Advances in Colloid and Interface Science 80 1999.

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, Cantocks 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 SFEP. 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 e.g. osmotic de-swelling.. The polyNIPAM. NIPAM s N-isopropylacrylamide. microgel system is considered in detail in terms of swelling, rheological, small-angle neutron scattering SANS. and kinetic data. The review concludes with a discussion of the internal structure for microgel particles and consideration of areas for further research. 1999 Elsevier Science B.V. All rights reserved. Keywords: Microgel particles; Synthesis; Properties; Internal structure

Contents
1. 2. 3. 4.
U

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

Corresponding author.

0001-8686r99r$ - see front matter 1999 Elsever Science B.V. All rights reserved. P I I: S 0 0 0 1 - 8 6 8 6 9 8 . 0 0 0 7 1 - 2

B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

5. Properties of microgel particles . . . . . . . . . . . . . . . . . . . . . . 6. Osmotic de-swelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. Stability of dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8. Swelling control by addition of alkanols: co-non-solvency . . . . . 9. Small-angle neutron scattering investigations of microgel particles 10. Internal structure of microgel particles . . . . . . . . . . . . . . . . . 11. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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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 the abbreviations employed in this paper are listed in Table 1.. PolyNIPAM. 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 e.g. toluene.. The ionic microgel particles prepared to date frequently contain carboxylate groups derived from acrylic acid or methacrylic acid. There is considerable 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 LCST.. PolyNIPAM. undergoes thermally induced de-swelling when the solution temperature is increased above the LCST 32 C in water.. Heskins and Guillet were the first to extensively study the LCST for linear polyNIPAM. 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 hydrophobic 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 depending 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

Fig. 1. Structures of the monomers frequently used to prepare microgel particles. The monomers are a. methylmethacrylate, b. methacrylic acid, c. styrene, d. divinylbenzene, e. acrylic acid, f. N-isopropylacrylamide, g. N, N -methylene bisacrylamide and h. 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 d . is an important parameter for industrial applications and rheological studies. The value of d is proportional to the volume fraction of polymer in the dispersion p . and is independent of particle size. The relationship between d , p and 2 is simply:
d

p 2

1.

where: mp
p

s m p
p

ms
s

2.

m p , m s are the mass of polymer and solvent, respectively; p and s are the densities of polymer and solvent. 2 is the volume fraction of polymer in each particle. The most important property for microgel particles is the extent of swelling. The

B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

Table 1 Abbreviations used Abbreviation AA AC AL ALHCl AMPS AN BA BAlc BC BCA Bz DMF DVB EA EB HA LCST MAA MADQUAT d-MEOD MeOH MMA NIPAM PAA PCS PEG d-PEO PrOH PS QAC SDS SFEP Sty TBA Tol THF 2VP W Meaning Acrylic acid Acrylamide Alcohol Allylamine hydrochloride 2-Acrylamido-2-methylpropanesulfonate Acrylonitrile N, N -methylenebisacrylamide Benzyl alcohol Butylcarbazole Butylcarbazole acetate Benzene Dimethylformamide Divinylbenzene Ethylacrylate Ethylbenzene Hydroxamic acid Lower critical solution temperature Methacrylic acid 2-Methacryloyloxy.ethyl.trimethylammonium Deuterated methanol Methanol Methylmethacrylate N-isopropylacrylamide Polyacrylic acid. Photon correlation spectroscopy Polyethyleneglycol. Deuterated polyethylene oxide. 2-Propanol Polystyrene Quarternary ammonium chloride Sodium dodecyl sulfate Surfactant-free emulsion polymerization Styrene Tert-butylmethacrylate Toluene Tetrahydrofuran 2-Vinylpyridine Water

extent of swelling is usually determined from changes in the hydrodynamic diameters measured using PCS. It is experimentally convenient to measure swelling changes relative to the fully swollen hydrodynamic diameter d o .. The extent of particle de-swelling is expressed as the de-swelling ratio . which is simply: s drd o . 3 , where d is the measured hydrodynamic diameter at a given temperature etc. The de-swelling ratio and 2 are related by: s d crd o . 3r 2 where d c , is the diameter of the particles in the fully collapsed state i.e. particles contain no

B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

Fig. 2. Diagram depicting a microgel particle in a poor a, respectively.

