Advances in Colloid and Interface Science

80 Ž1999. 1]25

Microgel particles as model colloids: theory,

properties and applications

Brian R. Saunders a,U , Brian Vincent b

a
Department of Chemistry, Uni¨ ersity of Adelaide, North Terrace, Adelaide, 5005, Australia
b
School of Chemistry, Uni¨ ersity of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK

Abstract

This review presents an overview of the literature concerning microgel particles with
emphasis on work performed during the past 5 years. Microgel particles are cross-linked
latex particles that are swollen in a good solvent. The particles are conveniently prepared by
surfactant-free emulsion polymerisation ŽSFEP. and may be viewed as sterically stabilised
particles without a core. The narrow particle size distribution combined with the inherent
steric stabilisation of particles prepared by SFEP makes them ideal model systems for the
study of solution-dependent phenomena Že.g. osmotic de-swelling.. The polyŽNIPAM.
ŽNIPAM s N-isopropylacrylamide. microgel system is considered in detail in terms of
swelling, rheological, small-angle neutron scattering ŽSANS. and kinetic data. The review
concludes with a discussion of the internal structure for microgel particles and consideration
of areas for further research. Q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Microgel particles; Synthesis; Properties; Internal structure

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Applications involving microgel particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Microgel particle synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Particle swelling theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

U
Corresponding author.

0001-8686r99r$ - see front matter Q 1999 Elsever Science B.V. All rights reserved.
P I I: S 0 0 0 1 - 8 6 8 6 Ž 9 8 . 0 0 0 7 1 - 2
2 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

5. Properties of microgel particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

6. Osmotic de-swelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7. Stability of dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
8. Swelling control by addition of alkanols: co-non-solvency . . . . . . . . . . . . . . . . . . 19
9. Small-angle neutron scattering investigations of microgel particles . . . . . . . . . . . . 20
10. Internal structure of microgel particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
11. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

1. Introduction

A microgel particle is a cross-linked latex particle which is swollen by a good

solvent. The term ‘microgel’ was first introduced by Baker w1x. However, Staudinger
and Husemann were the first to prepare microgel particles w2x. They polymerised
DVB at high dilution in a good solvent to achieve swollen cross-linked polymer
particles. Microgel particles were the subject of a review in 1995 w3x. A large
amount of work has been performed on new microgel systems in recent years and
some of the older systems have been re-investigated using advanced techniques or
novel methods. This work aims to bring the reader up to date with the current
position of microgel research.
The structures of the monomers commonly used to prepare microgels appear in
Fig. 1 Žthe abbreviations employed in this paper are listed in Table 1.. PolyŽNIPAM.
is the most well studied water-swellable microgel system. The best example of an
organic swellable microgel is PS; these particles are swollen by aromatic solvents
Že.g. toluene.. The ionic microgel particles prepared to date frequently contain
carboxylate groups derived from acrylic acid or methacrylic acid. There is consider-
able scope for variation of microgel properties by changes in the structure of the
monomers. For example, N-vinyl-n-butyramide w4x is isomorphous with NIPAM
and is a good candidate for microgel preparation. Variations of this type will allow
fine control of the lower critical solution temperature ŽLCST..
PolyŽNIPAM. undergoes thermally induced de-swelling when the solution tem-
perature is increased above the LCST Ž328C in water.. Heskins and Guillet were
the first to extensively study the LCST for linear polyŽNIPAM. chains in water w5x.
Water behaves as a good solvent through hydrogen bonding with the amide groups
at room temperature. This hydrogen bonding with water is increasingly disrupted
on heating causing water to act as a poorer solvent leading to gradual chain
collapse. Inter- and intra-polymer hydrogen bonding and polymer]polymer hy-
drophobic interactions become dominant above the LCST.
Fig. 2 depicts a microgel particle dispersed in good and poor solvents. The
particle is fully swollen or collapsed in good and poor solvents, respectively.
Microgel particles swell considerably in a good solvent Ždepending on the
crosslinking level. and the turbidity of dispersions is often observed to decrease
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 3

Fig. 1. Structures of the monomers frequently used to prepare microgel particles. The monomers are Ža.
methylmethacrylate, Žb. methacrylic acid, Žc. styrene, Žd. divinylbenzene, Že. acrylic acid, Žf. N-isopro-
pylacrylamide, Žg. N, N9-methylene bisacrylamide and Žh. ethyleneglycol dimethacrylate.

dramatically on swelling. The exact structure of the interior of microgel particles is

not yet settled.
The volume fraction of dispersion occupied by microgel particles Ž f d . is an
important parameter for industrial applications and rheological studies. The value
of f d is proportional to the volume fraction of polymer in the dispersion Ž f p . and
is independent of particle size. The relationship between f d , f p and f 2 is simply:
fp
fd s Ž1.
f2

where:
mp
rp
fp s m ms Ž2.
p
q
rp rs

m p , m s are the mass of polymer and solvent, respectively; r p and r s are the
densities of polymer and solvent. f 2 is the volume fraction of polymer in each
particle.
The most important property for microgel particles is the extent of swelling. The
4 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Table 1
Abbreviations used

