Yuzhan Li

Photoresponsive Liquid Crystalline Epoxy Networks with Shape Memory Behavior and Dynamic Ester Bonds.

Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. All three functional building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively.

Thermomagnetic processing of liquid-crystalline epoxy resins and their mechanical characterization using nanoindentation.

A thermomagnetic processing method was used to produce a biphenyl-based liquid-crystalline epoxy resin (LCER) with oriented liquid-crystalline (LC) domains. The orientation of the LCER was confirmed and quantified using two-dimensional X-ray diffraction. The effect of molecular alignment on the mechanical and thermomechanical properties of the LCER was investigated using nanoindentation and thermomechanical analysis, respectively. The effect of the orientation on the fracture behavior was also examined. The results showed that macroscopic orientation of the LC domains was achieved, resulting in an epoxy network with an anisotropic modulus, hardness, creep behavior, and thermal expansion.

Photo-responsive liquid crystalline epoxy networks with exchangeable disulfide bonds

The increasing demand for intelligent materials has driven the development of polymers with a variety of functionalities. However, combining multiple functionalities within one polymer is still challenging because of the difficulties encountered in coordinating different functional building blocks during fabrication. In this work, we demonstrate the fabrication of a multifunctional liquid crystalline epoxy network (LCEN) using the combination of thermotropic liquid crystals, photo-responsive azobenzene molecules, and exchangeable disulfide bonds. In addition to shape memory behavior enabled by the reversible liquid crystalline phase transition and photo-induced bending behavior resulting from the photo-responsive azobenzene molecules, the introduction of dynamic disulfide bonds into the LCEN resulted in a structurally dynamic network, allowing the reshaping, repairing, and recycling of the material.

Cure kinetics of liquid crystalline epoxy resins based on biphenyl mesogen

The cure kinetics of a biphenyl-based liquid crystalline (LC) epoxy resin (LCER) was studied using differential scanning calorimetry (DSC) and polarized optical microscopy. The effects of LC phase formation on the cure kinetics were investigated. Both a model-free isoconversional method and a model-fitting method were used to analyze the DSC data. Results from the isoconversional analysis were applied to develop tentative multi-step kinetic models describing the curing reaction. Kinetic analysis showed that compared to the resins cured in amorphous phase, LCERs exhibited higher values of reaction enthalpy and a complex dependence of activation energy on the degree of cure. The formation of the LC phase resulted in a decrease in activation energy, leading to higher degree of reaction.

Bio-based reactive diluents as sustainable replacements for styrene in MAESO resin

Four different biorenewable methacrylated/acrylated monomers, namely, methacrylated fatty acid (MFA), methacrylated eugenol (ME), isobornyl methacrylate (IM), and isobornyl acrylate (IA) were employed as reactive diluents (RDs) to replace styrene (St) in a maleinated acrylated epoxidized soybean oil (MAESO) resin to produce bio-based thermosetting resins using free radical polymerization. The curing kinetics, gelation times, double bond conversions, thermal–mechanical properties, and thermal stabilities of MAESO-RD resin systems were characterized using DSC, rheometer, FT-IR, DMA, and TGA. The results indicate that all four RD monomers possess high bio-based carbon content (BBC) ranging from 63.2 to 76.9% and low volatilities (less than 7 wt% loss after being held isothermally at 30 °C for 5 h). Moreover, the viscosity of the MAESO-RD systems can be tailored to acceptable levels to fit the requirements for liquid molding techniques. Because of the introduction of RDs to the MAESO resin, the reaction mixtures showed an improved reactivity and an accelerated reaction rate. FT-IR results showed that almost all the CC double bonds within MAESO-RD systems were converted. The glass transition temperatures (Tg) of the MAESO-RDs ranged from 44.8 to 100.8 °C, thus extending the range of application. More importantly, the Tg of MAESO-ME resin (98.1 °C) was comparable to that of MAESO-St resin (100.8 °C). Overall, this work provided four potential RDs candidates to completely replace styrene in the MAESO resin, with the ME monomer being the most promising one.

Liquid Crystalline Epoxy Resins

The idea of developing crosslinked liquid crystalline (LC) networks was proposed by Nobel laureate, Pierre-Gilles de Gennes in 1969 (Gennes and Prost 1995). Subsequent efforts in this area resulted in a group of materials known as liquid crystalline thermosets (LCTs), which combines the outstanding properties of both liquid crystals and crosslinked thermosets (Shiota and Ober 1997a; Douglas 2002; Barclay and Ober 1993). A great number of LCTs have been synthesized using a variety of monomers, including epoxy (Carfagna et al. 1997; Giamberini et al. 1995; Mallon and Adams 1993), acrylate (Hikmet and Broer 1991; Hikmet et al. 1992; Litt et al. 1993; Holter et al. 1996), maleimide (Hoyt and Benicewicz 1990a, b), and cyanate ester (Mormann and Zimmermann 1995, 1996; Barclay et al. 1992a; Mormann and Kuckertz 1998). These materials exhibit properties that transcend their amorphous counterparts because of a polydomain structure. Among all the LCTs synthesized, liquid crystalline epoxy resins (LCERs) have received the most attention because of their diverse applications, such as microelectronics packaging materials, optical wave guides, adhesives, color filters, and structural materials. LCERs are generally formed upon curing of low molecular weight, rigid rod epoxy monomers with amines or anhydrides, resulting in the retention of a LC phase by the three dimensional crosslinking networks. Early investigation of LCERs focused on molecular architecture of the epoxy monomers and the related LC phase transition. Subsequent work involves studies on cure kinetics, phase evolution, molecular orientation and thermomechanical characterization of the LCERs. More recently, there have been efforts on fabrication of composites and nanocomposites using LCERs.