritical fluids (SCFs) with a variety of surfactants, and high temperature supercritical fluids as shown in Table 1 [22].
adsorbed and bonded stabilizing ligands, and particle stabilizers as One of the factors that enabled nanocrystal and nanowire chem-
shown in Table 1. A variety of low-molecular weight and polymeric istry in SCFs was the discovery of low molar mass steric stabilizers
surfactants have been designed for stabilizing microemulsions for colloids in SCF hydrocarbons and in carbon dioxide (Table 1).
[12,13], polymer latexes [14], emulsions [15–18], and inorganic sus- For example, fluoroalkane and oligomeric perfluoropolypropylene
pensions [19] as reviewed elsewhere [20–22]. oxide groups utilized in surfactant tails designed for water-in-
The primary focus of this article is on microemulsions and emul- carbon dioxide microemulsions [12,29,30] were also successful for
sions, although new developments are described involving protein the stabilization of metal nanocrystals in CO2 [31–33]. The tun-
colloids, electrostatic stabilization of inorganic particles and the use ability of SCFs may be used to achieve size control during arrested
of CO2 as an antisolvent for separation of metal colloids. Microemul- precipitation nanocrystal synthesis [28] and size-selective precip-
sion droplets are thermodynamically stable and typically 2–10 nm itation [28,34,35].
in diameter making them optically transparent, whereas kineti-
cally stable emulsion droplets and latexes in the range of 200 nm 2. Interfacial properties and surfactant design for
to 10 ␮m are opaque and thermodynamically unstable, as shown microemulsions and emulsions
in Table 2. Ironically, the early studies of the W–C interface focused
more on microemulsions [23] than macroemulsions, despite the The bulk phase behavior and curvature of an adsorbed surfac-
challenges of higher surfactant adsorption and lower  required for tant monolayer, and thus the nature and stability of the resulting
the former. Because of these challenges, large numbers of hydro- microemulsion or macroemulsion, can be manipulated by varying
carbon surfactants that stabilize CO2 -based macroemulsions do not a so-called formulation variable, such as the hydrophilic–lipophilic
stabilize microemulsions [13,16,18,24,25]. balance (HLB) of the surfactant, salinity, and temperature [36]. An
The tunable solvation strength of supercritical CO2 with tem- analogous hydrophilic–CO2 -philic balance (HCB) has been defined
perature and pressure (Tc = 31.1 ± 0.1 ◦ C, Pc = 7.38 MPa) has a large and characterized for high pressure CO2 –water systems [37,38].
influence on interfacial properties and stability of colloids. For
1 ATC − ATT − ACC
CO2 –water macroemulsions and microemulsions, the design of sur- = (1)
factant structures is highly challenging because of the weak van HCB AHW − AHH − AWW
der Waals forces of CO2 , as characterized by the low polarizabil- where Aij is the interaction energy for the various interactions
ity/volume, and low dielectric constant [26]. Limited solvation of between CO2 (C), the surfactant tail (T), water (W) and the surfac-
tant headgroup (H). For a CO2 -philic surfactant, for which 1/HCB > 1,
Table 2 the surfactant partitions more towards the CO2 phase and bends
Properties of micro-, mini-, and macroemulsions in supercritical fluids. about water, forming a W/C microemulsion or macroemulsion,
Micro Mini Macro as schematically shown in Fig. 1. When 1/HCB < 1, the surfactant
prefers the aqueous phase and the interface is concave with respect
Appearance Transparent Opaque Opaque
Radius (nm) <10 50–500 >500
to CO2 , resulting in a C/W macro- or microemulsion [17,39,40]. The
Area/vol (cm−1 ) 107 106 105 emulsion undergoes a phase inversion at the balanced state when
 (mN/m) <2 <2 <10 HCB = 1, when the surfactant exhibits an equal affinity for both
Settling rate (cm/h) Thermo. stable 0.5 × 10−3 0.5 phases. This condition may result in a three phase region (depend-
H2 O/surf (mol/mol) 5–60 >1000 >1000
ing on surfactant concentration Cs ), where a middle-phase macro or
 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530 525