12

) 0.5. and good b,

12

s 0. solvent,

solvent.. This definition of 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 resin. 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 see below.. Microgel systems also show promise in the printing and pharmaceutical industries. Microgel particles may be functionalised to yield photo-cross-linkable particles. 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.

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 lymph nodes etc.. within the body. This micro-encapsulation technique relies on developing sensitive trigger mechanisms whereby binding of the microgel surface groups to specific sites on target cells e.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 conventional emulsion polymerisation. or in the absence of added surfactant surfactant-free emulsion polymerisation, SFEP.. In the latter method, the continuous phase must have a high dielectric constant e.g. water. and ionic initiators are employed e.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 microgel particles i.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 preparation of polyNIPAM., PS and polyMMA. microgel systems w9,15,16x. SFEP is ideally suited to the preparation of polyNIPAM.. Typically, NIPAM is polymerised in the presence of persulfate and cross-linking monomer at a temperature of ; 70 C. The particles gradually swell when the temperature is decreased with the maximum degree of swelling occurring around 32 C; 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 2y initiator S 2 O 8 . 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 of 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

Fig. 3. Mechanism for the preparation of microgel particles by SFEP. The steps shown are initiator decomposition a., initiation b., propagation c., particle nucleation d., particle aggregation e., particle growth in a poor solvent. f. and particle swelling in a good solvent g.. The counter-cations and the particle charges for steps f. and g. have been omitted for clarity. M represents a vinyl monomer.

For particles other than polyNIPAM., particle swelling is achieved by removal of the particles from the continuous phase e.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 polyNIPAM. 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 crosslinking monomers e.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. Bulk macrogel would have resulted if the monomer concentration employed was

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 cf. 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. Poly2VP-b-sty-b-2VP. copolymer micelles were reacted with 1,4-di-idobutane in a hemi-solvent a 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. Nanogel 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 consisted of anionic 2-acrylamido-2-methylpropanesulfonate AMPS. and cationic 2-methacryloyloxy.ethyl.trimethylammonium MADQUAT. monomers in addition to BA. The copolymerisation was initiated using UV irradiation and the product isolated and re-dispersed in aqueous electrolyte solution to yield polyampholyte 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 polyNIPAM. microgel particles. Microgel particles based on PS and polyMMA. 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 polyNIPAM.. NIPAM is commercially available and polyNIPAM. particles are easily prepared. These particles

B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

usually contain between 80 and 99% water in the swollen state 0.001 - 2 - 0.20.. These particles are very sensitive to environmental changes as judged by swellingrde-swelling transitions .. PS and polyMMA. microgel particles have also been well studied Table 2.. PolyMMA. 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 polyNIPAM. and PS microgel particles w15,16,39x. PolyNIPAM. 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 typeb Prep methodc Collapsed particle size nm. 60 1000 300 50 Swollen particle size nm.
d 2

Refs.

PolyAC. PolyAN. PolyALHCl. Poly AMPSr MADQUAT. PolyEArMAA. PolyMMA. PolyMMA. PolyMMA. Poly MMArAA. Poly MMArAArHA. Poly MMArMAA. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM. PolyNIPAM.

WrAL DMF W W

N N I I

PP EP PPC IMP

735 22 26 100 250

0.068

w21x w22x w12x w13x w23x w24x w25x w26x w27x w28x

W Bz BCA BAlc W W W W W W W W W W W W W W W W W W W

I N N N I I I N N N N N N N N N N N N N N N I

EP EP EP EP EP EP SFEP SFEP SFEP SFEP SFEP SFEP EP SFEP SFEP SFEP SFEP SFEP SFEP SFEP EP SFEP EP

60 100 205 230 300 75 140

140 355 135 650 85 40

600 480 205 255

0.08 0.11 0.07 0.10 0.17

0.005 0.20 0.28 0.69

310 500 240 135 120 240 375 400 120 23 50 150 325 335 145 315 200 880

750

0.07

w16x

450 270 520 450 950 700 520 130 470 340 590 685

0.17 0.12 0.012 0.15 0.062 0.19

590

w9x w29x w30x w31x w32x w33x w34x w35x w36x 0.012 0.001 0.006 w37x w38x 0.085 w39x 0.14 0.17 w16x w40x w41x 0.15 0.010 0.10 w42x