Abbreviation Meaning

AA Acrylic acid
AC Acrylamide
AL Alcohol
ALHCl Allylamine hydrochloride
AMPS 2-Acrylamido-2-methylpropanesulfonate
AN Acrylonitrile
BA N, N9-methylenebisacrylamide
BAlc Benzyl alcohol
BC Butylcarbazole
BCA Butylcarbazole acetate
Bz Benzene
DMF Dimethylformamide
DVB Divinylbenzene
EA Ethylacrylate
EB Ethylbenzene
HA Hydroxamic acid
LCST Lower critical solution temperature
MAA Methacrylic acid
MADQUAT Ž2-ŽMethacryloyloxy.ethyl.trimethylammonium
d-MEOD Deuterated methanol
MeOH Methanol
MMA Methylmethacrylate
NIPAM N-isopropylacrylamide
PAA PolyŽacrylic acid.
PCS Photon correlation spectroscopy
PEG PolyŽethyleneglycol.
d-PEO Deuterated polyŽethylene oxide.
PrOH 2-Propanol
PS Polystyrene
QAC Quarternary ammonium chloride
SDS Sodium dodecyl sulfate
SFEP Surfactant-free emulsion polymerization
Sty Styrene
TBA Tert-butylmethacrylate
Tol Toluene
THF Tetrahydrofuran
2VP 2-Vinylpyridine
W Water

extent of swelling is usually determined from changes in the hydrodynamic diame-

ters measured using PCS. It is experimentally convenient to measure swelling
changes relative to the fully swollen hydrodynamic diameter Ž d o .. The extent of
particle de-swelling is expressed as the de-swelling ratio Ž a . which is simply:
a s Ž drd o . 3, where d is the measured hydrodynamic diameter at a given tempera-
ture etc. The de-swelling ratio and f 2 are related by: a s Ž d crd o . 3rf 2 where d c ,
is the diameter of the particles in the fully collapsed state Ži.e. particles contain no
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 5

Fig. 2. Diagram depicting a microgel particle in a poor Ža, x 12 ) 0.5. and good Žb, x 12 s 0. solvent,
respectively.

solvent.. This definition of a stems from the fact that it is difficult to obtain a
reliable value of d c , for microgel particles, i.e. it is experimentally easier to
determine the de-swelling ratio, than the swelling ratio.

2. Applications involving microgel particles

The main applications involving microgel particles have been in the surface
coatings industry. Microgel particle dispersions are shear thinning and provide
rheological control for automotive surface coatings w6x. The particles also have
good film forming properties and favour the alignment of added metallic flakes
parallel to the substrate surface.
The original motive for employing microgel particles in surface coatings arose
from US EPA regulations that required a decrease in the volatile component of
surface coating formulations. This was achieved by increasing the total solids
content by decreasing the molecular weight of the linear polymer Žresin. w7x;
however, this led to an unacceptably low viscosity. Microgel particles were added in
order to increase the dispersion viscosity. The microgel particles had the added
effect of imparting a yield stress to the dispersion. Surface coating formulations
often contain residual linear polymer which may affect microgel particle swelling.
Our work has shown that dispersion of microgel particles in the presence of added
polymer results in partial de-swelling of the particles by osmotic de-swelling Žsee
below..
Microgel systems also show promise in the printing and pharmaceutical indus-
tries. Microgel particles may be functionalised to yield photo-cross-linkable parti-
cles. The high surface area and good surface-coating characteristics have allowed
functionalised microgel particles to be used as printing offset plates with impressive
results w8x.
6 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Alternatively, microgel particles should have application as drug delivery systems

once they have been designed to swell in the vicinity of the target sites Žlymph
nodes etc.. within the body. This micro-encapsulation technique relies on develop-
ing sensitive trigger mechanisms whereby binding of the microgel surface groups to
specific sites on target cells Že.g. cancer cells. triggers particle swelling and release
of the drug molecule from the particle interior.

3. Microgel particle synthesis

Four methods have been reported for the preparation of microgel particles:
emulsion polymerisation w9,10x, anionic copolymerisation w11x, cross-linking of
neighbouring polymer chains w12x and inverse micro-emulsion polymerisation w13x.
Emulsion polymerisation is a versatile technique which yields narrow particle size
distributions. Emulsion polymerisation can be performed in the presence of added
surfactant Žconventional emulsion polymerisation. or in the absence of added
surfactant Žsurfactant-free emulsion polymerisation, SFEP.. In the latter method,
the continuous phase must have a high dielectric constant Že.g. water. and ionic
initiators are employed Že.g. K 2 S 2 O 8 .. The charged polymer chains formed during
polymerisation act as surfactant molecules and stabilise the growing particles.
Conventional emulsion polymerisation enables preparation of very small mi-
crogel particles Ži.e. particle diameters less than ; 150 nm.; however, a problem
with this technique is the difficulty of completely removing residual surfactant.
SFEP does not suffer from residual surfactant contamination. The seminal work on
SFEP was performed by Goodwin et al. w14x who used the technique to prepare
non-swollen polystyrene latex particles. SFEP has been widely used for the prepa-
ration of polyŽNIPAM., PS and polyŽMMA. microgel systems w9,15,16x.
SFEP is ideally suited to the preparation of polyŽNIPAM.. Typically, NIPAM is
polymerised in the presence of persulfate and cross-linking monomer at a tempera-
ture of ; 708C. The particles gradually swell when the temperature is decreased
with the maximum degree of swelling occurring around 328C; this avoids the need
to transfer the particles from a good to poor solvent after preparation.
Fig. 3 shows the salient features of SFEP. Thermal decomposition of the ionic
initiator ŽS 2 O 82y . initiates free-radical polymerisation. The oligomers produced are
surface active and form nuclei when the length of the oligomers exceeds the
solubility limit of the solvent. The nuclei then undergo limited aggregation, thereby
increasing the surface charge until electrostatic stabilisation is achieved w14x.
Further particle growth occurs through absorption of monomer andror oligomeric
chains. This process results in a decrease in the concentration of oligomers to
below the critical value required for particle formation. Polymerisation continues
within the particles until another radical species enters the growing particle and
termination occurs. The key feature of SFEP is that the particle nucleation period
is very short Žof the order of minutes. which ensures a narrow particle size
distribution. The final particle size achieved by SFEP increases with electrolyte
concentration and decreasing initiator concentration w14x.
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 7

Fig. 3. Mechanism for the preparation of microgel particles by SFEP. The steps shown are initiator
decomposition Ža., initiation Žb., propagation Žc., particle nucleation Žd., particle aggregation Že.,
particle growth Žin a poor solvent. Žf. and particle swelling in a good solvent Žg.. The counter-cations
and the particle charges for steps Žf. and Žg. have been omitted for clarity. M represents a vinyl
monomer.