microemulsion coexists with excess water and CO2 phases [40]. The
CO2 density, which may be tuned with pressure and temperature,
also has a profound effect on the emulsion phase behavior and the
curvature of the surfactant monolayer. The temperature response in
Fig. 1 is depicted for a nonionic surfactant system, in which increas-
ing temperature results in partitioning of the surfactant away from
water into CO2 .
The interfacial tension () is a minimum at the balanced state
(with respect to a formulation variable), where the surfactant favors
the two phases equally (Fig. 1). A minimum in the interfacial tension
vs. formulation variable plot, which has been observed in oil–water
systems [41,42], has also been established for the W–C interface
[16,43]. Microemulsions with high interfacial areas are favored by
low  at conditions not far from the balanced state.
To date, relatively few studies have examined the formation,
stability, and interfacial properties of emulsions of water and CO2
[39,40,44]. To enhance the solvation of surfactant tails with CO2 , Fig. 2. (LHS) Surfactant concentration vs. tension () at the CO2 –water interface.
by reducing ATT , most studies have focused on surfactants con- Critical microemulsion concentration (c␮c) is defined at the point where the change
in slope in tension vs. concentration diagram is observed. (RHS) The area per sur-
taining fluorinated or siloxane tails with weak van der Waals
factant molecule (same surfactant—chemical structure of the surfactant above the
interactions [12,45,46]. Surfactants containing hydrocarbon tails diagram) at the CO2 –water vs. oil–water interface. The area per molecule from
without branching and methylation such as C8 E5 (pentaethylene molecular dynamics simulations for the same surfactant structure at the CO2 –water
glycol n-octyl ether) [47] and bis-(2,4,4-trimethylpentyl)phosphate interface is also shown.
(2,4,4TMC5-PO4 − X+ ) [48] often do not form W/C microemulsions
or have limited solubility in CO2 . W/C microemulsions, first formed how they influence emulsion morphology and stability would
with fluorinated surfactants [12], were later produced with highly be highly beneficial for designing novel surfactants for enhanced
methylated and branched or “stubby” tails [38,49]. Stubby tails oil recovery (EOR) and other applications. The combination of
block the interface between CO2 and water lowering  as shown surface-sensitive experimental techniques, such as sum-frequency
by molecular dynamics simulation [50] and  measurements [48]. vibrational spectroscopy, interfacial rheological measurements,
Steric repulsion also lowers ATT , thus increasing the CO2 -philicity and SANS, with computational approaches, as for example molec-
and adsorption of the surfactant at the W–C interface [48,51]. ular dynamics (for probing both the equilibrium and dynamic
Finally, a lower ATT also reduces attractive interdroplet interactions interfacial properties) and Monte Carlo methods with accurate
between surfactant tails, which are unusually strong in the weak force fields may be used to address fundamental issues to help
solvent, CO2 , as shown by SANS [52,53]. advance this technology.
Ab initio calculations have also been successfully employed to
understand solvation in CO2 . The optimized structures and ener- 3. W/C and C/W microemulsions
getics obtained from binding energy calculations between CO2
and CO2 -philes (ATC ) have lead to the development of rational Whereas most of the early work utilized fluorinated surfac-
approaches for the design of CO2 -philic moieties, thus aiding in tants, recent advancements have been made with hydrocarbon
the design of stabilizers for CO2 -based dispersions [54–61]. surfactants, although with somewhat limited water-to-surfactant
There are many opportunities in this field of research. So far, ratios and thus small polar water domains. Ryoo et al. [38]
relatively few CO2 –CO2 -phile pairs have been investigated. The demonstrated that a highly branched nonionic hydrocarbon sur-
development of a library of energies/structures of CO2 –solute factant, octa(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether, could
pairs may help in the design of new stabilizers. Recent binding form a W/C microemulsion with up to 2% water and solubilize
energy studies in another compressible solvent (hydrofluoroalka- proteins such as lysozyme. The branching of the hydrocarbon
nes) has suggested that the inclusion of tail–tail interactions (ATT ), tails reduces attractive interdroplet interactions and increases
and methodologies to deconvolute the electrostatic and dispersive the degree of separation between water and CO2 , resulting in a
contributions to the total stabilization energy of solvent–solute lower interfacial tension [51]. Branching of the surfactant tails also
complexes may be used to obtain information not only on sol- increases surfactant adsorption at the water–CO2 interface [48].
vency, but may also be better predictors of solubility, and stability AOT-based designer surfactants, with vinyl acetate-modified tail
of dispersions in the bulk solvent [62–64]. groups have been shown to form W/C microemulsions with large
The  between water and compressed CO2 is about water-to-surfactant molar ratios. One significant challenge of such
20–30 mN/m, much lower than the surface tension of pure aggregates is the strong interdroplet interactions typically observed
water, 72 mN/m. Consequently, the area per surfactant at the even with fluorinated amphiphiles [53], and the yet restrictive
planar W–C interface is often larger than that at water–oil (W–O) water uptakes of less expensive and more environmentally friendly
and water–air (W–A) interfaces as shown by experiment [25,65] surfactants.
and molecular dynamics simulations [66]—see Fig. 2. The typically
lower adsorbed amounts at the C–W interface is a consequence of 4. W/C macroemulsions
the lower surface energy of that system, and the enhanced pene-
tration of the CO2 molecules in the surfactant tail region (entropic Similar to microemulsions, the formation of stable reverse W/C
nature), which are smaller when compared to typical organic macroemulsions is more challenging than (regular) C/W emulsions.
solvents [25]. For emulsions of water and CO2 , measurements of This is related to the fact that the solvation of surfactant tail groups
interfacial tension, surfactant adsorption, with complimentary is weaker in CO2 (compared to traditional organic solvents), and
measurements of phase behavior, rheology and emulsion stability to the enhanced collision frequency and settling rates observed in
are scarce [37]. A better understanding of the equilibrium and fluids with low viscosities as CO2 . As a result, few surfactants have
dynamic properties of the surfactant-laden C–W interface and been shown to form W/C emulsions that are highly stable against
526 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530