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B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

Table 2 Continued. Polymer Solvent Microgel typeb Prep methodc Collapsed particle size nm. 300 30 100 405 520 75 130 345 355 328 425 26 84 24 35 0.11 0.23 60 80 250 380 75 185 600 1100 135 35 80 250 700 0.035 0.28 Swollen particle size nm. 700 900 140 425 490 1150
d 2

Refs.

Poly NIPAMrAA. Poly NIPAMrMAA. PS PS PS PS PS PS PS PS PS PolystyrAA. PolystyrMAA. PolystyrQAC. Polystyr2VP. Polystyr2VP. Poly styrmercapto. PolyTBA. Poly4VP.
a b

W W EB Various Tol EB THF W Tol Tol W Dioxan THFrW W Tol W W Heptane W

I I N N N N N I N N I I I I N I N N NrI

SFEP EP EP EP EP SFEP EP EP FC FC FC FC BC EP BC EP SFEP AN EP

0.04 0.08 0.005 0.045 0.098 0.63

w43x w44x w10x w45x w46x w15x w47x w48x w49x w18x w8x w50x w51x w52x w20x w53x w54x w19x w55x

570 660 700 42 240 24 208

0.16 0.22 0.224 0.042 0.23

150 200

0.006 0.035

See Table 1 for abbreviations used for the polymers and solvents. N, neutral; I, ionic. c EP, emulsion polymerization; SFEP, surfactant-free emulsion polymerization; IMP, inverse microemulsion polymerization; BC, via block copolymers; AN, anionic polymerization; PP, percipitation polymerization; 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 polyNIPAM. and PS microgel particles show that the particles deformed to a pancake structure during solvent evaporation see 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 a. and water b.. The particles are viewed at an angle of 30 to the sample plane. The average size of the particles shown in b. was measured as 355 nm from TEM measurements.

anionic. However, a notable exception is polystyr4VP.. Loxley and Vincent w53x examined the pH-dependent swelling and swelling kinetics . of the polystyr4VP.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

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B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

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

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

4. Particle swelling theory Florys 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 2 . obtained at equilibrium 2 s 1 in the collapsed state.. Florys theory leads to w56x: s

X 1 Vc 1 y 2
12

3r5

3.

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 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 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 monomer B. and a minor proportion of normally. difunctional cross-linking segments A.; the mole fraction of the latter 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 Vc s 2 xA MB
B

4.

where M B and B are the molecular weight and density of the B segments, respectively. Substitution of Eq. 4. into Eq. 3. and assuming B s 1 leads to a simple expression describing the dependence of the volume fraction of the microgel particles on the network composition and solvency: s

2 xAV1
12

3r5

MB

5.

where the excluded volume parameter, 12 s 0.5 y 12 .. The polymer volume fraction increases particles de-swell. if the cross-link density increases or the solvency becomes poorer 12 decreases.. Florys 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 free. 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 Florys theory of gel swelling: i. it assumes a uniform cross-link density within the network. There is evidence that this is not the case for many microgel systems see below.. ii. The concentration dependence of is not included Napper 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 concentration varies with swelling. A more appropriate model though complex. for describing the swelling of polyNIPAM. networks has been employed by Lele et al. w60x. They applied the lattice-fluid-hydrogen bonding theory LFHB. to the swelling of polyNIPAM. networks in aqueous alcohol solutions. The theory incorporated a number of different hydrogen bonding interactions within the polyNIPAM.-water-alcohol system. The extended LFHB model predicted re-entrant swelling for the system and qualitatively described the experimental data. PolyNIPAM. microgel particles dispersed in water alcohol mixtures also exhibit re-entrant swelling w41x and this is discussed in more detail below.