For particles other than polyŽNIPAM., particle swelling is achieved by removal

of the particles from the continuous phase Že.g. by freeze-drying. and re-dispersion
in a solvent with a good solvency for the polymer.
Work performed at the University of Adelaide has shown that monodisperse
polyŽNIPAM. particles may be formed during SFEP in the absence of added
cross-linking monomer w17x. Thus, NIPAM appears to act as its own cross-linking
monomer; however, the efficiency of cross-linking is clearly improved when cross-
linking monomers Že.g. BA. are employed.
An alternative method used for the preparation of microgel systems involves
polymerisation using a good solvent. Staudinger and Husemann polymerised w2x
dilute DVB solutions and obtained soluble products with low intrinsic viscosity.
ŽBulk macrogel would have resulted if the monomer concentration employed was
8 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

such that the polymer concentration exceeded the critical overlap concentration
cU .. Antionetti and Rosenauer w18x re-investigated the DVB system and reported
broad particle size distributions. Okay and Funke w19x used an analogous anionic
polymerisation method whereby 4-tert-butylstyrene was copolymerised with DVB
in heptane to yield microgel particles. The size distributions for these products
were also broad.
The above examples reveal that particle formation using good solvents for the
polymer suffers from poor particle size uniformity. The primary reason for this is a
lack of electrostatic stabilisation during polymerisation; pendant vinyl groups are
able to react with radical sites on neighbouring polymer chains. Network growth
may therefore occur by reaction with neighbouring particles at any time during the
polymerisation, resulting in broad particle size distributions. However, it is likely
that particles formed using this method have a relatively uniform distribution of
comonomers Žcf. SFEP. because precipitation of high molecular weight chains does
not occur.
Saito and Ishizu w20x have recently reported an elegant approach for the
synthesis of microgel particles. PolyŽ2VP-b-sty-b-2VP. copolymer micelles were
reacted with 1,4-di-idobutane in a hemi-solvent Ža solvent that was selective for the
polystyrene block.. The cross-linking reaction transformed the flower-type micelles
into microgel particles with a particle size of 75]185 nm. The particle size range
reported indicates considerable aggregation of the block copolymer within micelles
prior to cross-linking. The initial micelle size will determine the final microgel
particle size. It should be possible to produce monomolecular micelles by control of
copolymer architecture using this method. The micelles could then be cross-linked
to yield nanogel particles. ŽNanogel particles are defined as cross-linked particles
with swollen particle sizes of less than 50 nm.. The method discussed above should
produce monodisperse particle distributions since micelle particle distributions of
block copolymers dispersed in hemi-solvents are usually narrow.
Neyret and Vincent have developed a new approach for the formation of
microgel particles; inverse microemulsion polymerisation w13x. The oil phase con-
sisted of anionic 2-acrylamido-2-methylpropanesulfonate ŽAMPS. and cationic
Ž2-Žmethacryloyloxy.ethyl.trimethylammonium ŽMADQUAT. monomers in addi-
tion to BA. The copolymerisation was initiated using UV irradiation and the
product isolated and re-dispersed in aqueous electrolyte solution to yield polyam-
pholyte microgel particles. The particles swelled in the presence of high electrolyte
concentrations as a result of screening of the attractive electrostatic interactions
between neighbouring chains.
Table 2 shows particle size data extracted from a representative selection of the
literature reports on microgel systems. SFEP is the most common method used to
prepare polyŽNIPAM. microgel particles. Microgel particles based on PS and
polyŽMMA. are usually prepared by EP; although SFEP has also been used. EP
and SFEP typically yield microgel particles with diameters between 100 and 1000
nm.
The most actively studied microgel system is polyŽNIPAM.. NIPAM is commer-
cially available and polyŽNIPAM. particles are easily prepared. These particles
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 9

usually contain between 80 and 99% water in the swollen state Ž0.001 - f 2 - 0.20..
These particles are very sensitive to environmental changes Žas judged by
swellingrde-swelling transitions ..
PS and polyŽMMA. microgel particles have also been well studied ŽTable 2..
PolyŽMMA. and PS particles swell in organic solvents. PS microgel particles
dispersed in EB and THF usually contain between 30 and 90 vol.% solvent
depending on the preparation conditions.
Figs. 4 and 5 show TEM and SEM micrographs for polyŽNIPAM. and PS
microgel particles w15,16,39x. PolyŽNIPAM. particles exhibit a pronounced tendency
to form ordered structures when deposited on TEM grids. A definite spacing is

Table 2
Summary of literature reports concerning microgel particles a

Polymer Solvent Microgel Prep Collapsed Swollen f2d Refs.

typeb methodc particle size particle size
Žnm. Žnm.

PolyŽAC. WrAL N PP 60]1000 w21x

PolyŽAN. DMF N EP 300 735 0.068 w22x
PolyŽALHCl. W I PPC 22]26 w12x
Poly W I IMP 50 100]250 } w13x
ŽAMPSr
MADQUAT.
PolyŽEArMAA. W I EP 60]100 140]600 0.08]0.005 w23x
PolyŽMMA. Bz N EP 205]230 355]480 0.11]0.20 w24x
PolyŽMMA. BCA N EP 135]205 0.07]0.28 w25x
PolyŽMMA. BAlc N EP 300 650 0.10 w26x
Poly W I EP 75]140 85]255 0.17]0.69 w27x
ŽMMArAA.
Poly W I EP 40 w28x
ŽMMArAArHA.
Poly W I SFEP 310 750 0.07 w16x
ŽMMArMAA.
PolyŽNIPAM. W N SFEP 500 w9x
PolyŽNIPAM. W N SFEP 240 450 0.17 w29x
PolyŽNIPAM. W N SFEP 135 270 0.12 w30x
PolyŽNIPAM. W N SFEP 120 520 0.012 w31x
PolyŽNIPAM. W N SFEP 240 450 0.15 w32x
PolyŽNIPAM. W N EP 375 950 0.062 w33x
PolyŽNIPAM. W N SFEP 400 700 0.19 w34x
PolyŽNIPAM. W N SFEP w35x
PolyŽNIPAM. W N SFEP 120 520 0.012 w36x
PolyŽNIPAM. W N SFEP 23]50 130]470 0.001]0.006 w37x
PolyŽNIPAM. W N SFEP 150 340 0.085 w38x
PolyŽNIPAM. W N SFEP 325]335 590]685 0.14]0.17 w39x
PolyŽNIPAM. W N SFEP w16x
PolyŽNIPAM. W N EP 145 w40x
PolyŽNIPAM. W N SFEP 315 590 0.15 w41x
PolyŽNIPAM. W I EP 200]880 0.010]0.10 w42x
10 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Table 2 Ž Continued.