coalescence. Even more challenging is to prevent the rapid floccu-

lation and settling of water droplets in CO2 . Particular challenges
arise to disperse small volume fractions of water. Recent advance-
ments in the electrostatic stabilization of colloidal dispersions in
low dielectric CO2 , which may offer some opportunities in this area,
are discussed below.
Emulsions are unstable near the balanced state, since the mono-
layer has near zero curvature and the thin film between dispersed
phase droplets can bend and rupture easily resulting in a high rate of
coalescence [67]. Marangoni–Gibbs stabilization of the emulsions
is caused by interfacial tension gradients that oppose the flow of
surfactant during drainage of the thin film between the dispersed
phase droplets. This stabilization becomes weaker at the balanced
state, as  and consequently, gradients in , become smaller. At
a moderate distance from the balanced state, emulsions become
more stable [68] as it becomes more difficult to bend the interface
to form holes that lead to coalescence [67]. Eventually, at points too
far from the balanced state surfactant, adsorption at the interface
becomes insufficient to stabilize the emulsion. Interfacial tension Fig. 3. Concentrated CO2 -in-water emulsions stabilized with thin films between
maps, as shown in Fig. 1, are useful for understanding the HCB for CO2 bubbles stabilized by octa(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether (5b-
C12 E8 ).
a given surfactant.
da Rocha et al. reported W/C [16] and C/W emulsions [39] sta-
bilized with nonionic block copolymers, where the CO2 -philic tails as is well known for oil–water emulsions at ambient pressure. The
were composed of oligomers of propylene oxide or butylene oxide network of polyhedral cells over the entire height of the emulsion
with branches on the polymer backbone [16,21,39]. Studies of  vs. are capable of arresting creaming, by removing space for translation
HCB have been reported for a homologous series of block copoly- of the CO2 cells. As the pressure was varied, differences in coales-
mers of propylene oxide and ethylene oxide and of PDMS and cence rates were observed at the microscopic level. The size of the
ethylene oxide as a function of the ratio of the mass fractions of the cells grew more rapidly at 207 bar than 345 bar indicating a less
blocks [16]. These maps of interfacial tension may be used directly stable emulsion. The stability of concentrated emulsions increases
to guide the design of surfactant architecture to stabilize either with pressure, or likewise CO2 density, because of several factors. At
microemulsions or macroemulsions. low pressures the surfactant favors water strongly over CO2 . With
High internal phase C/W emulsions have been used to template an increase in pressure, the greater solvation of the surfactant tail
highly porous polymers including biomaterials [69]. These emul- drives the surfactant from water towards the water–CO2 interface,
sions are easier to stabilize than W/C emulsions as the tails point decreasing  and increasing the surfactant adsorption. The greater
inward and are not need to provide steric stabilization between surfactant adsorption enhances the resistance of the thin film to
droplets. C/W emulsions have also been used to synthesize parti- resist rupture and bubble coalescence. The role of ion adsorption at
cles with intricate morphology [4] and in electroplating [70], among the EO headgroup on electrostatic repulsion in the thin film would
