Absolute local conformation of poly(methyl methacrylate) chains adsorbed on a quartz surface.

Polymer chains at a buried interface with an inorganic solid play a critical role in the performance of polymer nanocomposites and adhesives. Sum frequency generation (SFG) vibrational spectroscopy with a sub-nanometer depth resolution provides valuable information regarding the orientation angle of functional groups at interfaces. However, in the case of conventional SFG, since the signal intensity is proportional to the square of the second-order nonlinear optical susceptibility and thereby loses phase information, it cannot be unambiguously determined whether the functional groups face upward or downward. This problem can be solved by phase-sensitive SFG (ps-SFG). We here applied ps-SFG to poly(methyl methacrylate) (PMMA) chains in direct contact with a quartz surface, shedding light on the local conformation of chains adsorbed onto the solid surface. The measurements made it possible to determine the absolute orientation of the ester methyl groups of PMMA, which were oriented toward the quartz interface. Combining ps-SFG with all-atomistic molecular dynamics simulation, the distribution of the local conformation and the driving force are also discussed.

Effect of Oligomer Segregation on the Aggregation State and Strength at the Polystyrene/Substrate Interface.

The interfacial strength of polystyrene (PS) with and without PS oligomers in contact with a glass substrate was examined to determine the relationship between the interfacial aggregation state and adhesion. The shear bond strength and adsorbed layer thickness of neat PS exhibited a similar dependence on the thermal annealing time: they increased to constant values within almost the same time. This implies that the adhesion of the polymer is closely related to the formation of an adsorbed layer at the adhesion interface. Nevertheless, in the case of PS with a small amount of oligomer, the shear bond strength decreased, while the adsorbed layer thickness was almost the same as that of neat PS. Based on the results of interfacial analyses, we propose that the interfacial segregation of the oligomer reduced the entanglement between the interfacial free chains in the adsorbed layer and the bulk chains.

A Facile Surface Functionalization Method for Polymers Using a Nonsolvent.

Surface treatment of polymeric solids without impairing their bulk properties is a crucial functionalization strategy for the promotion of their wider application. We here propose a facile method using a nonsolvent which can subtly alter or swell the polymer surface to be modified. A thin film of poly(methyl methacrylate) (PMMA) was immersed in a methanol solution of poly(2-methoxyethyl acrylate) (PMEA). Electron spectroscopy for chemical analysis and neutron reflectometry revealed that a PMEA layer formed on the PMMA film with a diffused interface. The PMEA layer was very swollen in water and exhibited the ability to suppress serum protein adsorption and platelet adhesion on it. The functionalization technique using a nonsolvent was also applicable to the surface of other polymeric solids such as polyurethane.

Dynamics Gradient of Polymer Chains near a Solid Interface.

The relaxation dynamics of polyisoprene (PI) and nitrile butadiene rubber (NBR) chains at the SiO2 interface were directly probed as a function of distance from the SiO2 surface using time-resolved evanescent wave-induced fluorescence anisotropy, dielectric relaxation spectroscopy, and sum-frequency generation spectroscopy. We found the presence of the dynamics gradient of chains in the interfacial region with the SiO2 surface and tried to assign it to the two kinds of adsorbed chains, namely, loosely and strongly adsorbed, at the interface. The segmental relaxation of chains in the strongly adsorbed layer at the interface could be slower than that of bulk chains by more than 10 orders.

Chiral Nucleating Agents Affecting the Handedness of Lamellar Twist in the Banded Spherulites in Poly(ε-Caprolactone)/Poly(Vinyl Butyral) Blends.

Chiral silica, which acts as a nucleating agent of poly(ε-caprolactone) (PCL), was demonstrated to induce excess handedness of lamellar twist in the banded spherulites of PCL blended with poly(vinyl butyral). The d- and l-forms of silica enhanced the right- and left-handed twists, respectively. The influences of chiral silica on the twist handedness were statistically significant. These results indicate that the handedness of twisting can be controlled upon primary nucleation. The organic substances used as chiral templates of silica had no effect on the handedness; silica was shown to govern the handedness. The possible mechanisms of the chirality transfer are discussed.

Adhesion Control of Elastomer Sheet on the Basis of Interfacial Segregation of Hyperbranched Polymer.

Adhesion of a model rubbery material, cross-linked poly(dimethylsiloxane) (PDMS), onto a solid surface was studied by sum-frequency generation spectroscopy and X-ray photoelectron spectroscopy. To do so, here, we have focused on the adhesive deposit and insoluble layer. The former and latter were defined as the residual amount on the substrate after the peeling and residual layer after washing with a good solvent, respectively. The peel strength of a PDMS sheet adhered onto a glass plate increased with the contact time. Both adhesive deposit and insoluble layer also exhibited comparable contact time dependence. Once a hyperbranched polymer (HBP), which was segregated to the adhesive interface, was incorporated into PDMS, the peel strength and adhesive deposit decreased, although the thickness of the insoluble layer remained almost unchanged. These results suggest that the formation of loosely adsorbed chains on the solid surface, which possess not only trains but also many loop portions and tail parts, plays an important role in the macroscopic adhesion behavior of the PDMS sheet and the interfacial segregation of HBP can prevent it.

Reorientation Kinetics of Local Conformation of Polyisoprene at Substrate Interface.

