Mesoscale simulations of the behavior of charged polymer brushes under normal compression and lateral shear forces

Dissipative particle dynamics (DPD) was used to investigate the behavior of two opposing end-grafted charged polymer brushes in aqueous media under normal compression and lateral shear. The effect of polymer molecular weight, degree of ionization, grafting density, ionic strength, and compression on the polymer conformation and the resulting shear force between the opposing polymer layers were investigated. The simulations were carried out for the poly(tert-butyl methacrylate)-block-poly(sodium sulfonate glycidyl methacrylate) copolymer, referred as PtBMA-b-PGMAS, end-attached to a hydrophobic surface for comparison with previous experimental data. Mutual interpenetration of the opposing end-grafted chains upon compression is negligible for highly charged polymer brushes for compression ratios ranging from 2.5 to 0.25. Under electrostatic screening effects or for weakly charged polymer brushes, a significant mutual interpenetration was measured. The variation of interpenetration thickness with separation distance, grafting density, and polymer size follows the same scaling law as the one observed for two opposing grafted neutral brushes in good solvent. However, compression between two opposing charged brushes results in less interpenetration relative to neutral brushes when considering equivalent grafting density and molecular weight. The friction coefficient between two opposing polymer-coated surfaces sliding past each other is shown to be directly correlated with the interpenetration thickness and more specifically to the number of polymer segments within the interpenetration layer.     

Friction and normal interaction forces between irreversibly attached weakly charged polymer brushes

Polyelectrolyte brushes were built on mica by anchoring polystyrene-poly(acrylic acid) (PS-b-PAA) diblock copolymers at a controlled surface density in a polystyrene monolayer covalently attached to OH-activated mica surfaces. Compared to physisorbed polymer brushes, these irreversibly attached charged brushes allow the polymer grafting density to remain constant upon changes in environmental conditions (e.g., pH, salt concentration, compression, and shear). The normal interaction and friction forces as a function of surface separation distance and at different concentrations of added salt (NaCl) were investigated using a surface forces apparatus. The interaction force profiles were completely reversible both on loading and receding and were purely repulsive. For a constant polymer grafting density, the influence of the polyelectrolyte charges and the Debye screening effect on the overall interaction forces was investigated. The experimental interaction force profiles agree very well with scaling models developed for neutral and charged polymer brushes. The variation of the friction force between two PAA brushes in motion with respect to each other as a function of surface separation distance appeared to be similar to that observed with neutral brushes. This similarity suggests that the increase in friction is associated with an increase in mutual interpenetration upon compression as observed with neutral polymers. The effect of the PAA charges and added ions was more significant on the repulsive normal forces than on the friction forces. The reversible characteristics of the normal force profiles and friction measurements confirmed the strong attachment of the PAA brushes to the mica substrate. High friction coefficients (ca 0.3) were measured at relatively high pressures (40 atm) with no surface damage or polymer removal.     

Effect of temperature on the frictional forces between polystyrene brushes

Normal and shear forces between opposing polystyrene (PS) brushes made from preferentially assembled PS–polyvinylpyridine diblock copolymers were measured in toluene and in near‐theta cyclohexane at 32, 40, and 50 °C, using a modified surface forces apparatus. In cyclohexane, over the temperature window probed, the normal forces of interaction are repulsive and the range of those force profiles changes only slightly; however, for both of the PS brushes studied, the onset of shear forces in near‐theta cyclohexane is strongly influenced by changes in temperature: As the temperature is increased, the onset of the frictional interactions between the brushes in cyclohexane shifts to smaller distances, approaching the distances where frictional forces are observed for brushes in the good solvent toluene. The pattern of behavior seen in the frictional response between the limits of good and theta condition is attributed to composition fluctuations, which increase near the theta condition because of the decrease in excluded volume interactions. These fluctuations may give rise to increased drag during shearing motion because of interfacial roughness or interchain coupling across the brush–brush interface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 649–655, 2006     

