Switching of Polymer Brushes

Polymer coatings of brushlike monolayers composed of two different polymers, polystyrene and poly(2-vinylpyridine), are grafted by radical polymerization on the surface of silicon wafers. Thickness, grafting density, molecular weight of grafted chains, and the composition of the coatings were regulated by grafting time, monomer concentration, and additional initiator in solution. A typical dry film thickness is between 10 and 100 nm, and the molecular weights of the components range from 100 to 300 kg/mol. The fabricated coatings turn out to be sensitive to the composition of the environment. For instance after exposition to toluene the layer becomes hydrophobic and the top of the layer is …

Orientation and order in thin films of a combined liquid crystalline polymer

The order in thin films of a combined liquid crystalline polymer is studied by X-ray reflection. Films of thicknesses of less than 200 nm on float glass are investigated as a function of temperature. The polymer with mesogenic groups in the main and side-chains exhibits smectic and cholesteric mesophases. Measurements in the smectic phases show a Bragg peak and smectic layers are oriented parallel to the substrate. The sample is thus macroscopically ordered by the influence of substrate and free surface. The film surface is very smooth after spincoating; surface roughness is typically 0.8 nm. First annealing of samples leads to a significant roughening of the free surface; roughness increas…

Adsorption of di-and triblock copolymers with functionalized butadiene-styrene blocks from dilute solution

Abstract The adsorption behaviour of functionalized polystyrene-block-polybutadiene diblock copolymers, P(S-b-B), and polybutadiene-block-polystyrene-block-polybutadiene triblock copolymers, P(B-b-S-b-B), from dilute solutions in toluene onto silicon wafers was investigated by means of null-ellipsometry. Polar 4-(3,5-dioxo- 1,2,4-triazolidin-4-yl) benzoic acid groups (urazole groups) were attached randomly to the butadiene blocks. The PS blocks and the PB blocks adsorb not on the substrate surface, but only on the polar functional groups. It was verified that the adsorbed amount does not depend on the number of functional groups nor on the degree of polymerization of the polybutadiene block…

Lateral versus perpendicular segregation in mixed polymer brushes.

Grafting of incompatible polymers on a substrate prevents macrophase separation and the chains self-assemble laterally. Mixed brushes are exposed to different solvents and the morphology is observed via atomic force and x-ray photoemission microscopy. In a nonselective solvent the different species segregate into parallel cylinders ("ripple structure"). Upon exposure to a selective solvent, we encounter a transition to a "dimple" structure, in which the unfavored component forms clusters. Simultaneously, we observe an enhanced perpendicular segregation. The experimental observations are compared to self-consistent field calculations, where qualitative agreement is found.

Mixed Polymer Brushes: Switching of Surface Behavior and Chemical Patterning at the Nanoscale

Calculation of small-angle neutron scattering by macromolecules in the semicrystalline state

The conformation of macromolecules in the semicrystalline state has been studied by various authors with respect to the validity of the adjacent re-entry — or switchboard model by application of small-angle neutron scattering. Analytical as well as Monte-Carlo calculations show that the experimental results for melt crystallized polyethylene and isotactic polypropylene can be interpreted on the basis of the solidification model. In this model it is assumed that crystallization occurs by straightening of coil sequences without a long range diffusion process.

Nanostructured Polymer Brushes With Reversibly Changing Properties

AbstractWe investigated the interplay between different mechanisms of the lateral and vertical segregation in the synthesized via “grafting from” approach symmetric A/B (where A and B are poly(styrene-co-2,3,4,5,6-pentafluorostyrene) and poly(methylmethacrylate), respectively) polymer brushes upon exposure to different solvents. We used X-ray photoemission electron spectroscopy and microscopy (X-PEEM), AFM, water contact angle measurements, and oxygen plasma etching to study morphology of the brushes. The ripple morphology after toluene (nonselective solvent) revealed elongated lamellar-like domains of A and B polymers alternating across the surface. The dimple-A morphology consisting of ro…

Mixed silane self assembled monolayers and their in situ modification

Mixed self assembled silane monolayers were prepared by coadsorption of Br and methyl terminated trichlorosilanes. By subsequent in situ modification the Br groups were converted into amino groups which can be used to tether polyglutamates to the surface. Here we describe the characterization of the monolayers by means of contact angle measurements and X-ray photoelectron spectroscopy (XPS). Both methods clearly indicate that the Br terminated silane is preferentially adsorbed from the solution. Following the in situ modification by XPS a yield of approximately 80% was determined for the substitution of the bromine by azide, whereas the yield for subsequent reduction to the amine is close t…

Switchable assembly of stable, ordered molecular layers

Bisamidines can be assembled on self-assembled monolayers of mercaptoalkanoic acids on gold to form stable and ordered but pH-switchable layers (see diagram). At basic pH the layers are stable and charge selective towards charged surfactants and plasma proteins. The system can potentially be used to reversibly introduce new surface properties for given applications that use one single substrate.

Neutron reflectometry studies on the interfacial width between polystyrene and various poly(alkylmethacrylates)

From neutron reflectometry we have obtained the interfacial width (typically 2-8 nm) between incompatible polymers above the glass transition temperatures. The investigated polymer bilayers consist of a deuterated polystyrene top layer and various poly(alkylmethacrylates) as a bottom layer. We obtained interesting effects of the length of the alkyl group on the interfacial width. Using mean-field theory we calculate Flory-Huggins-Stavermann interaction parameters X from the interfacial width a I data. These results are compared with investigations of the interfacial width between deuterated poly(methylmethacrylate) and respective polyalkyl-methacrylates.

Photoreactive Langmuir–Blodgett–Kuhn multilayer assemblies from functionalized liquid-crystalline side chain polymers, I. Homopolymers containing azobenzene chromophores

Stable monomolecular layers of a liquid-crystalline homopolymer bearing azobenzene chromophores in the mesogenic side groups could be prepared at the water–air interface by slow compression at room temperature. From the area per monomer unit of A0≈0.25 nm2 a structural model with tightly packed azobenzene groups oriented nearly parallel to the surface normal was deduced. After transfer to a solid support in a Y-type mode the obtained Langmuir–Blodgett–Kuhn (LBK) multilayer assemblies of varying thicknesses (from a double layer to a thick film of d = 238 nm, capable of guiding optical modes) were prepared and analyzed by X-ray reflection and optical evanescent wave techniques. A monolayer th…

Competitive Adsorption of Functionalized Polymers

The adsorption and desorption of functionalized polystyrene-block-polybutadiene diblock copolymers from dilute solutions in toluene onto silicon wafers are investigated by means of null ellipsometry. The short polybutadiene block is functionalized by a reaction with 4-(3,5-dioxo-1,2,4-triazolidin-4-yl)benzoic acid. On the average there are six functional groups per chain. The polystyrene block does not adsorb on the surface. The adsorption depends on the length of the polystyrene block, and chains with short polystyrene blocks yield higher surface coverage than larger ones. When short and long chains are put together, the short chains displace the long ones in equilibrium conditions nearly …