Hyeonyeol Jeon

Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers

The most important properties of self-healing polymers are efficient recovery at room temperature and prolonged durability. However, these two characteristics are contradictory, making it difficult to optimize them simultaneously. Herein, a transparent and easily processable thermoplastic polyurethane (TPU) with the highest reported tensile strength and toughness (6.8 MPa and 26.9 MJ m-3 , respectively) is prepared. This TPU is superior to reported contemporary room-temperature self-healable materials and conveniently heals within 2 h through facile aromatic disulfide metathesis engineered by hard segment embedded aromatic disulfides. After the TPU film is cut in half and respliced, the mechanical properties recover to more than 75% of those of the virgin sample within 2 h. Hard segments with an asymmetric alicyclic structure are more effective than those with symmetric alicyclic, linear aliphatic, and aromatic structures. An asymmetric structure provides the optimal metathesis efficiency for the embedded aromatic disulfide while preserving the remarkable mechanical properties of TPU, as indicated by rheological and surface investigations. The demonstration of a scratch-detecting electrical sensor coated on a tough TPU film capable of auto-repair at room temperature suggests that this film has potential applications in the wearable electronics industry.

Tunable solubility parameter of poly(3-hexyl thiophene) with hydrophobic side-chains to achieve rubbery conjugated films.

A highly π-conjugated nanofibrillar network of poly(3-hexyl thiophene) (P3HT) embedded in polydimethylsiloxane (PDMS) elastomer films on SiO2 dielectrics was facilely developed via solution-blending of an ultrasound-assisted dilute P3HT solution with a PDMS precursor followed by spin-casting and curing. In contrast, simple blending without ultrasonication against the dilute P3HT solution yielded large agglomerates in cast films owing to a great difference in solubility parameter (δ) values (P3HT = 9.5 cal(1/2) cm(-3/2), PDMS = 7.3 cal(1/2) cm(-3/2)). In the ultrasound-assisted 0.1 vol % P3HT solutions, the π-conjugated polymer could develop crystalline nanofibrils surrounded by nonpolar hexyl side chains with the same δ value as that of PDMS, yielding homogeneously dispersed 10 wt % loaded P3HT/PDMS blend films. Spun-cast P3HT/PDMS blend films could yield high electrical properties in organic field-effect transistor, including mobilities of up to 0.045 cm(2) V(-1) s(-1) and on/off current ratios of >5 × 10(5), as well as excellent environmental stability owing to the outer PDMS layer.

A Physicochemical Approach Toward Extending Conjugation and the Ordering of Solution-Processable Semiconducting Polymers

Poly(3-hexylthiophene)s (P3HTs) were synthesized with a well-controlled molecular weight (Mw) and degree of regioregularity; additionally, π-conjugated P3HT structures in both solutions and films were systematically investigated. Conjugated P3HT phases in spin-cast films significantly changed from ordered nanorods, -fibrils, and -ribbons to less-ordered granules, depending on the conformation of the P3HT chains in solutions. The chain conformations could be physicochemically adjusted by modifying chain lengths (from 5 to 45 kDa), solvents, and ultrasonication. Highly extended conformations of the P3HT in ultrasound-treated solutions yielded longer degree of conjugation both the intra- and intermolecularly. When toluene was used as a marginal solvent, ultrasonicated 0.1 wt % 29 kDa P3HT solutions could be used to yield highly ordered aggregates in spin-cast films, including nanoribbons or nanosheets, with field-effect mobility (μFET) up to ∼0.1 cm(2) V(-1) s(-1) being measured for organic field-effect transistors (OFETs). However, ultrasonicated chloroform systems with good P3HT solubility (for P3HT Mw ≥ 20 kDa) yielded featureless conducting layers even at 0.4 wt % P3HT content. However, these film-based OFETs yielded μFET values up to 0.04 cm(2) V(-1) s(-1), which were much greater than 0.004 cm(2) V(-1) s(-1) for the nonultrasonicated systems.

Air-processable silane-coupled polymers to modify a dielectric for solution-processed organic semiconductors.

Poly(styrene-r-3-methacryloxypropyltrimethoxysilane) (PSMPTS) copolymers were synthesized by the free radical polymerization of styrene and 3-methacryloxypropyltrimethoxysilane (MPTS) for use as surface modifiers. PSMPTS copolymers were spun-cast onto a hydrophilic SiO2 layer and were then annealed at 150 °C in ambient air. The polystyrene (PS)-based copolymer, with a molecular weight of 32 700 g mol(-1) and approximately 30 MPTS coupling sites, was easily grafted onto the SiO2 surface after annealing periods longer than 1 min, yielding a physicochemically stable layer. On the untreated and polymer-treated dielectrics, spin-casting of an ultrasonicated poly(3-hexyl thiophene) (P3HT) solution yielded highly interconnected crystal nanofibrils of P3HT. The resulting organic field-effect transistors (OFETs) showed similar mobility values of 0.01-0.012 cm(2) V(-1) s(-1) for all surfaces. However, the threshold voltage (Vth) drastically decreased from +13 (for bare SiO2) to 0 V by grafting the PSMPTS copolymers to the SiO2 surface. In particular, the interfacial charge traps that affect Vth were minimized by grafting the 11 mol % MPTS-loaded copolymer to the polar dielectric surface. We believe that this ambient-air-processable silane-coupled copolymer can be used as a solution-based surface modifier for continuous, large-scale OFET fabrication.

