Project description:In polymer nanocomposites, surface modification of silica aggregates can shield Coulombic interactions that inhibit agglomeration and formation of a network of agglomerates. Surface modification is usually achieved with silane coupling agents although carbon-coating during pyrolytic silica production is also possible. Pyrogenic silica with varying surface carbon contents were dispersed in styrene-butadiene (SBR) rubber to explore the impact on hierarchical dispersion, the emergence of meso-scale structures, and the rheological response. Pristine pyrogenic silica aggregates at concentrations above a critical value (related to the Debye screening length) display correlated meso-scale structures and poor filler network formation in rubber nanocomposites due to the presence of silanol groups on the surface. In the present study, flame synthesized silica with sufficient surface carbon monolayers can mitigate the charge repulsion thereby impacting network structural emergence. The impact of the surface carbon on the van der Waals enthalpic attraction, a* , is determined. The van der Waals model for polymer nanocomposites is drawn through an analogy between thermal energy, kBT , and the accumulated strain, γ . The rheological response of the emergent meso-scale structures depends on the surface density of both carbon and silanol groups.
Project description:The use of surfactant mixtures to affect both EOF and separation selectivity in electrophoresis with PDMS substrates is reported, and capacitively coupled contactless conductivity detection is introduced for EOF measurement on PDMS microchips. First, the EOF was measured for two nonionic surfactants (Tween 20 and Triton X-100), mixed ionic/nonionic surfactant systems (SDS/Tween 20 and SDS/Triton X-100), and finally for the first time, mixed zwitterionic/nonionic surfactant systems (TDAPS/Tween 20 and TDAPS/Triton X-100). EOF for the nonionic surfactants decreased with increasing surfactant concentration. The addition of SDS or TDAPS to a nonionic surfactant increased EOF. After establishing the EOF behavior, the separation of model catecholamines was explored to show the impact on separations. Similar analyte resolution with greater peak heights was achieved with mixed surfactant systems containing Tween 20 and TDAPS relative to the single surfactant system. Finally, the detection of catecholamine release from PC12 cells by stimulation with 80 mM K(+) was performed to demonstrate the usefulness of mixed surfactant systems to provide resolution of biological compounds in complex samples.
Project description:The use of mixtures of ionic and zwitterionic surfactants in poly(dimethylsiloxane) (PDMS) microchips is reported. The effect of surfactant concentration on electroosmotic flow (EOF) was studied for a single anionic surfactant (sodium dodecyl sulfate, SDS), a single zwitterionic surfactant (N-tetradecylammonium-N,N-dimethyl-3-ammonio-1-propanesulfonate, TDAPS), and a mixed SDS/TDAPS surfactant system. SDS increased the EOF as reported previously while TDAPS showed an initial increase in EOF followed by a reduction at higher concentrations. When TDAPS was added to a solution containing SDS, the EOF decreased in a concentration-dependent manner. The EOF for all three surfactant systems followed expected pH trends, with increasing EOF at higher pH. The mixed surfactant system allowed tuning of the EOF across a range of pH and concentration conditions. After establishing the EOF behavior, the adsorption/desorption kinetics were measured and showed a slower adsorption/desorption rate for TDAPS than SDS. Finally, the separation and electrochemical detection of model catecholamines in buffer and reduced glutathione in red blood cell lysate using the mixed surfactant system were explored. The mixed surfactant system provided shorter analysis times and/or improved resolution when compared to the single surfactant systems.