Normal and frictional forces between surfaces bearing polyelectrolyte brushes

Normal and shear forces were measured as a function of surface separation, D, between hydrophobized mica surfaces bearing layers of a hydrophobic-polyelectrolytic diblock copolymer, poly(methyl methacrylate)- block-poly(sodium sulfonated glycidyl methacrylate) copolymer (PMMA- b-PSGMA). The copolymers were attached to each hydrophobized surface by their hydrophobic PMMA moieties with the nonadsorbing polyelectrolytic PSGMA tails extending into the aqueous medium to form a polyelectrolyte brush. Following overnight incubation in 10 (-4) w/v aqueous solution of the copolymer, the strong hydrophobic attraction between the hydrophobized mica surfaces across water was replaced by strongly repulsive normal forces between them. These were attributed to the osmotic repulsion arising from the confined counterions at long-range, together with steric repulsion between the compressed brush layers at shorter range. The corresponding shear forces on sliding the surfaces were extremely low and below our detection limit (+/-20-30 nN), even when compressed down to a volume fraction close to unity. On further compression, very weak shear forces (130 +/- 30 nN) were measured due to the increase in the effective viscous drag experienced by the compressed, sliding layers. At separations corresponding to pressures of a few atmospheres, the shearing motion led to abrupt removal of most of the chains out of the gap, and the surfaces jumped into adhesive contact. The extremely low frictional forces between the charged brushes (prior to their removal) is attributed to the exceptional resistance to mutual interpenetration displayed by the compressed, counterion-swollen brushes, together with the fluidity of the hydration layers surrounding the charged, rubbing polymer segments.     

A Langevin dynamics simulation study of the tribology of polymer loop brushes

The tribology of surfaces modified with doubly bound polymer chains (loops) has been investigated in good solvent conditions using Langevin dynamics simulations. The density profiles, brush interpenetration, chain inclination, normal forces, and shear forces for two flat substrates modified by doubly bound bead-necklace polymers and equivalent singly bound polymers (twice as many polymer chains of 12 the molecular weight of the loop chains) were determined and compared as a function of surface separation, grafting density, and shear velocity. The doubly bound polymer layers showed less interpenetration with decreasing separation than the equivalent singly bound layers. Surprisingly, this difference in interpenetration between doubly bound polymer and singly bound polymer did not result in decreased friction at high shear velocity possibly due to the decreased ability of the doubly bound chains to deform in response to the applied shear. However, at lower shear velocity, where deformation of the chains in the flow direction is less pronounced and the difference in interpenetration is greater between the doubly bound and singly bound chains, some reduction in friction was observed.     

Attractive bridging interactions in dense polymer brushes in good solvent measured by atomic force microscopy

Using an atomic force microscope (AFM), we have investigated the interaction forces exerted by latex particles bearing densely grafted polymer brushes consisting of poly(N,N-dimethylacrylamide) (PDMA), poly(methoxyethylacrylamide) (PMEA), poly(N-isopropylacrylamide) (PNIPAM), and PMEA-b-PNIPAM in aqueous media (good solvent). The brushes were prepared by controlled surface-initiated atom transfer radical polymerization, and the hydrodynamic thicknesses were measured by dynamic light scattering. The molecular weight (Mn), grafting density (sigma), and polydispersity (PDI) of the brushes were determined by gel permeation chromatography and multiangle laser light scattering after cleaving the polymer from the latex surface by hydrolysis. Force profiles of PDMA (0.017 nm(-2) < or = sigma < or = 0.17 nm-2) and PMEA (sigma = 0.054 nm-2) brushes were purely repulsive upon compression, with forces increasing with Mn and a, as expected, due to excluded volume interactions. At a sufficiently low grafting density (sigma = 0.012 nm-2), PDMA exhibited a long-range exponentially increasing attractive force followed by repulsion upon further compression. The long-range attractive force is believed to be due to bridging between the free chain ends and the AFM tip. The PNIPAM brush exhibited a bridging force at a grafting density of 0.037 nm(-2), a value lower than the sigma needed to induce bridging in the PDMA brush. Bridging was therefore found to depend on grafting density as well as on the nature of the monomer. The grafting densities of these polymers were larger than those typically associated with bridging. Bridging interactions were used to confirm the presence of PNIPAM in a block copolymer PMEA-b-PNIPAMA brush given that the original PMEA homopolymer brush produced a purely repulsive force. The attractive force was first detected in the block copolymer brush at a separation that increased with the length of the PNIPAM block.     

