Longjian Xue

A New Method to Improve Poly(3-hexyl thiophene) (P3HT) Crystalline Behavior: Decreasing Chains Entanglement To Promote Order−Disorder Transformation in Solution

We promoted order-disorder transformation of poly(3-hexylthiophene) (P3HT) in solution by ultrasonic oscillation which substantially improved crystallinity in its pure film. P3HT with low molecular weight (M(w)) dispersed very well in p-xylene solvent and few aggregates generated in the solution. For P3HT with high M(w), the results suggested the coexistence of two phases: disordered coils in solution and ordered microcrystals in suspension. Upon ultrasonic oscillating, more ordered precursors generated in solution due to increased self-assembly from disordered to ordered configuration, which resulting from decreased extent of chains entanglement existing in high molecular system, and red shift at absorption maximum and growing intensity of the pi-pi* absorption at ca. 604 nm were observed in solution. The films prepared from the oscillated solution then showed increased degree of crystallinity, pi-pi interactions and homogeneously distributed nanofibrils, which should be attributed to the ordered precursors constructed in solution. Furthermore, the best crystallinity of the film was obtained at the oscillating time of 4 min, showing the equilibrium state between the increased content of crystalline molecules and the shortened crystalline length. This simple method paves the way for the decreasing chains entanglement during crystallizing process of conjugated polymer in solution, and it enriches the ways to improve crystalline order in thin films comprising crystallizable polymers.

The formation of different structures of poly(3-hexylthiophene) film on a patterned substrate by dip coating from aged solution

Different local morphologies of poly(3-hexylthiophene) (P3HT, M(w) = 87,000 and 30,000-40,000 g mol(- 1)) are grown on a patterned substrate, which is composed of octadecyltrichlorosilane (OTS area) stripes on a silicon wafer (SiO(x) area), via dip coating from the aged solutions. Bundles of P3HT (M(w) = 87,000 g mol(- 1)) nanorods on the SiO(x) area and long nanofibrillar crystals on the OTS area are generated simultaneously from the one-day-aged 1 mg ml(- 1) solution, while oriented P3HT (M(w) = 30,000-40,000 g mol(- 1)) nanofibrillar crystals parallel to the long axis of the OTS pattern form on the OTS area from the seven-days-aged solution (1 mg ml(- 1)). Different dimensional sizes of the P3HT aggregate in the toluene solution upon aging and the flow of the solution from SiO(x) to the OTS area, on which the receding contact angle is larger than that on the SiO(x) area, determines the local structures of the P3HT film on the patterned substrate.

Broadband antireflection of block copolymer/homopolymer blend films with gradient refractive index structures

The factors that influence the broadband antireflection of block copolymer/homopolymer blend films were systematically investigated. The gradient refractive index structure, which was generated by removing the PMMA content from a film of PS-b-PMMA/PMMA blends, contributed to the broadband antireflection. The volume fraction of the PMMA block (fPMMA), the total degree of polymerization (N) and the weight percent of the homopolymer played a key role in the formation of the gradient porosity index inner structure. By increasing χN, the PS porous structure was kept from collapsing after removal of the PMMA domain, which led to a stable gradient porosity ratio structure and higher transmittance. While increasing fPMMA, the PMMA domains changed from a dispersed phase to a continuous phase, which caused the residual PS structure to collapse more easily and the transmittance decreased. The best broadband antireflective properties were achieved from the 45 mg mL−1 solution of PS-b-PMMA (Mn = 68 000–33 500, fPMMA = ∼25%) blended with 30 wt% PMMA: a mean transmittance of 98.4% at full spectrum, and >98.0% in the visible–NIR range between 600 nm and 2000 nm.

Reversible Adhesion Switching of Porous Fibrillar Adhesive Pads by Humidity

We report reversible adhesion switching on porous fibrillar polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) adhesive pads by humidity changes. Adhesion at a relative humidity of 90% was more than nine times higher than at a relative humidity of 2%. On nonporous fibrillar adhesive pads of the same material, adhesion increased only by a factor of ~3.3. The switching performance remained unchanged in at least 10 successive high/low humidity cycles. Main origin of enhanced adhesion at high humidity is the humidity-induced decrease in the elastic modulus of the polar component P2VP rather than capillary force. The presence of spongelike continuous internal pore systems with walls consisting of P2VP significantly leveraged this effect. Fibrillar adhesive pads on which adhesion is switchable by humidity changes may be used for preconcentration of airborne particulates, pollutants, and germs combined with triggered surface cleaning.

Autophobic Dewetting of a Poly(methyl methacrylate) Thin Film on a Silicon Wafer Treated in Good Solvent Vapor

The wettability of thin poly(methyl methacrylate) (PMMA) films on a silicon wafer with a native oxide layer exposed to solvent vapors is dependent on the solvent properties. In the nonsolvent vapor, the film spread on the substrate with some protrusions generated on the film surface. In the good solvent vapor, dewetting happened. A new interface formed between the anchored PMMA chains and the swollen upper part of the film. Entropy effects caused the upper movable chains to dewet on the anchored chains. The rim instability depended on the surface tension of solvent (i.e., the finger was generated in acetone vapor (gamma(acetone) = 24 mN/m), not in dioxane vapor (gamma(dioxane) = 33 mN/m)). The spacing (lambda) that grew as an exponential function of film thickness h scaled as approximately h(1.31), whereas the mean size (D) of the resulting droplets grew linearly with h.