Polymer Solvent Microgel Prep Collapsed Swollen f2d Refs.

typeb methodc particle size particle size
Žnm. Žnm.

Poly W I SFEP 300 700]900 0.04]0.08 w43x

ŽNIPAMrAA.
Poly W I EP 30]100 140]425 0.005]0.045 w44x
ŽNIPAMrMAA.
PS EB N EP 405]520 490]1150 0.098]0.63 w10x
PS Various N EP 75]130 w45x
PS Tol N EP w46x
PS EB N SFEP 345]355 570]660 0.16]0.22 w15x
PS THF N EP 328]425 700 0.224 w47x
PS W I EP w48x
PS Tol N FC 26]84 42]240 0.042]0.23 w49x
PS Tol N FC 24]208 w18x
PS W I FC 24]35 w8x
PolyŽstyrAA. Dioxan I FC 0.11]0.23 w50x
PolyŽstyrMAA. THFrW I BC 60]80 w51x
PolyŽstyrQAC. W I EP 250]380 w52x
PolyŽstyr2VP. Tol N BC 75]185 w20x
PolyŽstyr2VP. W I EP 150]200 600]1100 0.006]0.035 w53x
Poly W N SFEP 135 w54x
Žstyrmercapto.
PolyŽTBA. Heptane N AN 35]80 w19x
PolyŽ4VP. W NrI EP 250]700 0.035]0.28 w55x
a
See Table 1 for abbreviations used for the polymers and solvents.
b
N, neutral; I, ionic.
c
EP, emulsion polymerization; SFEP, surfactant-free emulsion polymerization; IMP, inverse microemul-
sion polymerization; BC, via block copolymers; AN, anionic polymerization; PP, percipitation polymer-
ization; FC, free-radical copolymerization; PPC, post-polymerization cross-linking.
d
Volume fraction of polymer in swollen particles.

evident between the particles. This effect was first reported by Pelton et al. w9x and
attributed to particle shrinkage during solvent evaporation.
The SEM data for polyŽNIPAM. and PS microgel particles show that the
particles deformed to a ‘pancake’ structure during solvent evaporation Žsee Fig.
4a.. Clearly, TEM data cannot be used to obtain accurate measurements of the
particle size for particles deposited from the swollen state. PCS data are more
accurate in this regard.
A range of anionic microgel systems has also been investigated. The anionic
monomers most frequently incorporated are either AA or MAA. Microgel particles
containing these monomers swell at high pH. This effect may be described in terms
of internal electrostatic repulsion or, equivalently, the osmotic contribution from
mobile counter-ions in the ionic particles. The swelling mechanism for ionic
microgels is discussed in more detail below.
The overwhelming majority of the ionic microgel systems listed in Table 2 are
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 11

Fig. 4. Scanning electron micrographs of PS microgel particles deposited from ethylbenzene Ža. and
water Žb.. The particles are viewed at an angle of 308 to the sample plane. The average size of the
particles shown in Žb. was measured as 355 nm from TEM measurements.

anionic. However, a notable exception is polyŽstyr4VP.. Loxley and Vincent w53x

examined the pH-dependent swelling Žand swelling kinetics . of the
polyŽstyr4VP.rwater system using PCS and stop-flow techniques. The particles
swell at low pH due to protonation of the 4VP group.
The data listed in Table 2 reveal that the number of microgel systems reported
12 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Fig. 5. Transmission electron micrograph of polyŽNIPAM. microgel particles. The average particle
diameter was 450 nm.

to date is rather limited; the majority of the work relates to polyŽNIPAM. and PS
systems. Clearly, it should be possible to prepare microgel particles using any
flexible, cross-linked polymer system.

4. Particle swelling theory

Flory’s theory of network swelling has been used to describe the swelling of
microgel particles in organic solvents w56x. A polymer network immersed in a good
solvent imbibes solvent in order to balance the solvent chemical potential inside
and outside the gel network; the presence of cross-links restricts the extent of
swelling. Thus, swelling continues until the sum of the elastic forces between
cross-links is equal to the osmotic force. The extent of network swelling is usually
described by the polymer volume fraction Ž f 2 . obtained at equilibrium Ž f 2 s 1 in
the collapsed state.. Flory’s theory leads to w56x:

3r5
X¨ 1
f2 s ½ Vc Ž 12 y x 12 . 5 Ž3.

where X is the number of cross-links present within a collapsed network volume,

Vc . The subscripts 1 and 2 refer to the solvent and network polymer, respectively;
¨ 1 is the molar volume of the solvent and x 12 represents the Flory solvent]poly-
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 13

mer interaction parameter. The term Ž xrVc . represents the average density of
cross linked units in the collapsed particle.
Microgel particles usually contain a high proportion of non-cross-linking polymer
segments Žmonomer B. and a minor proportion of Žnormally. difunctional cross-lin-
king segments ŽA.; the mole fraction of the latter Ž XA . being typically less than 0.1.
If it is assumed that the molecular weights of the A and B segments are the same
and that each mole of di-functional cross-linking monomer introduces two moles of
cross-linked units, it is readily shown that:
X 2 xA r B
s Ž4.
Vc MB

where M B and r B are the molecular weight and density of the B segments,
respectively. Substitution of Eq. Ž4. into Eq. Ž3. and assuming r B s 1 leads to a
simple expression describing the dependence of the volume fraction of the mi-
crogel particles on the network composition and solvency:
3r5
2 xAV1
f2 s
ž n 12 M B / Ž5.

