Liquid Crystalline Fibers Research Articles

Patterned Hydrophobic Liquid Crystalline Fibers Fabricated from Defect Arrays of Reactive Mesogens via Electric Field Modulation.

We have fabricated patterned fibers using a small-molecular-weight liquid crystal (LC) and reactive mesogens (RMs) under controlled electric fields in which defect arrays are generated depending on the electrode configuration. For this, the AC electric field with interdigitated electrodes is used to develop versatile defect structures of the LC phase. Hydrophobic LC network (LCN) fibers exhibiting porous morphologies have been made by removing the LC part after the polymerization of RM. The resulting LCN fibers show a surface tension reduction characteristic compared to the neat RM film and a sticky characteristic with the water droplet, suggesting a facile way to fabricate the hydrophobic surface that can be used in microdroplet transport.

Confinement-Induced Fabrication of Liquid Crystalline Polymeric Fibers.

In aqueous media, liquid crystalline droplets typically form spherical shapes in order to minimize surface energy. Recently, non-spherical geometry has been reported using molecular self-assembly of surfactant-stabilized liquid crystalline oligomers, resulting in branched and randomly oriented filamentous networks. In this study, we report a polymerization of liquid crystalline polymeric fibers within a micro-mold. When liquid crystal oligomers are polymerized in freely suspended aqueous media, curvilinear and randomly networked filaments are obtained. When reactive liquid crystalline monomers are oligomerized in a micro-channel, however, highly aligned linear fibers are polymerized. Within a top-down microfabricated mold, a bottom-up molecular assembly was successfully achieved in a controlled manner by micro-confinement, suggesting a unique opportunity for the programming architecture of materials via a hybrid approach.

(Digital Presentation) Chemically Modified Graphene for Real-World Applications: Graphene Oxide Liquid Crystal & Single Atom Catalysts

Graphene Oxide Liquid Crystal (GOLC) is an emerging 2D carbon based soft material, which exhibits nematic type colloidal discotic liquid crystallinity with the orientational ordering of graphene oxide flakes in good solvents, including water. Since our first discovery of GOLC in aqueous dispersion at 2009, this interesting mesophase has been utilized over world-wide for many different application fields, such as liquid crystalline graphene fiber spinning, highly ordered graphene membrane/film production, prototype liquid crystal display and so on. Interestingly, GOLC also allow us a valuable opportunity for the highly ordered molecular scale assembly of functional nanoscale structures. This presentation will introduce our current status of GOLC research particularly focusing on the nanoscale assembly of functional nanostructures, including highly oriented 1D fibers, 2D films and 3D nanoporous structures. Besides, relevant research works associated to the nanoscale assembly and chemical modification of various low dimensional materials, including 1D carbon nanotubes, 2D TMDs and MXene, will be presented particularly aiming at energy and environmental applications. In the last part of presentation, our wold-first discovery of single atom catalyst will be introduced also, including other research efforts exploiting customized heteroelement doping of graphene based strucures.

Thermotropic liquid crystalline copolyester fibers according to various heat treatment conditions

Thermotropic liquid crystal copolyester (TLCP) was synthesized using a melt polymerization method, with a molar ratio composition of 2,5-diethoxy terephthalic acid (ETA), hydroquinone (HQ), and p-hydroxybenzoic acid (HBA) of 1:1:3. TLCP exhibited nematic liquid crystalline mesophase and maintained nematic textures under all heat treatment conditions applied. The synthesized TLCP was processed into fibers using a capillary rheometer. The liquid crystalline mesophase, thermo-mechanical properties, and morphology of TLCP fibers obtained under various heat treatment conditions were investigated. The thermo-mechanical properties of the heat-treated fibers were improved compared to those of the as-spun fibers. The best results were obtained for TLCP fibers annealed at 230 °C for 9 h. The heat-treated fibers showed a well-developed microfiber morphology compared to the as-spun fibers. In the spun fibers, a skin–core morphology was observed regardless of the heat treatment conditions, and a well-developed fiber morphology better than the core area was observed in the skin area. The diameter of the fiber heat-treated at 230 °C for 9 h was approximately 60–110 nm.