Project description:When polymer composites containing magnetic nanoparticles (MNPs) are exposed to an alternating magnetic field, heat is generated to melt the surrounding polymer locally, partially filling voids across any cracks or deformities. Such materials are of interest for structural applications; however, structural polymers with high melting temperatures pose the challenge of generating high localised temperatures enabling self-healing. A method to prepare a multiferroic-Polyamide 6 (PA6) nanocomposite with tuneable magnetocaloric properties is reported. Tunability arises from varying the MNP material (and any coating, its dispersion, and agglomerate sizes in the nanocomposite). The superparamagnetic MNPs (SMNPs) and iron oxide MNPs with and without surface functionalization were dispersed into PA6 through in situ polymerization, and their magnetic properties were compared. Furthermore, computer simulations were used to quantify the dispersion state of MNPs and assess the influence of the interaction radius on the magnetic response of the self-healable magnetic nanoparticle polymer (SHMNP) composite. It was shown that maintaining the low interaction radius through the dispersion of the low coercivity MNPs could allow tuning of the bulk magnetocaloric properties of the resulting mesostructures. An in-situ polymerization method improved the dispersion and reduced the maximum interaction radius value from ca. 806 to 371 nm and increased the magnetic response for the silica-coated SMNP composite. This sample displayed ca. three orders of magnitude enhancement for magnetic saturation compared to the unfunctionalized Fe3O4 MNP composite.
Project description:Polymer electrolytes offer great potential for emerging wearable electronics. However, the development of a polymer electrolyte that has high ionic conductivity, stretchability and security simultaneously is still a considerable challenge. Herein, we reported an effective approach for fabricating high-performance poly(ionic liquids) (PILs) copolymer (denoted as PIL-BA) electrolytes by the interaction between flexible units (butyl acrylate) and counteranions. The introduction of butyl acrylate units and bis(trifluoromethane-sulfonyl)imide (TFSI-) counteranions can significantly enhance the mobility of polymer chains, resulting in the effective improvement of ion transport, toughness and self-healability. As a result, the PIL-BA copolymer-based electrolytes containing TFSI- counterions achieved the highest ionic conductivity of 2.71 ± 0.17 mS cm-1, 1129% of that of a PIL homopolymer electrolyte containing Cl- counterions. Moreover, the PIL-BA copolymer-based electrolytes also exhibit ultrahigh tensile strain of 1762% and good self-healable capability. Such multifunctional polymer electrolytes can potentially be applied for safe and stable wearable electronics.
Project description:Switchable mechanically induced changes in the wetting behavior of surfaces are of paramount importance for advanced microfluidic, self-cleaning and biomedical applications. In this work we show that the well-known polydimethylsiloxane (PDMS) elastomer develops self-patterning when it is coated with nanostructured TiO2 films prepared by physical vapor deposition at glancing angles and subsequently subjected to a mechanical deformation. Thus, unlike the disordered wrinkled surfaces typically created by deformation of the bare elastomer, well-ordered and aligned micro-scaled grooves form on TiO2/PDMS after the first post-deposition bending or stretching event. These regularly patterned surfaces can be reversibly modified by mechanical deformation, thereby inducing a switchable and reversible wetting petal effect and the sliding of liquid droplets. When performed in a dynamic way, this mechanical actuation produces a unique capacity of liquid droplets (water and diiodomethane) transport and tweezing, this latter through their selective capture and release depending on their volume and chemical characteristics. Scanning electron and atomic force microscopy studies of the strained samples showed that a dual-scale roughness, a parallel alignment of patterned grooves and their reversible widening upon deformation, are critical factors controlling this singular sliding behavior and the possibility to tailor their response by the appropriate manufacturing of surface structures.
Project description:Chitosan (CS)/poly(ethylene oxide) (PEO)-based nanofiber mats have attracted particular attention as advanced materials for medical and pharmaceutical applications. In the scope of present studies, solution blow spinning was applied to produce nanofibers from PEO and CS and physicochemical and biopharmaceutical studies were carried out to investigate their potential as wound nanomaterial for skin healing and regeneration. Additional coating with hydrophobic poly(dimethylsiloxane) was applied to favor removal of nanofibers from the wound surface. Unmodified nanofibers displayed highly porous structure with the presence of uniform, randomly aligned nanofibers, in contrast to coated materials in which almost all the free spaces were filled in with poly(dimethylsiloxane). Infrared spectroscopy indicated that solution blow technique did not influence the molecular nature of native polymers. Obtained nanofibers exhibited sufficient wound exudate absorbency, which appears beneficial to moisturize the wound bed during the healing process. Formulations displayed greater tensile strength as compared to commercial hydrofiber-like dressing materials comprised of carboxymethylcellulose sodium or calcium alginate, which points toward their protective function against mechanical stress. Coating with hydrophobic poly(dimethylsiloxane) (applied to favor nanofiber removal from the wound surface) impacted porosity and decreased both mechanical properties and adherence to excised human skin, though the obtained values were comparable to those attained for commercial hydrofiber-like materials. In vitro cytotoxicity and irritancy studies showed biocompatibility and no skin irritant response of nanofibers in contact with a reconstituted three-dimensional human skin model, while scratch assay using human fibroblast cell line HDFa revealed the valuable potential of CS/PEO nanofibers to promote cell migration at an early stage of injury.