where the excluded volume parameter, n 12 s Ž0.5 y x 12 .. The polymer volume

fraction increases Žparticles de-swell. if the cross-link density increases or the
solvency becomes poorer Ž n 12 decreases..
Flory’s theory of network swelling has been applied to PS microgel particles
dispersed in ethylbenzene and was also extended to consider the effect of added
non-adsorbing Žfree. polymer w15x. It was found that the ‘effective’ concentration of
incorporated cross-linking monomer was less than that actually used during the
preparation; hence there may have been a significant proportion unreacted,
pendant, vinyl groups present in the microgel particles.
There are a number of problems with Flory’s theory of gel swelling: Ži. it assumes
a uniform cross-link density within the network. There is evidence that this is not
the case for many microgel systems Žsee below.. Žii. The concentration dependence
of x is not included ŽNapper w57x, amongst others, has considered this problem..
There is a particular problem here with aqueous gel systems w58,59x related to
changes in H-bonding and hydrophobic bonding, as the segmentrwater concentra-
tion varies with swelling.
A more appropriate model Žthough complex. for describing the swelling of
polyŽNIPAM. networks has been employed by Lele et al. w60x. They applied the
lattice-fluid-hydrogen bonding theory ŽLFHB. to the swelling of polyŽNIPAM.
networks in aqueous alcohol solutions. The theory incorporated a number of
different hydrogen bonding interactions within the polyŽNIPAM.-water-alcohol
system. The extended LFHB model predicted re-entrant swelling for the system
and qualitatively described the experimental data. PolyŽNIPAM. microgel particles
dispersed in water]alcohol mixtures also exhibit re-entrant swelling w41x and this is
discussed in more detail below.
14 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

As referred to earlier, microgel particles containing ionic co-monomers exhibit

pH-dependent swelling w23x. The contribution of strong Žacid or base, i.e. pH-inde-
pendent. groups from within microgel particles Žwhich have been extensively
dialysed against distilled water. to the swelling of those particles is best viewed in
terms of the increase in internal osmotic pressure due to the mobile counter-ions
contained within the microgel particles. This balances the internal electrostatic
repulsion. The total charge of the microgel particles plus their counter-ions must
be zero. It may be that some of the counter-ions are bound to charged sites,
effectively forming neutralised ion pairs. It is only the free Žmobile. counter-ions
which contribute to the osmotic pressure } at least to the ideal component; there
may be minor contributions from the ion-pairs to the non-ideal component of the
osmotic pressure through small changes in the x-parameter.
The addition of inert electrolyte to a dispersion of microgel particles with strong
acidrbase groups leads to de-swelling of those particles. A Donnan equilibrium is
set up, whereby the free ions distribute themselves between the inside and outside
of the microgel particles. There is a net reduction in the osmotic pressure
difference between the inside and outside of the microgel particles, which may,
alternatively, be viewed as additional screening of the electrostatic repulsion within
the particles.
The case of microgel particles containing weak Žacid or base, i.e. pH-dependent.
groups is more complex. The ionisation of the sample is governed by the p K a , or
p K b of the groups concerned, but these parameters are functions of the local
charge group chemistry Ža higher charge density suppresses ionisation. and back-
ground ionic strength Žscreens local electrostatic repulsion.. Irrespective of the
addition of any inert electrolyte, adjustment of pH itself inevitably leads to changes
in background ionic strength.
Fig. 6 shows the effect of increasing pH for a polyŽMMArMAA. microgel
system Žthe background ionic strength was not systematically controlled. w16x. On
increasing the pH from low values to high values, the swelling extent increases as
the Žweak. carboxylic acid groups inside the microgel particles ionise. The rate of
increase levels off at higher pH values partly because the ionisation attains its
maximum value; in addition, the increasing ionic strength screens the internal
repulsion, or, equivalently, reduces the osmotic pressure difference between the
inside and outside of the microgel particles.

5. Properties of microgel particles

When a collapsed microgel particle swells in a good solvent, previously buried

segments become accessible to the continuous phase. If the radius of the collapsed
particles is rc and that of the polymer segments is r s , then the total number of
segments per particle is Ž rcrr s . 3 and the total on the surface is Ž rcrr s . 2 . Hence, the
ratio of segments exposed to the continuous phase, in the swollen and collapsed
state, varies as rcrr s . Hence, for a collapsed particle with rc s 150 nm and
r s s 0.15 nm, the value for rcrr s is 1000. Thus, particle swelling results in a
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 15

Fig. 6. Effect of dispersion pH on the hydrodynamic diameter of polyŽMMArMAA. microgel particles.

substantial increase in the accessible segments for a microgel particle. This result
shows that microgel particles have considerable potential for applications that
make use of functionalised monomer units residing within the particles as well as
on the surface e.g. pollution control w43x and catalysis.
Another beneficial feature of microgel particles is their rapid swellingrde-swell-
ing kinetics in comparison to macrogels. Tanaka et al. w61x investigated the
dependence of the swelling transition rate on particle size for spherical
polyŽacrylamide. gels. A characteristic time, t , described the rate of swelling; t
represents the point where ; 75% of the total swelling has occurred. Tanaka et al.
w61x showed that t was proportional to the square of the collapsed particle radius,
rc . Assuming this relationship is applicable to microgel particles Ž rc s 100 nm., the
value of t for microgel particles is expected to be eight orders of magnitude faster
than for a macrogel Ž rc s 0.5 mm. with the same composition. Microgel particles
respond rapidly to changes in solvency.
The deformable nature of microgel particles has important implications for their
rheological properties. Buscall w62x reported that the rheological behaviour of
microgel particles is equivalent to that of hard particles with a thin, soft shell.
Dilute microgel dispersions exhibit Newtonian flow, whereas concentrated disper-
sions are highly shear thinning w25x. When compared, at the same number concen-
tration, to hard-sphere particles, swollen microgel particles greatly increase the
dispersion viscosity w37x; due to the much larger effective hydrodynamic diameter of
the swollen particles. It is for this reason that microgel particles have potential
application in the surface coatings industry as filler materials.
The electrophoretic mobility is an important property of microgel particles that
16 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