The performance of a polymer composite material, in which inorganic fillers are dispersed, is closely related to the aggregation states and dynamics of polymer chains at the interface with the filler. In this study, the local conformation of polyisoprene (PI) at a quartz substrate interface was studied as a model system for the rubber/filler composite material. PI films were prepared from a toluene solution onto quartz substrates by a spin-coating method. Sum-frequency generation spectroscopy revealed that the local conformation of PI chains at the quartz interface depended on the spinning rate. The tilt angle of methyl groups increased with the rotational speed, probably due to the centrifugal force applied to chains and probably also the evaporation rate of the solvent during the solidification process. This result indicates that the interfacial orientation of PI chains can remain even at room temperature, which is 87 K higher than the bulk glass transition temperature (Tgb). The interfacial orientation disappeared at a temperature approximately 120 K higher than Tgb.

Direct Observation of Conformational Relaxation of Polymer Chains at Surfaces.

Sum-frequency generation spectroscopy was employed to follow the conformation evolution of polystyrene chains at the surface of a spin-coated film in a temperature-ramping mode as well as under isothermal annealing. The conformation of surface chains in an as-cast film was observed to be in a nonequilibrium state, in accordance with reported results for polymer chains in thin spin-coated films. While the relaxation of surface nonequilibrium chains was induced by the enhanced surface mobility, the whole chain motion such as reptation might be a key factor in determining the time scale for equilibrating the surface chain conformation.

Depth-resolved local conformation and thermal relaxation of polystyrene near substrate interface.

By means of sum-frequency generation spectroscopy, we report a depth-resolved measurement of the local conformation and chain relaxation of polystyrene (hPS) located at different distances from the quartz interface. To control the distance from the quartz interface, deuterated polystyrene (dPS) layers with thicknesses of 3.4, 7.5, and 20 nm were coated on the quartz substrates. The hPS chains in direct contact with the substrate surface predominantly orient their phenyl rings in a direction normal to the substrate. This conformation was found to be barely relaxed when the film was annealed for 24 h at 423 K, higher than the bulk glass transition temperature. In contrast, for the hPS chains supported on the dPS layer, the orientation of phenyl rings of hPS became weaker with the annealing and this trend was more significant with increasing distance from the quartz substrate. In particular, the orientation of phenyl rings of hPS after annealing vanished at a distance of 20 nm. These results might provide an important evidence of the difference in the relaxation dynamics of the PS chains located at different distances from the quartz interface.

Dynamics of a bioinert polymer in hydrated states by dielectric relaxation spectroscopy.

The chain dynamics of well-defined poly(2-methoxyethyl acrylate) (PMEA), which has been used in practice as a bioinert coating for heart-lung machines, was examined as a function of water content by dielectric relaxation spectroscopy (DRS). Two relaxation processes observed in both dried and hydrated films were assigned to the segmental motion (α-process) and the relatively smaller scale motion such as the hindered rotation of side chains (ß-process). Water molecules adsorbed on PMEA made the α-process faster, meaning that water molecules in PMEA played the role of a plasticizer. Combining the above knowledge with the depth dependence of water content in the PMEA film previously obtained by neutron reflectivity, the segmental dynamics of PMEA at the water interface, which should be crucial to bio-inertness, is discussed. We found that the segmental motion was markedly faster than that in the bulk and almost comparable to the side chain motion.

Aggregation States of Polymers at Hydrophobic and Hydrophilic Solid Interfaces.

Aggregation states of polystyrene (PS) and poly(methyl methacrylate) (PMMA) at hydrophobic deuterated-octadecyltrichlorosilane (OTS-d) and hydrophilic SiOx interfaces are discussed, focusing on the interaction strength between polymer and substrate. Sum-frequency generation spectroscopy revealed that PS exhibited oriented phenyl groups along the normal direction at the interface in a spin-coated film because of the centrifugal force generated during the film solidification process, whereas it did not in a solvent-cast film. This result was common for both hydrophobic and hydrophilic substrates. That is, the aggregation states of PS depended little on which kind of substrate was used. This is because the interaction between PS and the surfaces is weak. In the case of a PMMA film on the hydrophobic OTS-d substrate, the interfacial local conformation was also dependent on the method of film preparation. PMMA at the hydrophilic SiOx interface, however, exhibited oriented ester methyl groups along the direction normal to the interface, regardless of the film preparation method. This is due to a stronger interaction via hydrogen bonding between carbonyl groups of PMMA and the substrate surface.

High Density Polymer Brush Spontaneously Formed by the Segregation of Amphiphilic Diblock Copolymers to the Polymer/Water Interface.

A self-repairable high density polymer brush of poly(ethylene glycol) (PEG) is formed at the interface between cross-linked poly(dimethyl siloxane) (PDMS) and water by spontaneous surface segregation of an amphiphilic diblock copolymer consisting of PEG and PDMS. The surface reconstruction by the formation of the brush was observed as the large hysteresis of the contact angle of the water droplet. Neutron reflectivity measurement revealed that the grafting density of the polymer brush is 2.8 chain/nm2, which is comparable to those of polymer brushes by the surface-initiated polymerization method. The formation of such a remarkably dense polymer brush by segregation can be well supported by the balance between the mixing enthalpy of PEG and water and the stretching energy of PEG.