Linear shear viscoelasticity of confined,end-attached polymers in a near-theta solvent

Diblock copolymers of polystyrene and polyvinylpyridine, end-attached to mica by the traditional method of selecting one block to be insoluble and the other block to be soluble in the solvent, were studied with surface-force experiments while immersed in trans-decalin, a near-theta solvent for the polystyrene block, with special attention given to the small-amplitude shear viscoelastic response. The relaxation time, defined as the inverse frequency at which the effective loss modulus equaled the effective storage modulus, was studied not only as a function of the film thickness but also as a function of the grafting density. The relaxation times started to slow in direct proportion to diminishing surface separation when the surface separation took the value D ≈ L_o/3 (where L_o is the thickness of the uncompressed end-attached layer). Attempts to make comparisons with available theories met with limited success. To test experimentally the origin of this shear viscoelastic slowdown, similar measurements were made with adsorbed polystyrene with a molecular weight similar to that of the polystyrene moiety of the diblock copolymer, and it was found that high magnitudes of the effective viscoelastic shear moduli appeared only when the compression was much larger. In a control experiment in which interpenetration between opposed end-attached chains was precluded, we also studied the case of adsorbed polystyrene–polyvinylpyridine on one side and a bare mica surface on the other side, and the effective viscoelastic shear forces were reduced by nearly 1 order of magnitude. By inference, in the opposed diblock copolymer systems, we attributed the slowdown of the relaxation times with decreasing film thickness to the interpenetration of end-attached chains. Additional comments are made regarding the ratio of shear forces to compressive forces, which is called the small-strain friction coefficient. This is believed to be the first quantification of the linear-response relaxation time of end-attached polymer layers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3487–3496, 2005     

Simple model for grafted polymer brushes

The first theories of grafted polymer brushes assumed a step profile for the monomer density. Later, the real density profile was obtained from Monte Carlo or molecular dynamics simulations and calculated numerically using a self-consistent field theory. The analytical approximations of the solutions of the self-consistent field equations provided a parabolic dependence of the self-consistent field, which in turn led to a parabolic distribution for the monomer density in neutral brushes. As shown by numerical simulations, this model is not accurate for dense polymer brushes, with highly stretched polymers. In addition, the scaling laws obtained from the analytical approximations of the self-consistent field theory are identical to those derived from the earlier step-profile-approximation and predict a vanishing thickness of the brush at low graft densities, and a thickness exceeding the length of the polymer chains at high graft densities. Here a simple model is suggested to calculate the monomer density and the interaction between surfaces with grafted polymer brushes, based on an approximate calculation of the partition function of the polymer chains. The present model can be employed for both good and poor solvents, is compatible with a parabolic-like profile at moderate graft densities, and leads to an almost steplike density for highly stretched brushes. While the thickness of the brush depends strongly on solvent quality, it is a continuous function in the vicinity of the temperature. In good and moderately poor solvents, the interactions between surfaces with grafted polymer brushes are always repulsive, whereas in poor solvents the interactions are repulsive at small separations and become attractive at intermediate separation distances, in agreement with experiment. At large separations, a very weak repulsion is predicted.     

Direct measurement of shear forces between polymer-bearing surfaces sliding past each other

We have used a recently developed surface force balance to measure, with extreme sensitivity, both lateral and normal forces between interacting surfaces, for the case of simple liquids and particularly with surface-attached polymers. The presence of polymers on the surfaces reduces drastically the force required to maintain them in sliding motion, under a given normal load, relative to the bare surface case. We believe this is due to the long range steric repulsion which can sustain a large normal load while maintaining a very fluid interfacial layer. The effect is much more marked for end-tethered chains in a good solvent than for adsorbed chains in a θ-solvent. This is attributed to the different extents of interpenetration of the compressed polymer layers.     

Preparation and characterization of V-shaped PS-b-PEO brushes anchored on planar gold substrate through the trithiocarbonate junction group

Trithiocarbonate group was introduced into the polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymers as the junction of the blocks through RAFT polymerization. Mixed PS and PEO brushes with a V-shape were prepared by anchoring the trithiocarbonate group on the planar gold substrate. The morphology of the V-shaped brushes was characterized by atomic force microscopy (AFM) and the surface composition responsive to solvent treatment was detected by X-ray photoelectron spectroscopy (XPS). Different morphologies were observed for the V-shaped PS-b-PEO brushes, depending on the chain structure and solvent treatment. The highly selective solvent for PEO, ethanol, can intensify or induce microphase separation of the V-shaped brushes, leading to vertical microphase separation. When the V-shaped brushes are treated with the co-solvent, THF, miscible morphology, lateral microphase separation, and vertical microphase separation are observed as the PS block length increases. After treatment with the non-selective poor solvent, cyclohexane, the V-shaped PS(106)-b-PEO(113) brush, exhibits a laterally microphase-separated morphology, but the V-shaped PS(52)-b-PEO(113) and PS(253)-b-PEO(113) brushes are vertically microphase-separated.     