is frequently reported. Miller et al. w63x reported electrophoretic mobility measure-

ments for an organic swellable microgel system. They measured mobilities of
approximately y4 = 10y1 0 m2 sy1 Vy1 for PS microgel particles dispersed in
toluene using phase analysis light scattering ŽPALS.. Snowden et al. w30x have
reported mobilities for polyŽNIPAM. microgel particles dispersed in water in the
range y1 to y3 = 10y8 m2 sy1 Vy1. Oshima et al. w64x has developed a theory
that is applicable to soft particles with a hard core which may be adapted for
microgel particles w65x, with an assumed uniform space charge density. If the
frictional coefficient of the segments in the swollen microgel particles is known,
then the space charge density may, in principle, be derived.

6. Osmotic de-swelling

The first report of an osmotic de-swelling mechanism for microgel particles was
by Sieglaff w45x in 1963 for the PSŽmicrogel.rtoluenerPSŽfree polymer. system.
Sieglaff suggested that an ‘exclusion shell’ for PS free polymer would be produced
around the microgel particles; exclusion results when the polymer conformations
required to penetrate the particle interior become entropically unfavourable.
A theoretical model has been developed w15x that describes the change of
polymer volume fraction of the microgel particle Ž f 2 . with volume fraction of
excluded free polymer Ž f 3 . in the continuous phase. The theory is based on Flory’s
theory of network swelling and incorporates the effect of the osmotic pressure due
to excluded free polymer on the solvent chemical potential, m 1. The condition that
m 1 in the particle interior and in the continuous phase must equate at equilibrium
yields the following equation w15x:

f 3 M1 r 3 M1 XA r B
Ž 12 y x 13 . f 32 q s f 22 Ž 12 y x 12 . y 2 f 21r3
r 1 M3 ž /ž
r1 MB / Ž6.

The subscripts 1, 2, 3 and B refer to the solvent, polymer network, added free
polymer and non-cross-linking segments, respectively. M x and r x Ž x s 1, 3 and B.
represent the molecular weight and density, respectively. Eq. Ž6. has been applied
to the PSŽmicrogel.rEBrPSŽfree polymer. system and predicted osmotic de-swell-
ing w15x. However, the experimental data were believed to have been affected by
partial penetration of PS free polymer into the microgel particle interior. In
addition, the swellingrde-swelling of the PS microgel particles is believed to be
kinetically limited, due to the high Tg value for PS. Both of the above factors
resulted in a smaller experimental value for f 2 than predicted by Eq. Ž6..
Fig. 7 shows the variation of the de-swelling ratio for polyŽNIPAM.rwaterrPEG,
PSŽmicrogel.rEBrPSŽfree polymer. and polyŽMMArMAA.rwaterrPEG systems
as a function of the molecular weight of added free polymer at fixed values of f 3 .
The data show the greatest de-swelling for the polyŽNIPAM.rwaterrPEG system.
The polyŽMMArMAA. particles have an electrostatic component which opposes
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 17

Fig. 7. Osmotic de-swelling of polyŽNIPAM. ŽB., PS Žl. and polyŽMMArMAA. Ž^. microgel particles
by addition of free polymer of different molecular weight. The free polymers used in the aqueous
systems Ž f 3 s 0.13. and non-aqueous system Ž f 3 s 0.19. were PEG and PS, respectively.

de-swelling and is responsible for the modest osmotic de-swelling observed for that
system.
The rheological properties of microgel particle dispersions in the presence of
added free polymer have been investigated by Racquois et al. w66x. The particles
were based on styrene and copolymerised with unspecified acrylic co-monomers. A
reduction in viscosity was reported upon the addition of free polymer and this was
attributed to osmotic de-swelling of the particles } corresponding to a lower f d
ŽEq. Ž1...
Osmotic de-swelling of polyŽacrylate. microgel particles in the presence of the
sodium salt of PAA has been investigated by Kiefer et al. w67x using viscosity
measurements. The results implied that added PAA did, indeed, cause de-swelling
of the microgel particles. Excluded PAA may be expected to induce de-swelling of
the particles due to the osmotic pressure of the mobile ions associated with the
polyelectrolyte in addition to the contribution from excluded free polymer itself.
However, low molecular weight PAA chains were believed to penetrate the
microgel particle interior.
PCS measurements of microgel particlerfree polymer systems are useful for
characterising the swelling behaviour of microgel particles. In mixed particlerfree
polymer systems it is important to ensure that the scattered intensity from the
particles is at least an order of magnitude greater than that from the polymer
solution. In calculating the hydrodynamic diameter from the measured diffusion
coefficient ŽStokes]Einstein equation. the viscosity is taken to be that of the
continuous polymer solution phase. Microgel particles usually have diameters at
least an order of magnitude greater than the surrounding free polymer chains, so
that the autocorrelation function may be deconvoluted to obtain the diffusion
coefficient for the microgel particles.
18 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