others. be of interest future studies. In the future, it will be possible to
design surfactants that will form stable polyhedral foams at much
5. Future directions in colloid science in supercritical fluids lower pressures, for example 80 bar, and to understand how these
foams influence mobility control in CO2 EOR.
5.1. C/W emulsions
5.2. Protein colloids in CO2
Concentrated, surfactant-stabilized C/W emulsions with CO2
volume fractions greater than 70% (also referred to as CO2 foams) Since the first report in the field of biocatalysis by Randolph et
are attractive as mobility-control agents in enhanced oil recovery al. [73], over two decades ago, there have been many advances in
[71]. These foams lower the relative mobility of CO2 through high the field of biocatalysis in supercritical fluids (SCFs) and these have
permeability regions and thus improve the sweep efficiency of the been recently reviewed in detail [74]. Here, the anionic CO2 -soluble
reservoir. Typically, the design of C/W emulsions for EOR have been perfluoropolyether (PFPE) surfactant is ion paired to the surface
based on results for air/water foams, where the air is essentially an of the enzyme (hydrophobic ion pairing) forming an enzyme-
ideal gas [71,72]. This approach may not lead to optimal surfactants, surfactant complex soluble in fluorinated solvents and dispersible
since C/W emulsions have very different interfacial properties and in SCF CO2 [74]. Two biomolecules, cytochrome c (Cc) and ␣-
phase behavior than air/water foams. chymotrypsin (CMT) were readily ion paired with the fluorinated
Previously, da Rocha et al. [39] reported C/W emulsions sta- surfactant KDP 4606 and were shown to form either solutions or
bilized with nonionic block copolymers with up to 70% CO2 dispersions in perfluoromethylcyclohexane (PFMC) and in SCF CO2
in the dispersed phase. These emulsions were stable against which were optically clear to the naked eye, in all cases.
both flocculation and coalescence for greater than 48 h. These Fig. 4 shows a series of photographs of the Candida rugosa
emulsions can also be stabilized with low-molecular weight sur- lipase CRL-PFPE dispersion in CO2 with perfluoromethylcyclohex-
factants. A nonionic-methylated branched hydrocarbon surfactant, ane (PFMC) cosolvent at 25 ◦ C in a custom made variable volume
octa(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether (5b-C12 E8 ) view cell (VVVC). At higher pressures (>3500 psi) the majority of
emulsifies at 25 ◦ C and 345 bar up to 90% CO2 in water with the CRL-PFPE complex was dispersed giving a characteristic orange
polyhedral cells smaller than 10 ␮m, as characterized by optical translucent state (5050 psi).
microscopy, in Fig. 3. The high volume fraction of dispersed CO2 The mean diameters of the CRL-PFPE particles as a function of
phase leads to the formation of polyhedral structures smaller than CO2 density were determined from DLS measurements as shown in
10 ␮m, separated by thin films of the aqueous continuous phase, Fig. 5. Interestingly, the mean diameter for CRL-PFPE dispersed in
 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530 527

Fig. 4. Lipase ion paired with perfluoropolyether surfactant (CRL-PFPE) states in variable volume view cell (VVVC) at 25 ◦ C at various pressures. At higher pressures CRL-PFPE
is almost fully soluble (orange translucent). Decreasing pressure leads to an increase in turbidity.

