Hydration and Dehydration Kinetics: Comparison between Poly( N-isopropyl methacrylamide) and Poly(methoxy diethylene glycol acrylate) Films.

Thermoresponsive films of poly( N-isopropyl methacrylamide) (PNIPMAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) are compared with respect to their hydration and dehydration kinetics using in situ neutron reflectivity. Both as-prepared films present a homogeneous single-layer structure and have similar transition temperatures of the lower critical solution temperature type (TT, PNIPMAM 38 °C and PMDEGA 41 °C). After hydration in unsaturated D2O vapor at 23 °C, a D2O enrichment layer is observed in PNIPMAM films adjacent to the Si substrate. In contrast, two enrichment layers are present in PMDEGA films (close to the vapor interface and the Si substrate). PNIPMAM films exhibit a higher hydration capability, ascribed to having both donor (N-H) and acceptor (C═O) units for hydrogen bonds. While the swelling of the PMDEGA films is mainly caused by the increase of the enrichment layers, the thickness of the entire PNIPMAM films increases with time. The observed longer relaxation time for swelling of PNIPMAM films is attributed to the much higher glass transition temperature of PNIPMAM. When dehydrating both films by increasing the temperature above the TT, they react with a complex response consisting of three stages (shrinkage, rearrangement, and reswelling). PNIPMAM films respond faster than PMDEGA films. After dehydration, both films still contain a large amount of D2O, and no completely dry film state is reached for a temperature above their TTs.

Effect of chain architecture on the swelling and thermal response of star-shaped thermo-responsive (poly(methoxy diethylene glycol acrylate)-block-polystyrene)3 block copolymer films.

The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)3) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)3 films show a transition temperature (TT) at 33 °C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)3 films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)3. However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)3 films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)3 films depends on the final temperature. It decreases from (9.7 ± 0.3)% to (7.0 ± 0.3)% or (6.0 ± 0.3)% when the final temperatures are set to 35 °C, 45 °C and 50 °C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.

Comparative Investigation of the Thermoresponsive Behavior of Two Diblock Copolymers Comprising PNIPAM and PMDEGA Blocks.

The thermoresponsive behavior of two diblock copolymers PS- b-PNIPAM and PS- b-PMDEGA, which both comprise a hydrophobic polystyrene (PS) block but different thermoresponsive blocks, also differing in length, poly( N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA), respectively, was comparatively investigated in a wide temperature range. Concentrated aqueous solutions containing 25 wt % polymer were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS). DSC measurements show that, during the demixing phase transition, the hydration number per oligo(ethylene glycol) side chain in the PS- b-PMDEGA solution decreases rather gradually, even up to 20 °C above the onset of the transition, i.e., the cloud point (CP). In contrast, the PS- b-PNIPAM solution exhibits an abrupt, stepwise dehydration behavior at its CP, indicated by the sharp, narrow endothermic peak. BDS measurements suggest that the organization of the expelled water during the phase transition and the subsequent evolution of the micellar aggregates are different for the two copolymers. In the PS- b-PMDEGA solution, the long-range charge transport process changes significantly at its CP and strong interfacial polarization processes appear, probably due to charge accumulation at the interfaces between the micellar aggregates and the aqueous medium. On the contrary, in the PS- b-PNIPAM solution, the phase transition has only a marginal effect on the long-range conduction process and is accompanied by a reduction in the high-frequency (1 MHz) dielectric permittivity, ε'. The latter effect is attributed to the reduced polarization strength of local chain modes due to an enhancement of intra- and interchain hydrogen bonds (HBs) in the polymer-rich phase during the water detaching process. Surprisingly, our BDS measurements indicate that prior to both the demixing and remixing processes the local chain mobility increases temporally. Our dielectric studies suggest that for PS- b-PNIPAM the water detaching process initiates a few degrees below CP and that the local chain mobility and intra- and/or interchain HBs of the PNIPAM blocks may control its thermoresponsive behavior. Dielectric "jump" experiments show that the kinetics of micellar aggregation in the PS- b-PMDEGA solution is slower than that in the PS- b-PNIPAM solution and is independent of the target temperature within the two-phase region. From the experimental point of view, it is shown that the dielectric susceptibility, especially, the dielectric permittivity, ε', is a well-suited probe for monitoring both the reversible changes in the molecular dipolar bond polarizability and the long-range interfacial polarization at the phase transition.