Crystallization-Induced Phase Segregation Based on Double-Crystalline Blends of Poly(3-hexylthiophene) and Poly(ethylene glycol)s.

Crystallization-induced vertical stratified structures were constructed based on double-crystalline poly(3-hexylthiophene) (P3HT)/poly(ethylene glycol)s (PEG) systems at room temperature, in which the P3HT crystallinity and the mechanism were investigated. Vertical stratified microstructures with highly crystalline P3HT network on the surface were formed when depositing from marginal solvents, while lateral phase-separated structures or low P3HT crystallinity were observed for good solvents. The morphological differences came from the solvent effect. In marginal solvents, p-xylene and dichloromethane, P3HT large-scale microcrystallites were generated in solution, which ensured the priority of P3HT crystalline sequence, and phase separation began in the liquid states. When the PEG matrix began to crystallize, great energy from which the second phase separation was induced drove P3HT crystallites to the surface, resulting in the formation of vertical stratified microstructures with highly crystalline P3HT network on the surface. The method, crystallization-induced phase segregation of crystalline-crystalline blends in marginal solvent, provides a facile way to construct vertically stratified structures, in which P3HT highly crystalline network is favored.

Tailoring Normal Adhesion of Arrays of Thermoplastic, Spring-like Polymer Nanorods by Shaping Nanorod Tips

The tip shape of contact elements in hairy adhesion systems is crucial for proper contact formation and adhesion enhancement. While submicrometer terminal contact elements show much better adhesion performance than their larger counterparts, shaping their tips so as to maximize normal adhesion has remained challenging. We prepared durable nanorod arrays consisting of stiff, highly entangled thermoplastic polymers with rationally shaped tips by replication of anodic aluminum oxide (AAO). Nanorod arrays with pancake-like tips showed pronounced normal dry adhesion already for small loading forces. For small loading forces, adhesion forces significantly exceeded the loading forces. Both the absence of hysteresis in force/displacement curves and the pronounced durability of the nanorods in series of repeated attachment/detachment cycles suggest that the nanorods behave like elastic springs. Experimental load-adhesion curves were reproduced with a modified Schargott-Popov-Gorb (SPG) model, assuming that contacts between probe and individual nanorods are sequentially formed with increasing indentation depth.

Humidity-enhanced wet adhesion on insect-inspired fibrillar adhesive pads

Many insect species reversibly adhere to surfaces by combining contact splitting (contact formation via fibrillar contact elements) and wet adhesion (supply of liquid secretion via pores in the insects’ feet). Here, we fabricate insect-inspired fibrillar pads for wet adhesion containing continuous pore systems through which liquid is supplied to the contact interfaces. Synergistic interaction of capillarity and humidity-induced pad softening increases the pull-off force and the work of adhesion by two orders of magnitude. This increase and the independence of pull-off force on the applied load are caused by the capillarity-supported formation of solid–solid contact between pad and the surface. Solid–solid contact dominates adhesion at high humidity and capillarity at low humidity. At low humidity, the work of adhesion strongly depends on the amount of liquid deposited on the surface and, therefore, on contact duration. These results may pave the way for the design of insect-inspired adhesive pads.

Hybrid Surface Patterns Mimicking the Design of the Adhesive Toe Pad of Tree Frog

Biological materials achieve directional reinforcement with oriented assemblies of anisotropic building blocks. One such example is the nanocomposite structure of keratinized epithelium on the toe pad of tree frogs, in which hexagonal arrays of (soft) epithelial cells are crossed by densely packed and oriented (hard) keratin nanofibrils. Here, a method is established to fabricate arrays of tree-frog-inspired composite micropatterns composed of polydimethylsiloxane (PDMS) micropillars embedded with polystyrene (PS) nanopillars. Adhesive and frictional studies of these synthetic materials reveal a benefit of the hierarchical and anisotropic design for both adhesion and friction, in particular, at high matrix-fiber interfacial strengths. The presence of PS nanopillars alters the stress distribution at the contact interface of micropillars and therefore enhances the adhesion and friction of the composite micropattern. The results suggest a design principle for bioinspired structural adhesives, especially for wet environments.

Effect of interfacial roughness on dewetting behavior of polystyrene/poly(methyl methacrylate) bilayer film

The dewetting behavior of polystyrene (PS) film on poly(methyl methacrylate) (PMMA) sublayer was investigated by changing the short-range roughness of the PMMA sublayer systemically. When the bilayer film was heated to the temperature above both Tgs, the protuberances formed in both layers to reduce the system energy. By tracing the dewetting process of the PS up-layer, the dewetting velocity was found to increase with the roughness of the sublayer. It was demonstrated theoretically and experimentally that the equilibrium contact angle, the apparent equilibrium contact angle, and dewetting velocity of PS film on PMMA sublayer were determined by the roughness of PMMA sublayer.