CO2 is over 10 fold greater than that of CRL-PFPE in PFMC (6.5 nm), to limit this ion pairing [75]. Electrostatic stabilization of colloids
indicating that the molecules form aggregates under these high- is extremely beneficial in CO2 since CO2 in many cases does not
pressure conditions. At both temperatures, decreasing CO2 density solvate surfactant tails well enough to provide steric stabilization.
increases the mean diameter of CRL-PFPE particles. As the solvation Electrostatic repulsion stabilizes micrometer-sized water
strength of CO2 decreases, the interactions between particles led droplets with spacings greater than 10 ␮m in an ultra-low
to growth of the aggregate size. In the future, a variety of other dielectric CO2 at elevated pressures, as shown in Fig. 6 [75]. The
stabilizing ligands and ion pairing stabilizers could be designed for counterions, stabilized with a nonionic highly branched stubby
protein colloids. hydrocarbon surfactant, form an extremely thick double layer with
a Debye screening length of 8.9 ␮m. As a result of the balance
5.3. Electrostatic stabilization in low dielectric CO2 between electrostatic repulsion and the downward force due to
gravity, the droplets formed a hexagonal crystalline lattice at the
Although numerous studies have reported the behavior of steric bottom of the high-pressure cell with spacings of over 10 ␮m.
stabilization in compressed supercritical fluids including carbon The inset of Fig. 6 shows monodisperse droplets of ca. 3 ␮m
dioxide, the possibility of electrostatic stabilization has not been diameter at the top of the emulsion sediment, which initially was
considered due to the exceptionally low values of the dielectric con- formed with 3 wt.% water and 3 wt.% surfactant. The emulsion
stant εr , typically 1.5. Any counterions in the double layer would was sheared for 15 min, and the photomicrograph was taken 2 h
have a strong tendency to ion pair with charges on the surface after shear had been stopped. The 2-dimensional pair-correlation
of the colloid due to the low εr . However, one may achieve elec- function generated from video images (Fig. 6) clearly shows
trostatic stabilization by engulfing these counterions in micelles a hexagonal array of water droplets with an average spacing of
14.1 ␮m. The crystalline structure is the result of a balance between

Fig. 6. 2-Dimensional pair-correlation function of the droplets on the top layer of

Fig. 5. Protein diameter vs. CO2 density on decreasing and increasing pressure; () the emulsion sediment. The photomicrograph (inset) shows the crystalline structure
depressurizing at 25 ◦ C; () pressurizing at 25 ◦ C; (♦) depressurizing at 40 ◦ C; (×) of the droplets (ca. 3 ␮m diameter) on the top layer. 3 wt.% surfactant was used to
pressurizing at 40 ◦ C. disperse the same wt.% of water in CO2 at 55 ◦ C and 386 bar.
528 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530

electrostatic repulsion among droplets and the gravitational force

which tends to decrease interdroplet distances. Electrostatic
stabilization of micrometer-sized inorganic particles at long range
(several micrometers) in liquid and supercritical CO2 has also been
observed [76]. The counterions were solubilized in dry reverse
micelles, formed with a low-molecular-weight cationic perfluo-
ropolyether trimethylammonium acetate surfactant, to prevent
ion pairing with the particle surface. Dynamic light scattering and
settling velocities indicate a particle diameter of 620–740 nm. This
new field of electrostatic stabilization of colloids in supercritical
fluids may be further advanced with the design of surfactants to
stabilize the counterions against ion pairing with the surface.