7. Stability of dispersion

The interaction between swollen microgel particles comprises contributions from

steric and electrostatic terms. Microgel particles contain a large volume fraction of
solvent in the fully swollen state. Thus, the effective Hamaker constant for the
swollen particle is similar to the Hamaker constant for the solvent, resulting in a
negligible van der Waals attraction between the swollen particles. Thus, in the fully
swollen state, dispersions of microgel particles are intrinsically stable. As de-swell-
ing occurs so the van der Waals forces become increasingly more significant.
If charged groups are incorporated Žin the surface andror in the interior. into
the particles during polymerisation then electrostatic interactions play a role in
determining the stabilisation. The surface groups on polyŽNIPAM. particles are
responsible for the fact that these dispersions remain stable during synthesis, even
though the temperature is much higher than the LCST of polyŽNIPAM. in water,
such that the particles are de-swollen.
The importance of steric interactions to the stability of microgel dispersions is
illustrated by the fact that polyŽNIPAM. dispersions are stable in the presence of
high electrolyte concentrations Žsuch that electrostatic interactions are negligible.
provided the dispersion temperature is below the LCST w29x. In addition, PS
microgel particles are swollen Žand stable . in ethylbenzene w15x } even in the
presence of 20 wt.% free PS Žsee below.. These results show that steric stabilisation
makes a significant contribution to microgel dispersion stability. The magnitude of
the steric interaction depends on the polymerrsolvent interaction parameter Ž x .
and is linked to the degree of particle swelling through f 2 .
The stability of particular dispersions to flocculation is conveniently examined by
measurements of the ‘n-value’. ŽThe n-value is the gradient of log Žoptical density.
vs. log Žwavelength. plots Ž n s ydlogŽO.D.rdlogŽ l.. and has a magnitude which
decreases with average particle size Žin the Rayleigh-Gans-Debye scattering region..
In order to examine depletion interactions of free polymerrmicrogel systems the
n-value for a range of systems was investigated. Fig. 8 shows the variation of the
n-value for polyŽNIPAM.rwaterrPEG, PSŽmicrogel.rEBrPSŽfree polymer. and
polyŽMMArMAA.rwaterrPEG dispersions w15,16,39x. The data reveal that
polyŽNIPAM. and PS particles flocculate at high volume fractions of PEG10K and
PS17K, respectively. The flocculation for both systems is attributable to depletion
interactions. Bridging interactions are not likely in either system under the condi-
tions employed. However, a study involving adsorbing polymer may provide some
interesting information about the interaction between solution polymers and
microgel particles as osmotic de-swelling may then occur simultaneously with
bridging.
Free polymer chains below a certain critical molecular weight may diffuse
through the microgel particle pores into the microgel particle interior of a particle
with a uniform pore size distribution. In such cases, the particle may swell. When
the polymer chains are too large to penetrate the microgel particle interior,
osmotic de-swelling results in collapse of the network. It is plausible that the pore
size of the particles increases from the centre of the particle to the periphery Žsee
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 19

Fig. 8. Variation of the n-values for polyŽNIPAMrwaterrPEG10K. ŽB., PSŽmicrogel.rEBrPS17KŽfree

polymer. Ž^. and polyŽMMArMAA.rwaterrPEG17K Že. with volume fraction of free polymer.

below.. Polymer chains below a certain size may be able to penetrate the pores at
the periphery. In that case, de-swelling of the particle core may occur to a greater
extent than the periphery. Osmotic de-swelling is expected to augment any non-
uniform pore size distribution already present within the particles.

8. Swelling control by addition of alkanols: co-non-solvency

Linear polyŽNIPAM. coils in water can be made to undergo a coil-to-globule

transition by addition of alkanols, even though the alkanols are good solvents for
the polymer w68x. The phenomenon whereby a polymer has poor solubility in a
mixture of solvents that are individually good solvents for that polymer is referred
to as co-non-solvency. This phenomenon is manifested as de-swelling for
polyŽNIPAM. microgel particles w16x and macrogels. The behaviour was first
reported for microgel particles by McPhee et al. w69x.
Fig. 9 shows the changes in the de-swelling ratio for polyŽNIPAM. and
polyŽMMArMAA. microgel particles dispersed in aqueous PrOH solutions as a
function of 2-PrOH volume fraction Ž f a .. The data for each system show de-swell-
ing at moderate values of f a and re-entrant swelling at higher values of f a . The
mechanism responsible for co-non-solvency most likely involves clathrate structure
formation w70x. In pure water the polyŽNIPAM. network is fully swollen by the
attractive water]polymer interactions Žhydrogen bonding.. Addition of moderate
amounts of alcohol leads to the formation of transient structures involving PrOH
molecules which are encapsulated by locally ordered water molecules Žclathrate
structure .. Competition for water molecules occurs between these clathrate struc-
20 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Fig. 9. The effect of added PrOH on the de-swelling ratio of polyŽMMArMAA. ŽB. and polyŽNIPAM.
Ž`. microgel particles dispersed in aqueous PrOH solutions.

tures and polyŽNIPAM. microgel particles; water molecules are removed from the
microgel particle interior causing de-swelling. The encapsulation of the alcohol
molecules breaks down at high volume fractions of PrOH leading to direct
solvation of the polymer chains Žhydrophobic interactions . by the alcohol and
re-entrant swelling.

9. Small-angle neutron scattering investigations of microgel particles

Neutron scattering results from a short-range repulsive interaction between the

neutrons and nuclei of a material. The small-angle neutron scattering ŽSANS.
experiment involves the measurement of the scattered intensity Ž I Ž Q .. of a neutron
beam with a wavelength, l, as a function of the scattering vector Ž Q .. The
scattering vector is related to the scattering angle Ž u . by:
4p u
Qs sin ž / Ž7.
l 2
For dilute colloidal dispersions, such as microgels, the scattered intensity, I Ž Q .,
is a function of the contrast factor Ž Dr ., the particle form factor Ž P Ž Q .. and the
particle concentration Ž Np ..
2
I Ž Q . s Vp2 Np Ž Dr . P Ž Q . Ž8.

where Vp is the particle volume. For spherical particles of uniform average density,
P Ž Q . is given by:
2
sin Ž Qr . y Qrcos Ž Qr .
P Ž Q. s 3 Ž9.
Ž Qr . 3
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 21