Project description:Rubber composites were prepared by mixing bromobutyl rubber (BIIR) with silica particles in the presence of 1-butylimidazole. In addition to pristine (precipitated) silica, silanized particles with aliphatic or imidazolium functional groups, respectively, were used as filler. The silanization was carried out either separately or in situ during compounding. The silanized particles were characterized by TGA, 1H-29Si cross polarization (CP)/MAS NMR, and Zeta potential measurements. During compounding, the bromine groups of BIIR were converted with 1-butylimidazole to ionic imidazolium groups which formed a dynamic network by ionic association. Based on DMA temperature and strain sweep measurements as well as cyclic tensile tests and stress-strain measurements it could be concluded that interactions between the ionic groups and interactions with the functional groups of the silica particles strongly influence the mechanical and viscoelastic behavior of the composites. A particularly pronounced reinforcing effect was observed for the composite with pristine silica, which was attributed to acid-base interactions between the silanol and imidazolium groups. In composites with alkyl or imidazolium functionalized silica particles, the interactions between the filler and the rubber matrix form dynamic networks with pronounced self-healing behavior and excellent tensile strength values of up to 19 MPa. This new approach in utilizing filler-matrix interactions in the formation of dynamic networks opens up new avenues in designing new kinds of particle-reinforced self-healing elastomeric materials with high technological relevance.
Project description:In flexible electronics, appropriate inlaid structures for stress dispersion to avoid excessive deformation that can break chemical bonds are lacking, which greatly hinders the fabrication of super-foldable composite materials capable of sustaining numerous times of true-folding. Here, mimicking the microstructures of both cuit cocoon possessing super-flexible property and Mimosa leaf featuring reversible scatheless folding, super-foldable C-web/FeOOH-nanocone (SFCFe) conductive nanocomposites are prepared, which display cone-arrays on fiber structures similar to Mimosa leaf, as well as non-crosslinked junctions, slidable nanofibers, separable layers, and compressible network like cuit cocoon. Remarkably, the SFCFe can undergo over 100 000 times of repeated true-folding without structural damage or electrical conductivity degradation. The mechanism underlying this super-foldable performance is further investigated by real-time scanning electron microscopy folding characterization and finite-element simulations. The results indicate its self-adaptive stress-dispersion mechanism originating from multilevel biomimetic structures. Notably, the SFCFe demonstrates its prospect as a super-foldable anode electrode for aqueous batteries, which shows not only high capacities and satisfactory cycling stability, but also completely coincident cyclic voltammetry and galvanostatic charge-discharge curves throughout the 100 000 times of true-folding. This work reports a mechanical design considering the self-adaptive stress dispersion mechanism, which can realize a scatheless super-foldable electrode for soft-matter electronics.
Project description:The research on self-healing polymers has been a hot topic. The encapsulated-monomer/catalyst, supramolecular self-assembly, and reversible or dynamic covalent bond formation are the prevailingly adopted strategies. The alternative of irreversible covalent bond formation is, however, to be further developed. In this contribution, self-healing hyperbranched poly(aroyltriazole)s of PI and PII sharing such mechanism were developed. The polymers were synthesized by our developed metal-free click polymerizations of bis(aroylacetylene)s and triazide. They are processible and have excellent film-forming ability. High quality homogeneous films and sticks free from defects could be obtained by casting. The scratched films could be self-repaired upon general heating. The cut films and sticks could be healed by stacking or pressing the halves together at elevated temperature. Thus, these hyperbranched polymers could find broad applications in diverse areas, and our design concept for self-healing materials should be generally applicable to other hyperbranched polymers with reactive groups on their peripheries.