The colloidal force of bead-spring chains in a good solvent

A recently developed density functional theory (DFT) for tethered bead-spring chains is used to investigate colloidal forces for the good solvent case. A planar surface of tethered chains is opposed to a bare, hard wall and the force exerted on the bare wall is calculated by way of the contact density. Previously, the case of large wall separation was investigated. The density profiles of the unperturbed chains, in that case, were found to be neither stepfunctions nor parabolas and were shown to accurately predict computer simulation results. In the present paper, the surface forces that result from the distortion of these density profiles at finite wall separation is studied. The resulting force function is analyzed for varying surface coverages, wall separations, and chain lengths. The results are found to be in near quantitative agreement with the scaling predictions of Alexander [S. Alexander, J. Phys. (Paris) 38, 983 (1977)] when the layer thickness is "correctly" defined. Finally, a hybrid Alexander-DFT theory is suggested for the analysis of experimental results.     

End‐Anchored Polymers: Compression by Different Mechanisms and Interpenetration of Apposing Layers

Summary: This paper presents a systematic study of the compression of end‐anchored polymer layers by a variety of mechanisms. We treat layers in both good and Θ solvents, and in the range of polymer densities that is normally encountered in experiments. Our primary technique is numerical self‐consistent field (NSCF) theory. We compare the NSCF results for the different mechanisms with each other, and with those of the analytic SCF theory. For each mechanism, we calculate the density profiles, layer thicknesses, and free energies, all as functions of the degree of polymerization and surface coverage. The free energy and the deformation of each layer depend on the compression mechanism, and they can be very different from the ASCF theory. For example, the energy of compression can be as much as three times greater than the analytical SCF (ASCF) prediction, and it does not reduce to simple, universal functions of the reduced distance between the surfaces. The overall physical picture simplifies if the free energy is expressed in terms of the layer deformation, rather than the reduced surface separation. We also examine and quantify the interpenetration of layers, discuss why ASCF theory applies better to some compression mechanisms than others, and end with comments on the difficulties in extracting quantitative information from surface‐forces experiments.

Comparisons of forces of compression in a good solvent for the three different systems, as functions of D/n_b. The lower three curves are for σ* = 3, and the upper three are for σ* = 23.     

Interaction forces and lubrication of dendronized surfaces

Dendron brushes provide excellent opportunities to tune mechanical properties of interfacial layers. Compared to linear brushes the dendronic version is more compact and thus gives more steep repulsive barriers upon brush overlap. Provided that the range is sufficient to overcome the Van der Waals forces, the many free ends may be used to functionalize the colloidal particles for ‘smart’ delivery applications. Brushes show little interpenetration upon lateral compression and therefore brushed surfaces feature low friction coefficients. Dendron brushes have comparatively lower interpenetration lengths and hence are expected to protect surfaces even better against wear. We argue that one can still improve on this: when the free ends of star-like or dendronic molecules are (chemically) linked to each other to form a brush with a peripheral layer of macrocycles, the interpenetration length is even less. The latter is shown to be the case in recent computer simulations and is reproduced here using the numerical self-consistent field method. We conclude that the role of branching of molecules, possibly in combination with charges in the brush, should be further investigated to come to a deeper understanding of lubrication and wear protection in aqueous media. The recent progress that is reviewed below has a small bias to theoretical developments. It contains solid stepping stones for more systematic experimental verifications and detailed computer simulations.     

Correlation between conformation change of polyelectrolyte brushes and lubrication

We directly monitor the absolute separation profiles that function as film thickness between a single glass disk and the charged polyelectrolyte brushes decorated steel slider in water using a home-made slider-on-disk apparatus, which reflects the structural conformation variations and interactions of polymer brushes under externally applied pressure, in addition to probing the relative variation of friction forces under different applied loads and sliding velocities. We find that the polyelectrolyte brushes modified surfaces can sustain high pressure and have extremely low friction coefficients(around 0.006 at pressures of 0.13 MPa; 0.5-0.6 without brushes). The water-lubrication characteristics are correlated to the structural conformation changes of the polyelectrolyte brushes that are mainly governed by electrostatic interactions and the osmotic pressure of counterions inside the polymer chains, which can be used to support and distribute the normal pressure. The apparent thickness of the brush decreases with the increase of loading forces, an increase in the ionic strength causes the polymer chains collapse, and the friction forces increase. This fundamental research is of great importance to understand the mechanical and structural properties of polyelectrolyte brushes and their influences on the tribological behaviors, and helps to design friction/lubrication-controlled surface/interface by taking advantage of polyelectrolyte brushes.     