Environmentally-Friendly Synthesis of Carbonate-Type Macrodiols and Preparation of Transparent Self-Healable Thermoplastic Polyurethanes

Carbonate-type macrodiols synthesized by base-catalyzed polycondensation of co-diols and dimethyl carbonate as an environmentally-friendly route were subsequently utilized for the preparation of transparent and self-healable thermoplastic polyurethanes (TPUs) containing a carbonate-type soft segment. Three types of macrodiols, obtained from mono, dual and triple diol-monomers for target molecular weights of 1 and 1.5 kg mol−1, were analyzed by 1H NMR integration and the OH titration value. Colorless transparent macrodiols in a liquid state at a room temperature of 20 °C were obtained, except the macrodiol from mono 1,6-hexanediol. Before TPU synthesis, macrodiols require pH neutralization to prevent gelation. TPUs synthesized by a solution pre-polymer method with 4,4′-methylene(bisphenyl isocyanate) and 1,4-butanediol as a chain extender exhibited moderate molecular weights, good transparencies and robust mechanical properties. Especially, the incorporation of 3-methyl-1,5-pentanediol within carbonate-type macrodiols enhanced the transparency of the resultant TPUs by decreasing the degree of microphase separation evidenced by ATR-FTIR and DSC. Interestingly, packing density of hard segments and the degree of microphase separation determined the self-healing efficiency of TPUs, which showed good performances in the case of sourced macrodiols from triple diol-monomers.

Butanol-mediated oven-drying of nanocellulose with enhanced dehydration rate and aqueous re-dispersion

AbstractThe application potential of nanocellulose has been previously hindered by the costly and slow drying methods that this material requires, including freeze/supercritical drying process. The main issue for nanocellulose commercialization is how effectively and rapidly its high water contents (90–99%) can be removed, all of which raise its transportation and processing costs. Oven-drying is the fastest, most economical, and most scalable method for dehydrating nanocellulose, but causes strong interfibrillar aggregation and leads to poor aqueous re-dispersion. Here, we report that the problems of nanocellulose oven-drying are comprehensively overcome by adding tert-butanol (t-BuOH) to the nanocellulose solution at >90%. In a lab-scale comparison, the t-BuOH-mediated oven-drying of aqueous nanocellulose showed lower drying times by a factor of 2–12 compared to water only oven-drying and freeze drying of the same material. The dispersibility of this dried nanocellulose is as high as the never-dried material in terms of particle size, light transmittance, and sedimentation. t-BuOH reduces interfibrillar shrinkage due to the lower surface tension of t-BuOH compared to water, and a remaining t-BuOH/water mixture decreases interfibrillar adhesion and contact. Graphical abstractThis paper suggests a strategy to improve the aqueous re-dispersibility of oven-dried nanocellulose, and to accelerate oven-drying rate.

Trans crystallization behavior and strong reinforcement effect of cellulose nanocrystals on reinforced poly(butylene succinate) nanocomposites

Correction for ‘Trans crystallization behavior and strong reinforcement effect of cellulose nanocrystals on reinforced poly(butylene succinate) nanocomposites’ by Taeho Kim et al., RSC Adv., 2018, 8, 15389–15398.

Fast and Scalable Hydrodynamic Synthesis of MnO2/Defect-Free Graphene Nanocomposites with High Rate Capability and Long Cycle Life

The integration of metal oxides and carbon materials provides a great potential for enhancing the high energy and power densities of supercapacitors, but the rational design and scalable fabrication of such composite materials still remain a challenge. Herein, we report a fast, scalable, and one-pot hydrodynamic synthesis for preparing ion conductive and defect-free graphene from graphite and MnO2/graphene nanocomposites. The use of this hydrodynamic method using Taylor-Couette flow allows us to efficiently fast shear-exfoliate graphite into large quantities of high-quality graphene sheets. Deposition of MnO2 on graphene is subsequently performed in a fluidic reactor within 10 min. The prepared MnO2/graphene nanocomposite shows outstanding electrochemical performances, such as a high specific capacitance of 679 F/g at 25 mV/s, a high rate capability of 74.7% retention at an extremely high rate of 1000 mV/s, and an excellent cycling characteristic (∼94.7% retention over 20 000 cycles). An asymmetric supercapacitor device is fabricated by assembling an anode of graphene and a cathode of MnO2/graphene, which resulted in high energy (35.2 W h/kg) and power (7.4 kW/kg) densities (accounting for the mass of both electrodes and the electrolyte) with a high rate capability and long cycle life.