Quantifying the Interactions in the Aggregation of Thermoresponsive Polymers: The Effect of Cononsolvency.

The aggregation kinetics of thermoresponsive core-shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering. Using the reversible association model, the interaction potential between the aggregates is determined from their growth rate in dependence on the cosolvents. The effect of the cosolvent is attributed to the interaction potential on the structured layer of hydration water around the aggregates. It is surmised that the latter is perturbed by the cosolvent and thus the residual repulsive hydration force between the aggregates is reduced. The larger the molar volume of the cosolvent, the more pronounced is the effect. This framework provides a molecular-level understanding of solvent-mediated effective interactions in polymer solutions and new opportunities for the rational control of self-assembly in complex soft matter systems.

Arrangement of Maghemite Nanoparticles via Wet Chemical Self-Assembly in PS-b-PNIPAM Diblock Copolymer Films.

The structure and magnetic behavior of hybrid films composed of maghemite (γ-Fe2O3) nanoparticles (NPs) and an asymmetric diblock copolymer (DBC) polystyrene61-block-polyN-isopropylacrylamide115 are investigated. The NPs are coated with PS chains, which allow for a selective incorporation inside the PS domains at different NP concentrations. Upon incorporation of low amounts of NPs into the DBC thin films, the initial parallel (to film surface) cylinder morphology changes to a well ordered, perpendicularly oriented one. The characteristic domain distance of the DBC is increased due to the swelling of the PS domains with NPs. At higher NP concentrations, the excess NPs which can no longer be embedded in the PS domains, are accumulated at the film surface, and NP aggregates form. Irrespective of NP concentration, a superparamagnetic behavior of the metal oxide-DBC hybrid films is found. Such superparamagnetic properties make the established hybrid films interesting for high density magnetic storage media and thermoresponsive magnetic sensors.

Thermoresponsive hydrogels from symmetrical triblock copolymers poly(styrene-block-(methoxy diethylene glycol acrylate)-block-styrene).

A series of symmetrical, thermo-responsive triblock copolymers was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization, and studied in aqueous solution with respect to their ability to form hydrogels. Triblock copolymers were composed of two identical, permanently hydrophobic outer blocks, made of low molar mass polystyrene, and of a hydrophilic inner block of variable length, consisting of poly(methoxy diethylene glycol acrylate) PMDEGA. The polymers exhibited a LCST-type phase transition in the range of 20-40 °C, which markedly depended on molar mass and concentration. Accordingly, the triblock copolymers behaved as amphiphiles at low temperatures, but became water-insoluble at high temperatures. The temperature dependent self-assembly of the amphiphilic block copolymers in aqueous solution was studied by turbidimetry and rheology at concentrations up to 30 wt %, to elucidate the impact of the inner thermoresponsive block on the gel properties. Additionally, small-angle X-ray scattering (SAXS) was performed to access the structural changes in the gel with temperature. For all polymers a gel phase was obtained at low temperatures, which underwent a gel-sol transition at intermediate temperatures, well below the cloud point where phase separation occurred. With increasing length of the PMDEGA inner block, the gel-sol transition shifts to markedly lower concentrations, as well as to higher transition temperatures. For the longest PMDEGA block studied (DP(n) about 450), gels had already formed at 3.5 wt % at low temperatures. The gel-sol transition of the hydrogels and the LCST-type phase transition of the hydrophilic inner block were found to be independent of each other.