Evaluation of an atomic force microscopy pull-off method for measuring molecular weight and polydispersity of polymer brushes: effect of grafting density

The accuracy of the molecular weights Mn and polydispersities of polymer brushes, determined by stretching the grafted chains using atomic force microscopy (AFM) and measuring the contour length distribution, was evaluated as a function of grafting density sigma. Poly(N,N-dimethylacrylamide) brushes were prepared by surface initiated atom transfer radical polymerization on latex particles with sigma ranging between 0.17 and 0.0059 chains/nm2 and constant Mn. The polymer, which could be cleaved from the grafting surface by hydrolysis and characterized by gel permeation chromatography (GPC), had a Mn of 30,600 and polydispersity (PDI) of 1.35. The Mn determined by the AFM technique for the higher density brushes agreed quite well with the GPC results but was significantly underestimated for the lower sigma. At high grafting density in good solvent, the extended structure of the brush increases the probability of forming segment-tip contacts located at the chain end. When the distance between chains approached twice the radius of gyration of the polymer, the transition from brush to mushroom structure presumably enabled the formation of a larger number of segment-tip contacts having separations smaller than the contour length, which explains the discrepancy between the two methods at low sigma. The PDI was typically higher than that obtained by GPC, suggesting that sampling of chains with above average contour length occurs at a frequency that is greater than their spatial distribution.     

Molecular weight and polydispersity estimation of adsorbing polymer brushes by atomic force microscopy

We have estimated the molecular weight, Mn, and polydispersity, PDI, of densely grafted poly(N-isopropylacrylamide) (PNIPAM) brushes using a novel atomic force microscopy (AFM) approach. When compression of a polymer brush induced adsorption of multiple chains to an AFM tip, the resulting decompression force profile exhibited a maximum attractive force at a separation, Lm, that decayed to zero with increasing tip-sample separation. We have found that the separation Lm approximates the average contour length, Lc, determined by gel permeation chromatography (GPC). The detection of a decaying attractive force at separations larger than Lc suggests that chains of above average length sequentially break free from the tip as they are stretched away from the grafting surface. The shape of the decompression profile in this region approximately paralleled the cumulative weight fraction of the grafted chains determined by GPC. The fraction of chains of a given molecular weight determined from a single force curve fit a log-normal distribution, having a standard deviation that provided an estimate of the PDI. We have characterized two PNIPAM brushes by this AFM technique as well as by GPC coupled to a multiangle laser light-scattering detector (MALLS). The values obtained by AFM-(1) Mn,AFM = (3.8+/-0.5) x 10(4), PDI,(AFM) = 1.3+/-0.1 and (2) Mn,AFM = (9.4+/-1.4) x 10(4), PDI,(AFM) = 1.3+/-0.1-agreed quite well with the corresponding GPC/MALLS values of (1) Mn,GPC = 4.77 x 10(4), PDI,GPC = 1.33 and (2) Mn,GPC = 9.49 x 10(4), PDI = 1.35. This technique requires only a single force curve to obtain a statistical distribution of contour lengths and provides a novel method for estimating the Mn and PDI of appropriate uniformly grafted dense polymer layers.     

Stability of polydimethylsiloxane-magnetite nanoparticle dispersions against flocculation: interparticle interactions of polydisperse materials

The colloidal stability of dispersions comprised of magnetite nanoparticles coated with polydimethylsiloxane (PDMS) oligomers was investigated theoretically and experimentally. Particle-particle interaction potentials in a theta solvent and in a good solvent for the PDMS were predicted by calculating van der Waals, electrostatic, steric, and magnetic forces as functions of interparticle separation distances. A variety of nanoparticle sizes and size distributions were considered. Calculations of the interparticle potential in dilute suspensions indicated that flocculation was likely for the largest 1% of the population of particles. Finally, the rheology of these complexes over time in the absence of a solvent was measured to probe their stabilities against flocculation as neat fluids. An increase in viscosity was observed upon aging, suggesting that some agglomeration occurs with time. However, the effects of aging could be removed by exposing the sample to high shear, indicating that the magnetic fluids were not irreversibly flocculated.     