‘Green’ composites based on liquid crystalline cellulose fibers and avocado seed starch

Fully biodegradable unidirectional green composites with excellent tensile properties were fabricated by combining one of the highest specific strength liquid crystalline cellulose (LCC) fibers as the reinforcement and microfibrillated cellulose (MFC) strengthened nonedible avocado seed starch (AVS)-based resin. MFC/AVS resin was crosslinked using 1,2,3,4-butane tetracarboxylic acid as well as plasticized using sorbitol or glycerol. Combination of alkali, mechanical and thermal treatments improved LCC fiber fracture stress from 1.5 GPa to over 1.9 GPa and Young’s modulus from 49 to 64 GPa. While the type and amount of plasticizer used changed the fracture strain of MFC/AVS resin, they also showed significant influence on the mechanical properties of the unidirectional composites. These composites prepared by hand lay-up, based on modified LCC fibers resulted in fracture stress of over 380 MPa and Young’s modulus of 19.5 GPa with less than 40% fiber content. Results suggest that there is scope to improve the properties further by using higher fiber content and automated manufacturing. These ‘green’ composites with excellent strength and stiffness may be used in many applications such as construction, automobile and others.

Multidisciplinary Materials Research in KAIST Over the Last 50 Years

Multidisciplinary Materials Research in KAIST Over the Last 50 Years

Self-Planarization of High-Performance Graphene Liquid Crystalline Fibers by Hydration.

Graphene fibers (GFs) are promising elements for flexible conductors and energy storage devices, while translating the extraordinary properties of individual graphene sheets into the macroscopically assembled 1D structures. We report that a small amount of water addition to the graphene oxide (GO) N-methyl-2-pyrrolidone (NMP) dispersion has significant influences on the mesophase structures and physical properties of wet-spun GFs. Notably, 2 wt % of water successfully hydrates GO flakes in NMP dope to form a stable graphene oxide liquid crystal (GOLC) phase. Furthermore, 4 wt % of water addition causes spontaneous planarization of wet-spun GFs. Motivated from these interesting findings, we develop highly electroconductive and mechanically strong flat GFs by introducing highly crystalline electrochemically exfoliated graphene (EG) in the wet-spinning of NMP-based GOLC fibers. The resultant high-performance hybrid GFs can be sewn on cloth, taking advantage of the mechanical robustness and high flexibility.

Modified tunicate nanocellulose liquid crystalline fiber as closed loop for recycling platinum-group metals

Rising demand and elemental rarity requires the recycling of precious metals such as platinum group elements (PGMs). Recently, biosorption has been focused on the capability of recovering precious metals, but in practice, recycling is inefficient or far away from a closed-loop material system. Here we use a polyethylenimine (PEI)-grafted spun-fiber made of cellulose nanofibril (CNF) extracted from a tunicate as a biosorbent for PGMs. Liquid crystallinity (LC) of TCNF suspension appears to contribute the generation of well-developed open porous structure in the fiber. We show the fiber has the selectivity and high capacity of Pt (120.2 mg/g, 86%) and Pd (26.5 mg/g, 74.2%) adsorption under the presence of other metals in simulated automobile waste. The adsorbed Pt and Pd with nano-scale clusters were uniformly distributed on the porous surface, which were directly applied as a catalyst. These results propose an easy approach to recover precious metals and reuse them directly, thereby closing loops of metal recycling.

Janus Graphene Liquid Crystalline Fiber with Tunable Properties Enabled by Ultrafast Flash Reduction

Flash photothermal treatment via Xenon lamp with a broad wavelength spectrum can effectively remove oxygen functionalities and restore sp2 domains at graphitic carbon materials. The chemical composition and relevant structure formation of flash reduced graphene oxide liquid crystal (GOLC) fibers are investigated in accordance with flash irradiation conditions. Owing to the spatial controllability of reduction level via anisotropic flash irradiation, the mechanical properties and electrical conductivity of graphene fibers can be delicately counterbalanced to attain desired properties. High sensitivity humidity sensors can be fabricated from the flash reduced fibers demonstrating notably higher sensitivity over the thermally reduced counterparts. This ultrafast flash reduction holds great promise for multidimensional macroscopic GO based structures, enabling a wide range of potential applications, including textile electronics and wearable sensors.

Graphene Fibers: Mussel‐Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity (Adv. Mater. 40/2018)

Graphene Fibers: Mussel‐Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity (Adv. Mater. 40/2018)

Mussel-Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity.

