A novel self-healing supramolecular polymer system

Utilising supramolecular pi-pi stacking interactions to drive miscibility in two-component polymer blends offers a novel approach to producing materials with unique properties. We report in this paper the preparation of a supramolecular polymer network that exploits this principle. A low molecular weight polydiimide which contains multiple pi-electron-poor receptor sites along its backbone forms homogeneous films with a siloxane polymer that features pi-electron-rich pyrenyl end-groups. Compatibility results from a complexation process that involves chain-folding of the polydiimide to create an optimum binding site for the pi-electron-rich chain ends of the polysiloxane. These complementary pi-electron-rich and -poor receptors exhibit rapid and reversible complexation behaviour in solution, and healable characteristics in the solid state in response to temperature. A mechanism is proposed for this thermoreversible healing behaviour that involves disruption of the intermolecular pi-pi stacking cross-links as the temperature of the supramolecular film is increased. The low T-g siloxane component can then flow and as the temperature of the blend is decreased, pi-pi stacking interactions drive formation of a new network and so lead to good damage-recovery characteristics of the two-component blend.

Ordering in thin films of block copolymers: fundamentals to potential applications

The ordering of block copolymers in thin films is reviewed, starting, from the fundamental principles and extending to recent promising developments as templates for nanolithography which may find important applications in the semiconductor industry. Ordering in supported thin films of symmetric and asymmetric AB diblock and ABA triblock copolymers is discussed, along with that of more complex materials such as ABC triblocks and liquid crystalline block copolymers Techniques to prepare thin films, and to characterise ordering within them, are summarized. Several methods to align Hock copolymer nanostructures, important in several applications are outlined A number of potential applications in nanolithography, production of porous materials, templating. and patterning of organic and inorganic materials are then presented. The influence of crystallization on the morphology of a block copolymer film is briefly discussed, as are structures in grafted block copolymer films. (C) 2009 Elsevier Ltd All rights reserved.

Design of mucoadhesive polymeric films based on blends of poly(acrylic acid) and (hydroxypropyl)cellulose

Mixing of aqueous solutions of poly(acrylic acid) and (hydroxypropyl) cellulose results in formation of hydrogen-bonded interpolymer complexes, which precipitate and do not allow preparation of homogeneous polymeric films by casting. In the present work the effect of pH on the complexation between poly(acrylic acid) and (hydroxypropyl)cellulose in solutions and miscibility of these polymers in solid state has been studied. The pH-induced complexation-miscibility-immiscibility transitions in the polymer mixtures have been observed. The optimal conditions for preparation of homogeneous polymeric films based on blends of these polymers have been found, and the possibility of radiation cross-linking of these materials has been demonstrated. Although the gamma-radiation treatment of solid polymeric blends was found to be inefficient, successful cross-linking was achieved by addition of N, N'- methylenebis(acrylamide). The mucoadhesive potential of both soluble and cross-linked films toward porcine buccal mucosa is evaluated. Soluble films adhered to mucosal tissues undergo dissolution within 30-110 min depending on the polymer ratio in the blend. Cross-linked films are retained on the mucosal surface for 10-40 min and then detach.

Optimization of electroless copper plating on polyethylene films modified by surface grafting of vinyl ether of monoethanolamine

Metallized plastics have recently received significant interest for their useful applications in electronic devices such as for integrated circuits, packaging, printed circuits and sensor applications. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. There are several techniques for metal deposition on surface of polymers such as evaporation, sputtering, electroless plating and electrolysis. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. Polyethylene films were subjected to gamma-radiation induced surface graft copolymerization with vinyl ether of monoethanolamine. Electroless copper plating was carried out effectively on the modified films. The catalytic processes for the electroless copper plating in the presence and the absence of SnCl2 sensitization were studied and the optimum activation conditions that give the highest plating rate were determined. The effect of grafting degree on the plating rate is studied. Electroless plating conditions (bath additives, pH and temperature) were optimized. Plating rate was determined gravimetrically and spectrophotometrically at different grafting degrees. The results reveal that plating rate is a function of degree of grafting and increases with increasing grafted vinyl ether of monoethanolamine onto polyethylene. It was found that pH 13 of electroless bath and plating temperature 40°C are the optimal conditions for the plating process. The increasing of grafting degree results in faster plating rate at the same pH and temperature. The surface morphology of the metallized films was investigated using scanning electron microscopy (SEM). The adhesion strength between the metallized layer and grafted polymer was studied using tensile machine. SEM photos and adhesion measurements clarified that uniform and adhered deposits were obtained under optimum conditions.