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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 acid or base, i.e. pH-independent. groups from within microgel particles which 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 mobile. 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 -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 acid 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 a higher charge density suppresses ionisation. and background ionic strength screens 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 polyMMArMAA. microgel system the background ionic strength was not systematically controlled. w16x. On increasing the pH from low values to high values, the swelling extent increases as the weak. 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 rcrr s . 3 and the total on the surface is 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 polyMMArMAA. 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-swelling kinetics in comparison to macrogels. Tanaka et al. w61x investigated the dependence of the swelling transition rate on particle size for spherical polyacrylamide. gels. A characteristic time, , described the rate of swelling; represents the point where ; 75% of the total swelling has occurred. Tanaka et al. w61x showed that was proportional to the square of the collapsed particle radius, rc . Assuming this relationship is applicable to microgel particles rc s 100 nm., the value of for microgel particles is expected to be eight orders of magnitude faster than for a macrogel 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 dispersions are highly shear thinning w25x. When compared, at the same number concentration, 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

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B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

is frequently reported. Miller et al. w63x reported electrophoretic mobility measurements 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 PALS.. Snowden et al. w30x have reported mobilities for polyNIPAM. 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 PSmicrogel.rtoluenerPSfree 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 2 . with volume fraction of excluded free polymer 3 . in the continuous phase. The theory is based on Florys theory of network swelling and incorporates the effect of the osmotic pressure due to excluded free polymer on the solvent chemical potential, 1. The condition that 1 in the particle interior and in the continuous phase must equate at equilibrium yields the following equation w15x: 1 y 2
2 3

13

3 M1 1 M3

21 2 2

12

.y2

/
1

M1

XA MB

1r3 2

6.

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 x x s 1, 3 and B. represent the molecular weight and density, respectively. Eq. 6. has been applied to the PSmicrogel.rEBrPSfree polymer. system and predicted osmotic de-swelling 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 2 than predicted by Eq. 6.. Fig. 7 shows the variation of the de-swelling ratio for polyNIPAM.rwaterrPEG, PSmicrogel.rEBrPSfree polymer. and polyMMArMAA.rwaterrPEG systems as a function of the molecular weight of added free polymer at fixed values of 3 . The data show the greatest de-swelling for the polyNIPAM.rwaterrPEG system. The polyMMArMAA. 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 polyNIPAM. B., PS . and polyMMArMAA. ^. microgel particles by addition of free polymer of different molecular weight. The free polymers used in the aqueous systems 3 s 0.13. and non-aqueous system 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 d Eq. 1... Osmotic de-swelling of polyacrylate. 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 Stokes 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.

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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-swelling occurs so the van der Waals forces become increasingly more significant. If charged groups are incorporated in 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 polyNIPAM. particles are responsible for the fact that these dispersions remain stable during synthesis, even though the temperature is much higher than the LCST of polyNIPAM. 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 polyNIPAM. dispersions are stable in the presence of high electrolyte concentrations such that electrostatic interactions are negligible. provided the dispersion temperature is below the LCST w29x. In addition, PS microgel particles are swollen and stable . in ethylbenzene w15x even in the presence of 20 wt.% free PS see 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 . and is linked to the degree of particle swelling through 2 . The stability of particular dispersions to flocculation is conveniently examined by measurements of the n-value. The n-value is the gradient of log optical density. vs. log wavelength. plots n s ydlogO.D.rdlog .. and has a magnitude which decreases with average particle size in 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 polyNIPAM.rwaterrPEG, PSmicrogel.rEBrPSfree polymer. and polyMMArMAA.rwaterrPEG dispersions w15,16,39x. The data reveal that polyNIPAM. 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 conditions 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 see

B.R. Saunders, B. Vincent r Ad . Colloid Interface Sci. 80 (1999) 1 25

19

Fig. 8. Variation of the n-values for polyNIPAMrwaterrPEG10K. B., PSmicrogel.rEBrPS17Kfree polymer. ^. and polyMMArMAA.rwaterrPEG17K . 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 nonuniform pore size distribution already present within the particles.

