Network topology and stability of homologous multiblock copolymer physical gels.

The mechanical properties of physical gels generated by selectively swelling a homologous series of linear multiblock copolymers are investigated by quasistatic uniaxial tensile tests. We use the slip-tube network model to extract the contributions arising from network crosslinks and chain entanglements. The composition dependence of these contributions is established and considered in terms of simulations that identify the probabilities associated with chain conformations. Dynamic rheology provides additional insight into the characteristics and thermal stability of the molecular networks.

Self-healing and self-cleaning clear coating.

Coatings exhibiting both self-cleaning and self-healing properties are envisioned for a wide range of applications. Herein we report a simple fabrication approach toward poly(urea-urethane) (PU) coatings having self-healing and self-cleaning properties. The self-cleaning component is a poly(dimethylsiloxane) (PDMS), which is affordable in cost and also has a lower environmental footprint relative to its fluorinated counterpart. The self-healing properties are imparted by dynamic urea bonds of the matrix. The obtained surfaces are evaluated for their anti-smudge properties such as water-, oil- and ink-repellency, as well as optical properties. The self-healing properties of these coatings are evaluated by making scores with a doctor blade and monitoring the healing under different conditions using optical microscopy. The resultant coatings are also investigated for their good mechanical properties. The surface chemical compositions are determined x-ray photoelectron spectroscopy, while atomic force microscopy is used for microstructural analysis of these coatings.

Dual-Layer Approach toward Self-Healing and Self-Cleaning Polyurethane Thermosets.

There is an urgent need for coatings that exhibit both self-healing as well as self-cleaning properties as they can be used for a wide range of applications. Herein we report a novel approach toward fabricating polyurethane thermosets possessing both self-cleaning and self-healing properties. The desired coating was achieved via casting a bottom layer of self-healable polyurethanes comprised of reversible phenolic urethane bonds followed by a subsequent dip-coating of the prepared layer in a solution of bis(3-aminopropyl)-terminated polydimethylsiloxane (PDMS-NH2). The PDMS was used to impart self-cleaning properties to the coating. While the self-healing behavior of the bottom polyurethane layer is achieved through phenolic urethane chemistry, via the exchange of phenolic urethane moieties. The prepared coatings were tested for their optical, mechanical, self-healing, and self-cleaning properties using a variety of characterization methods, which confirmed the successful fabrication of novel self-cleaning and self-healing clear urethane coatings.

A novel dual-layer approach towards omniphobic polyurethane coatings.

Omniphobic surfaces have a plethora of applications ranging from household paints to sensors. The predominant practice of fabricating those materials/surfaces is to use fluorinated materials which are environmentally harmful, and thus have limited practical applications. In this study, we report a novel dual-layer approach of fabrication towards omniphobic surfaces using polyurethane (PU) as a matrix and polydimethylsiloxane (PDMS) as a self-cleaning ingredient. This approach was also used to produce omniphobic PU nanocomposites, where nanofillers (e.g., nanoclay, cellulose nanocrystals (CNCs) and graphene oxide (GO)) were incorporated. The resultant coatings were investigated for their performance, such as optical clarity, durability, and self-cleaning properties. In addition, scanning electron microscopy (SEM) was used for microstructural analysis of the obtained coatings. The facile nature of fabrication and the use of PDMS, an environmentally benign material relative to fluorinated chemicals, thus offer an eco-friendly sustainable scheme for practical applications aimed at omniphobic purposes.

Communication: Molecular-level description of constrained chain topologies in multiblock copolymer gel networks.

Network characteristics in physical gels composed of solvated block copolymers varying in molecular design are examined here by dynamic rheology and computer simulations. In two triblock copolymer series, one with chain length (N) varied at constant copolymer composition (f) and the other with f varied at constant N, we discern the dependence of equilibrium network metrics on both N and f. Increasing the block number in a linear multiblock series at constant N and f escalates conformational complexity, which dominates network connectivity classified according to a midblock conformation index.

Thermoplastic Elastomer Systems Containing Carbon Nanofibers as Soft Piezoresistive Sensors.

Soft, wearable or printable strain sensors derived from conductive polymer nanocomposites (CPNs) are becoming increasingly ubiquitous in personal-care applications. Common elastomers employed in the fabrication of such piezoresistive CPNs frequently rely on chemically cross-linked polydiene or polysiloxane chemistry, thereby generating relatively inexpensive and reliable sensors that become solid waste upon application termination. Moreover, the shape anisotropy of the incorporated conductive nanoparticles can produce interesting electrical effects due to strain-induced spatial rearrangement. In this study, we investigate the morphological, mechanical, electrical, and electromechanical properties of CPNs generated from thermoplastic elastomer (TPE) triblock copolymer systems containing vapor-grown carbon nanofiber (CNF). Modulus-tunable TPE gels imbibed with a midblock-selective aliphatic oil exhibit well-behaved properties with increasing CNF content, but generally display nonlinear negative piezoresistance at different strain amplitudes and stretch rates due to nanofiber mobility upon CPN strain-cycling. In contrast, a neat TPE possessing low hard-block content yields a distinctive strain-reversible piezoresistive response, as well as low electrical hysteresis, upon cyclic deformation. Unlike their chemically cross-linked analogs, these physically cross-linked and thus environmentally benign CPNs are fully reprocessable by thermal and/or solvent means.

Complex Phase Behavior and Network Characteristics of Midblock-Solvated Triblock Copolymers as Physically Cross-Linked Soft Materials.

In the presence of a midblock-selective solvent, triblock copolymers not only self-organize but also form a molecular network. Thermoplastic elastomer gels constitute examples of such materials and serve as sealants and adhesives, as well as ballistic, microfluidic, and electroactive media. We perform Monte Carlo and dissipative particle dynamics simulations to investigate the phase behavior and network characteristics of these materials. Of particular interest is the existence of a truncated octahedral morphology that resembles the atomic arrangement of various inorganic species. Both simulation approaches quantify the midblock bridges responsible for network development and thus provide a detailed molecular picture of these composition-tunable soft materials.