Phase separated structures in tethered dPS–PMMA copolymer films revealed using X-ray scattering with a novel contrast enhancement agent

Tethered deuterated polystyrene-block-polymethyl methacrylate films have been examined by X-ray scattering both in their native state and following treatment with ruthenium tetroxide. The use of the stain, while increasing the thickness of the films, does not significantly alter the lateral structure or periodicity of the films and provides contrast between the two blocks. Both the periodicity of the films and the structure normal to the surface have been identified following staining. Experiments were also performed on films treated by a solvent exchange process, and the effects of staining on these films are discussed.

Phase separation in thin films of end-grafted block copolymers

An atomic force microscopy investigation was carried out on various thick (30–120 nm) polymethyl methacrylate-bpolystyrene and poly(2-(dimethyl amino)ethyl methacrylate)-b-polystyrene films prepared via a grafting-from method. The structure of the films was examined with both topographic and phase imaging. Several different morphologies were observed including a perforated lamellar phase with irregular perforations. In addition, complementary small-angle X-ray scattering and reflectometry results measurements on a non-grafted polymer are presented.

Structure variation and evolution in microphase-separated grafted diblock copolymer films

The phase behavior of grafted d-polystyrene-block-poly(methyl methacrylate) diblock copolymer films is examined, with particular focus on the effect of solvent and annealing time. It was observed that the films undergo a two-step transformation from an initially disordered state, through an ordered metastable state, to the final equilibrium configuration. It was also found that altering the solvent used to wash the films, or complete removal of the solvent prior to thermal annealing using supercritical CO2, could influence the structure of the films in the metastable state, though the final equilibrium state was unaffected. To aid in the understanding to these experimental results, a series of self-consistent field theory calculations were done on a model diblock copolymer brush containing solvent. Of the different models examined, those which contained a solvent selective for the grafted polymer block most accurately matched the observed experimental behavior. We hypothesize that the structure of the films in the metastable state results from solvent enrichment of the film near the film/substrate interface in the case of films washed with solvent or faster relaxation of the nongrafted block for supercritical CO2 treated (solvent free) films. The persistence of the metastable structures was attributed to the slow reorganization of the polymer chains in the absence of solvent.

High-strength, healable, supramolecular polymer nanocomposites

A supramolecular polymer blend, formed via π-π interactions between a π-electron rich pyrenyl endcapped oligomer and a chain-folding oligomer containing pairs of π-electron poor naphthalene-diimide (NDI) units, has been reinforced with cellulose nanocrystals (CNCs) to afford a healable nanocomposite material. Nanocomposites with varying weight percentage of CNCs (from 1.25 to 20.0 wt.%) within the healable supramolecular polymeric matrix have been prepared via solvent casting followed by compression molding, and their mechanical properties and healing behavior have been evaluated. It is found that homogeneously dispersed films can be formed with CNCs at less than 10 wt.%. Above 10 wt.% CNC heterogeneous nanocomposites were obtained. All the nanocomposites formed could be re-healed upon exposure to elevated temperatures although, for the homogeneous films, it was found that the healing rate was reduced with increasing CNC content. The best combination of healing efficiency and mechanical properties was obtained with the 7.5 wt.% CNC nanocomposite which exhibited a tensile modulus enhanced by as much as a factor of 20 over the matrix material alone and could be fully re-healed at 85 °C within 30 minutes. Thus it is demonstrated that supramolecular nanocomposites can afford greatly enhanced mechanical properties relative to the unreinforced polymer, while still allowing efficient thermal healing.

A thermoresponsive supramolecular polymer network comprising pyrene-functionalized gold nano-particles and a chain-folding polydiimide.