Impact of solvent quality on nanoparticle dispersion in semidilute and concentrated polymer solutions

We investigated how solvent quality affects the stability of polymer-grafted nanoparticles in semidilute and concentrated polymer solutions, which extends our previous studies on these types of dispersions in good solvents [Langmuir 2008, 24, 5260-5269]. As discussed in the current article, dynamic light scattering (DLS) was used to quantify the diffusion of polydimethylsiloxane-grafted silica nanoparticles, or PDMS-g-silica, in bromocyclohexane as well as in PDMS/bromocyclohexane solutions. We established that bromocyclohexane is a theta solvent for PDMS by varying the temperature of the solutions with PDMS-g-silica nanoparticles and detecting their aggregation at a theta temperature of T(Θ) = 19.6 °C. Using this temperature as a benchmark for the transition between good and bad solvent conditions, further stability tests were carried out in semidilute and concentrated polymer solutions of PDMS in bromocyclohexane at T = 10-60 °C. Irrespective of temperature, i.e., solvent quality, we found that the nanoparticles dispersed uniformly when molecular weight of the graft polymer was greater than that of the free polymer. However, when the free polymer molecular weight was greater than that of the graft polymer, the nanoparticles aggregated. Visual studies were also used to confirm the correspondence between nanoparticle stability and graft and free polymer molecular weights in a wide range of marginally poor solvents with PDMS. Further, the correspondence between nanoparticle stability and instability with graft and free polymer molecular weight and solvent quality was also supported with self-consistent mean-field calculations. Thus, by relating experiment and theory, our results indicate that nanoparticle stability in semidilute and concentrated polymer solutions is governed by interactions between the graft and free polymers under conditions of variable solvency.     

Controlled synthesis of hydrophilic concentrated polymer brushes and their friction/lubrication properties in aqueous solutions

Polymer brushes of water‐soluble polymers, poly(2‐hydroxyethyl acrylate) (PHEA) and poly(poly(oxyethyleneglycol)methylether acrylate) (PPEGA), were synthesized on a silicon wafer and a silica particle by applying photo‐induced organotellurium‐mediated radical polymerization to surface‐initiated graft polymerization. High graft densities were obtained, corresponding to reduced graft densities of about 0.32 and 0.42 for the PHEA and PPEGA brushes, respectively. These values were high enough to be categorized in the regime of “concentrated” polymer brushes (CPBs). Atomic force microscopic (AFM) study revealed that the CPB of PPEGA was allowed to be highly swollen in water but the CPB of PHEA did not. This means that water is reasonably good for PPEGA but not for PHEA. The AFM microtribological study between swollen brushes revealed two lubrication regimes, namely, boundary‐ and hydrodynamic‐lubrication regimes, with different shear‐velocity dependencies. Reflecting insufficient quality of water as a solvent, the CPB of PHEA showed adhesive interaction and thereby a higher frictional coefficient μ in the boundary lubrication. More interestingly, super lubrication was achieved for the CPB of PPEGA with a μ value in the order of 10^?4 in water and in 0.1 M aqueous NaCl solution (without the help of electrostatic repulsion). Super lubrication was concluded to be a characteristic feature of the CPB, even in an aqueous system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates: molecular weight effect

The effect of molecular weight on the solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes on silicon wafers was studied. For a series of mixed brushes with a fixed PMMA M(n) and systematically changed PS M(n), a transition in water advancing contact angle (theta(a)) from 74 degrees, the value for a flat PMMA surface, to 91 degrees, the value for a flat PS film, was observed with increasing PS M(n) after treatment with CHCl(3). Atomic force microscopy studies showed smooth surfaces for all samples. While no significant changes in surface morphologies were observed after treatment with cyclohexane, a selective solvent for PS, contact angle and XPS studies indicated that the mixed brushes with a PS M(n) slightly smaller than that of PMMA underwent self-reorganization, exhibiting a different theta(a). Intriguing surface morphologies composed of relatively ordered nanoscale domains were found from mixed brushes with PS M(n) slightly smaller than or similar to that of PMMA after treatment with acetic acid, a selective solvent for PMMA. The nanodomains are speculated to be of a micellar structure, with PS chains forming a core shielded by PMMA chains.