5.4. CO2 as an antisolvent for processing of colloids

The characteristic weak solvent strength of CO2 , along with

its low surface tension, may be advantageously used in the
size-selective fractionation, deposition and assembly of colloidal
domains [35,77]. In order to fully exploit the size-dependent prop-
erties of the nanoscale, the ability to control the size and the order of
assembled domains is of great importance. Antisolvent techniques
are typically employed for size-selective separation of nanoparti-
cles. Roberts and co-workers have demonstrated that CO2 may be
used to improve the deposition of ordered films of metal nanopar-
ticles from organic solvents [77]. The interactions between the
solvent and ligand-stabilized nanoparticles can be tuned by the Fig. 7. Size-selective separation of nanoparticles with the help of CO2 as the
addition of CO2 (gas-expanded solvent), thus decreasing the bulk antisolvent-CO2 -gas-expanded solvent technique [35].
solvent strength—an improvement in solvent capacity may be also
envisioned upon the addition of CO2 , depending on the chemistry Fig. 9. Hydrophilic particles, such as silica, are wetted more by the
of the solvent and ligand. Degradation of the film during solvent water phase leading to a C/W emulsion, in which the interface
evaporation is minimized by replacing the high surface tension bends around CO2 . Conversely, hydrophobic particles are oriented
organic solvent (that is soluble in CO2 ) with the low surface tension towards the CO2 phase, leading to a W/C emulsion [82]. Changes in
CO2 . the contact angle of a solid particle at the CO2 –water interface can
As the expansion of the organic solvent, and thus its solvent be accomplished via adjustments in the surface chemistry of parti-
strength, can be easily and fine-tuned by simply varying the pres- cles. Such a change may be more easily performed than alteration
sure of the gas head above, the gas-expanded solvent approach was of surfactant architecture to modify the HCB, given that HCB val-
successfully employed for the size-selective fractionation metal ues of surfactants are often high, particularly for those with ionic
nanoparticles, with fractions having small polydispersity [35]. The headgroups.
principle is illustrated in Fig. 7. Recursive fractionation was also The stabilization of emulsions with particles in CO2 circumvents
shown to further reduce the polydispersity [34]. This concept may the problem of poor solvation of surfactant tails. The particles can
also be used to deposit nanocrystals in porous materials for cataly- be thought of as a highly “stubby” surfactant tail that blocks more of
sis and other applications. A dispersion of iridium nanocrystals was the water–CO2 interface than traditional narrower surfactant tails.
infused into mesoporous silica by expanding the solvent toluene In addition, these particles overlap much less than long narrow sur-
with supercritical CO2 [78]. To achieve high nanocrystal loadings, factant tails upon the approach of two drops. Thus, the particles
up to 1.3 wt.%, the solvent quality was tuned to strengthen the
interactions of the nanocrystals with the pore walls, but without
precipitating the nanocrystals in the bulk solvent.
The ability to quantitatively determine forces in colloidal
aggregates in CO2 -gas-expanded solvents may help further the
applicability/limits of this technique. Development of direct (exper-
imental) techniques for the measurement of forces in compressible
media to validate/improve theoretical models and computational
methods would be a welcome addition to the field. The devel-
opment of multi-scale computational methods, where realistic
chemistries and explicit solvents may be used to gain insight into
the forces in colloidal aggregates dispersed in expanded solvents
could also prove relevant to the field.

5.5. Particle stabilized emulsions

Very recently, macroemulsions of water and carbon dioxide

have been stabilized with particles instead of surfactants [4,79,80],
as shown in Fig. 8. For colloidal particle stabilizers, the con- Fig. 8. Micrographs of W/C emulsion stabilized with 0.9 wt.%. Fumed-1.7 particles
tact angle of the particle with the liquid–liquid interface governs and 49.4 wt.% water and 49.7 wt.% CO2 at 34.5 MPa (0.99 g/ml), and 24 ◦ C. Average
emulsion stability and curvature [81] as schematically shown in size is 30 ␮m.
 K.P. Johnston, S.R.P. da Rocha / J. of Supercritical Fluids 47 (2009) 523–530 529

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