The contrast factor between the particles and the medium can be altered by
selective isotopic substitution Žusing deuterium. in order to simplify interpretation
of SANS data for multicomponent systems. Consequently, SANS is ideally suited
for studies of microgel particles in the presence of added free polymer.
Because of the presence of the cross-links, microgel particles do not have a
uniform density at the length scales of the neutron wavelength. Mears et al. w40x
were the first to examine polyŽNIPAM. microgel particles in the presence of SDS
Žsodium dodecyl sulfate . using SANS. They assumed that the scattered intensity
from the microgel particles obeyed the equation:

IL Ž 0 .
I Ž Q . s AQy4 q Ž 10.
1 q j 2 Q2

where A and ILŽ0. are constants and j is the correlation length which charac-
terises the mean separation between density fluctuations Že.g. the pore size.. Eq.
Ž10. assumes that the scattering from microgel particles has components from the
‘whole particle’ Žfirst term. and polymer in a solution-like environment Žsecond
term.. Mears et al. found that SDS caused swelling of the polyŽNIPAM. particles
and that small polymer-bound aggregates of less than five monomer units formed
within the particles. Presumably, SDS caused swelling due to the adsorption of the
surfactant molecules onto the polyŽNIPAM. network resulting in electrostatic
contributions to the osmotic swelling.
SANS has also been employed to investigate the structural changes for
polyŽNIPAM. particles as a result of thermally induced de-swelling, osmotic
de-swelling and co-non-solvency w71,72x. Representative scattering data appear in
Fig. 10. The scattering profile for the pure microgel particles at 508C shows linear
behaviour with a gradient of y4.22 ŽPorod scattering ., whereas a shallower
gradient is observed at 258C. These results indicate a change from collapsed Žhard
sphere. particles to swollen Ždiffuse. particles upon decreasing the temperature to
below the LCST. The data for the polyŽNIPAM. particles in the presence of added
d-PEO18K or d-MEOD exhibit smaller gradients over most of the Q range. The
scattering profiles for the latter systems are similar over the Q range 0.008]0.02.
PolyŽNIPAM. particles subjected to osmotic de-swelling and co-non-solvency ap-
pear to have a more diffuse network structure than pure particles heated to 508C.
The thermally de-swollen particles have sharp boundaries over the entire Q range.

10. Internal structure of microgel particles

The internal structure of microgel particles determines their swelling properties

and is of considerable importance. The most important structural information is
the distribution of the cross-linking monomer as a function of distance from the
particle center. Although the theories of microgel swelling, described above,
assume uniform swelling Ži.e. a uniform cross-link density. the situation is highly
unlikely. A more probable situation, for microgel particles prepared by emulsion
22 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25

Fig. 10. Small-angle neutron scattering profiles for polyŽNIPAM. microgel particles obtained under a
variety of conditions. Measurement for the pure microgel system was made at 258C Ž=. and 508C ŽB..
Data were also recorded at room temperature in the presence of d-MeOD Ž f a s 0.53, I. and of
d-PEO18K Ž f 3 s 0.13, v..

polymerisation, is that the cross-link density decreases from the center of the
particles toward the periphery. There is some support for this viewpoint from the
work of Nieuwenhuis et al. w24x. They examined polyŽMMA. ŽMMA s
methylmethacrylate . microgel particles dispersed in benzene and reported a varia-
tion in the microgel particle diameters measured using a range of techniques. It
was concluded that the particles contained an inhomogeneous cross-link distribu-
tion.
McPhee et al. w69x measured the efficiency of cross-linking monomer incorpora-
tion into growing particles during SFEP and concluded that a large proportion of
the cross-links were incorporated during the initial growth of the particles. This is
not surprising as the solubility of a polymer chain decreases with increasing
molecular weight and addition of cross-linking monomer facilitates a substantial
increase in its length. Accordingly, attainment of uniformly swollen microgel
particles may be more likely using polymerisation in a good solvent. The improved
homogeneity of the structure would be at the expense of a monodisperse particle
size distribution Žsee Section 3..

11. Outlook

Microgel particles have excellent potential for application. This is evidenced by

applications involving microgel particles in the surface coatings industry Žpaint..
 B.R. Saunders, B. Vincent r Ad¨ . Colloid Interface Sci. 80 (1999) 1]25 23

Future applications for microgel particles are expected to include catalysis Žmicro-
gel particle supported catalysis . and micro-encapsulation Žpharmaceutical industry..
There is considerable scope for enhanced drug delivery using core-shell microgel
particles. For example, future generations of microgel particles may contain
cis-platin and a cross-linked shell that undergoes spontaneous swelling when in
contact with cancer cells. Delivery systems for cisplatin that specifically target
cancer cells are urgently required.
Frictional drag-reduction offers considerable promise for reducing energy losses
during turbulent flow of fluids in pipes w73x. Addition of linear polymers to the
continuous phase has resulted in considerable drag reduction w74x. However, the
shear stability of the chains is poor with shear induced chain scission resulting in
diminished drag reduction as a function of time. Microgel particles are deformable
and are promising candidates for drag reduction. The shear induced deformation
of the network would be distributed over the entire network reducing chain
scission and improving shear stability. This approach is being pursued at the
University of Adelaide.
Another area for future application of microgel particles is in water purification.
PolyŽNIPAM-co-acrylic acid. microgel particles take up heavy metal ions w43x.
However, the efficiency of uptake is low due to the restricted proportions of acrylic
acid that can be used during preparation. Improvements are likely when microgel
particles containing high carboxyl contents are prepared. Moreover, it should be
possible to produce chelating monomers which will specifically bind target metal
ions.
There are a variety of possible applications for microgel particles. Some of the
applications have already been achieved Že.g. rheological control additives.; whereas
many more are yet to be realised. Microgel particles are versatile systems and are
expected to play an important role in pollution control and the surface coatings
and pharmaceutical industries in years to come. The understanding of microgel
particles has come a long way since their discovery and there is plenty of room for
research into these unusual model colloids.

Acknowledgements

The authors would like to thank the EPSRC ŽUK. and the Paint Research
Association ŽUK. for financial support. The co-non-solvency data supplied by
Helen Crowther ŽUniversity of Bristol. is gratefully acknowledged.

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