8. Swelling control by addition of alkanols: co-non-solvency Linear polyNIPAM. 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 polyNIPAM. 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 polyNIPAM. and polyMMArMAA. microgel particles dispersed in aqueous PrOH solutions as a function of 2-PrOH volume fraction a .. The data for each system show de-swelling at moderate values of a and re-entrant swelling at higher values of a . The mechanism responsible for co-non-solvency most likely involves clathrate structure formation w70x. In pure water the polyNIPAM. network is fully swollen by the attractive water polymer interactions hydrogen 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 clathrate 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 polyMMArMAA. B. and polyNIPAM. `. microgel particles dispersed in aqueous PrOH solutions.

tures and polyNIPAM. 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 hydrophobic 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 SANS. experiment involves the measurement of the scattered intensity I Q .. of a neutron beam with a wavelength, , as a function of the scattering vector Q .. The scattering vector is related to the scattering angle . by: Qs 4 sin

/
2 .2 P Q .

7.

For dilute colloidal dispersions, such as microgels, the scattered intensity, I Q ., is a function of the contrast factor ., the particle form factor P Q .. and the particle concentration Np .. I Q . s Vp2 Np 8.

where Vp is the particle volume. For spherical particles of uniform average density, P Q . is given by: P Q. s 3 sin Qr . y Qrcos Qr . Qr . 3
2

9.

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 using 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 polyNIPAM. microgel particles in the presence of SDS sodium dodecyl sulfate . using SANS. They assumed that the scattered intensity from the microgel particles obeyed the equation: I Q . s AQy4 q IL 0 . 1q
2

Q2

10.

where A and IL0. are constants and is the correlation length which characterises the mean separation between density fluctuations e.g. the pore size.. Eq. 10. assumes that the scattering from microgel particles has components from the whole particle first term. and polymer in a solution-like environment second term.. Mears et al. found that SDS caused swelling of the polyNIPAM. 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 polyNIPAM. network resulting in electrostatic contributions to the osmotic swelling. SANS has also been employed to investigate the structural changes for polyNIPAM. 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 50 C shows linear behaviour with a gradient of y4.22 Porod scattering ., whereas a shallower gradient is observed at 25 C. These results indicate a change from collapsed hard sphere. particles to swollen diffuse. particles upon decreasing the temperature to below the LCST. The data for the polyNIPAM. 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. PolyNIPAM. particles subjected to osmotic de-swelling and co-non-solvency appear to have a more diffuse network structure than pure particles heated to 50 C. 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 i.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 polyNIPAM. microgel particles obtained under a variety of conditions. Measurement for the pure microgel system was made at 25 C =. and 50 C B.. Data were also recorded at room temperature in the presence of d-MeOD a s 0.53, I. and of d-PEO18K 3 s 0.13, ..

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 polyMMA. MMA s methylmethacrylate . microgel particles dispersed in benzene and reported a variation in the microgel particle diameters measured using a range of techniques. It was concluded that the particles contained an inhomogeneous cross-link distribution. McPhee et al. w69x measured the efficiency of cross-linking monomer incorporation 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 see Section 3..

11. Outlook Microgel particles have excellent potential for application. This is evidenced by applications involving microgel particles in the surface coatings industry paint..

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 microgel particle supported catalysis . and micro-encapsulation pharmaceutical 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. PolyNIPAM-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 e.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 UK. and the Paint Research Association UK. for financial support. The co-non-solvency data supplied by Helen Crowther University of Bristol. is gratefully acknowledged. References
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w7x w8x w9x w10x w11x w12x w13x w14x w15x w16x w17x w18x w19x w20x w21x w22x w23x w24x w25x w26x w27x w28x w29x w30x w31x w32x w33x w34x w35x w36x w37x w38x w39x w40x w41x w42x w43x w44x w45x w46x w47x w48x w49x w50x w51x w52x w53x w54x w55x w56x w57x w58x w59x

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