A thermoresponsive, supramolecular nanocomposite has been prepared by the addition of pyrenyl functionalized gold nanoparticles (AuNPs) to a polydiimide that contains receptor residues designed to form defined complexes with pyrene. The novel pyrenyl-functionalized AuNPs (P-AuNPs) were characterized by transmission electron microscopy, with surface functionalization confirmed by infrared and UV–visible spectroscopic analyses. Mixing solutions of the P-AuNPs and a π-electron-deficient polydiimide resulted in the formation of electronically complementary, chain-folded and π–π-stacked complexes, so affording a new supramolecular nanocomposite network which precipitated from solution. The P-AuNPs bind to the polydiimide via π–π stacking interactions to create supramolecular cross-links. UV–visible spectroscopic analysis confirmed the thermally reversible nature of the complexation process, and transmission electron microscopy (TEM), infrared spectroscopy (IR), and differential scanning calorimetry (DSC) were used to characterize the supramolecular-nanocomposite material. The supramolecular polymer network is insoluble at room temperature, yet may be dissolved at temperatures above 60 °C. The thermal reversibility of this system is maintained over five heat/cool cycles without diminishment of the network characteristics. In contrast to the individual components, the nanocomposite formed self-supporting films, demonstrating the benefit of the supramolecular network in terms of mechanical properties. Control experiments probing the interactions between a model diimide compound that can also form a π-stacked complex with the π-electron rich pyrene units on P-AuNPs showed that, while complexation was readily apparent, precipitation did not occur because a supramolecular cross-linked network system could not be formed with this system.

Self-assembly and bioactivity of a polymer/peptide conjugate containing the RGD cell adhesion motif and PEG

The self-assembly and bioactivity of the peptide–polymer conjugate DGRFFF–PEG3000 containing the RGD cell adhesion motif has been examined, in aqueous solution. The conjugate is designed to be amphiphilic by incorporation of three hydrophobic phenylalanine residues as well as the RGD unit and a short poly(ethylene glycol) (PEG) chain of molar mass 3000 kg mol-1. Above a critical aggregation concentration, determined by fluorescence measurements, signals of b-sheet structure are revealed by spectroscopic measurements, as well as X-ray diffraction. At high concentration, a self-assembled fibril nanostructure is revealed by electron microscopy. The fibrils are observed despite PEG crystallization which occurs on drying. This suggests that DGRFFF has an aggregation tendency that is sufficiently strong not to be prevented by PEG crystallization. The adhesion, viability and proliferation of human corneal fibroblasts was examined for films of the conjugate on tissue culture plates (TCPs) as well as low attachment plates. On TCP, DGRFFF–PEG3000 films prepared at sufficiently low concentration are viable, and cell proliferation is observed. However, on low attachment surfaces, neither cell adhesion nor proliferation was observed, indicating that the RGD motif was not available to enhance cell adhesion. This was ascribed to the core–shell architecture of the self-assembled fibrils with a peptide core surrounded by a PEG shell which hinders access to the RGD unit.

Step edges in thin films of lamellar-forming diblock copolymer

Self-consistent field theory (SCFT) is used to study the step edges that occur in thin films of lamellar-forming diblock copolymer, when the surfaces each have an affinity for one of the polymer components. We examine film morphologies consisting of a stack of ν continuous monolayers and one semi-infinite bilayer, the edge of which creates the step. The line tension of each step morphology is evaluated and phase diagrams are constructed showing the conditions under which the various morphologies are stable. The predicted behavior is then compared to experiment. Interestingly, our atomic force microscopy (AFM) images of terraced films reveal a distinct change in the character of the steps with increasing ν, which is qualitatively consistent with our SCFT phase diagrams. Direct quantitative comparisons are not possible because the SCFT is not yet able to probe the large polymer/air surface tensions characteristic of experiment.

Hydrogen-bonded complexes and blends of poly(acrylic acid) and methylcellulose: nanoparticles and mucoadhesive films for Ocular Delivery of Riboflavin

Poly(acrylic acid) (PAA) and methylcellulose (MC) are able to form hydrogen-bonded interpolymer complexes (IPCs) in aqueous solutions. In this study, the complexation between PAA andMC is explored in dilute aqueous solutions under acidic conditions. The formation of stable nanoparticles is established,whose size and colloidal stability are greatly dependent on solution pH and polymers ratio in the mixture. Poly(acrylic acid) and methylcellulose are also used to prepare polymeric films by casting from aqueous solutions. It is established that uniform films can be prepared by casting from polymer mixture solutions at pH 3.4–4.5. At lower pHs (pH<3.0) the films have inhomogeneous morphology resulting from strong interpolymer complexation and precipitation of polycomplexes, whereas at higher pHs (pH 8.3) the polymers form fully immiscible blends because of the lack of interpolymer hydrogen-bonding. The PAA/MC films cast at pH 4 are shown to be non-irritant to mucosal surfaces. These films provide a platform for ocular formulation of riboflavin, a drug used for corneal crosslinking in the treatment of keratoconus. An in vitro release of riboflavin as well as an in vivo retention of the films on corneal surfaces can be controlled by adjusting PAA/MC ratio in the formulations.