Inspired by mussel adhesive polydopamine (PDA), effective reinforcement of graphene-based liquid crystalline fibers to attain high mechanical and electrical properties simultaneously is presented. The two-step defect engineering, relying on bioinspired surface polymerization and subsequent solution infiltration of PDA, addresses the intrinsic limitation of graphene fibers arising from the folding and wrinkling of graphene layers during the fiber-spinning process. For a clear understanding of the mechanism of PDA-induced defect engineering, interfacial adhesion between graphene oxide sheets is straightforwardly analyzed by the atomic force microscopy pull-off test. Subsequently, PDA could be converted into an N-doped graphitic layer within the fiber structure by a mild thermal treatment such that mechanically strong fibers could be obtained without sacrificing electrical conductivity. Bioinspired graphene-based fiber holds great promise for a wide range of applications, including flexible electronics, multifunctional textiles, and wearable sensors.

Structure and Properties of Thermotropic Liquid Crystalline Polyarylate Fibers

Thermotropic liquid crystalline polyarylate fiber is a kind of high performance fiber with high strength and modulus, high temperature and chemical resistance. In this paper, TLCPAR fibers were prepared by melt spinning and then heat-treated. The effects of spinneret draft ratio, heat-treatment temperature on aggregate structure and mechanical properties of the fibers were investigated.

Advanced Green composites using liquid crystalline cellulose fibers and waxy maize starch based resin

Advanced green composites have been fabricated by using modified liquid crystalline cellulose (M-LCC) fibers and micro-fibrillated cellulose (MFC) modified waxy maize starch (M-WMS) based resin. LCC fibers, as a reinforcement, were modified in terms of tensile properties by a combination of chemical and heat treatment, under a predetermined tension. The surface topography, crystallinity, molecular alignment, and mechanical properties of M-LCC fibers were investigated to determine the effects of combination modification process on the fibers. M-WMS, as a resin, was prepared by two steps. In the first step, an environment-friendly cross-linker, 1,2,3,4-butane tetracarboxylic acid (BTCA), was used to improve the water resistance and tensile properties of the resin. In the second step, ‘MFC’, as reinforcing agent, was dispersed in the cross-linked resin to obtain substantial improvements in its tensile properties. Unidirectional advanced green composites consisting of M-LCC fibers and M-WMS were fabricated using hand lay-up followed by a compression molding process. The results showed that the M-LCC fibers had strength close to 2 GPa and the composites had strength close to 800 MPa. These advanced green composites could be used in structural applications.

(Invited) Graphene Oxide Liquid Crystals and Relevant Functional Nanostructures

Graphene Oxide Liquid Crystal (GOLC) is a newly emerging graphene based material, which exhibits nematic type colloidal discotic liquid crystallinity with orientational ordering of graphene oxide flakes in good solvents, including water. Since our first discovery of GOLC in aqueous dispersion at 2009, this interesting mesophase has been utilized over world-wide for many different application fields, such as liquid crystalline graphene fiber spinning, highly ordered graphene membrane/film production, prototype liquid crystal display and so on. Interestingly, GOLC also allow us a valuable opportunity for the highly ordered molecular scale assembly of functional nanoscale structures. This presentation will introduce our current status of GOLC research particularly focusing on the nanoscale assembly of functional nanostructures. Besides, relevant research works associated to the nanoscale assembly and chemical modification of various nanoscale graphene based materials will be presented.

Photomechanical Motion of Liquid-Crystalline Fibers Bending Away from a Light Source

A series of photomechanical fibers was fabricated with a thermal drawing method by using liquid-crystalline random copolymers containing azobenzene and biphenyl groups in side chain. After being post-cross-linked under mild conditions, these fibers showed photoinduced bending motion away from the light source even though homogeneous alignment of mesogens was observed along the drawing direction. This abnormal photoinduced deformation of the obtained fibers is far different from previously reported light-directed motions about liquid-crystalline fiber and film materials. The interesting photomechanical deformation can be ascribed to the surface volume expansion caused by photoisomerization of azobenzene moieties. Then the photoinduced bending behaviors of these fibers containing different azobenzene concentrations and cross-linking densities were systematically investigated, suggesting that the location of photoresponsive azobenzene played an important role in deciding their photomechanical behaviors. This...

Graphene Oxide Liquid Crystals Special Issue, Editorial

Graphene Oxide Liquid Crystals Special Issue, Editorial

Amorphous Molybdenum Sulfide Deposited Graphene Liquid Crystalline Fiber for Hydrogen Evolution Reaction Catalysis

Amorphous Molybdenum Sulfide Deposited Graphene Liquid Crystalline Fiber for Hydrogen Evolution Reaction Catalysis

Mechanism of cement paste reinforced by ultra-high molecular weight polyethylene powder and thermotropic liquid crystalline copolyester fiber with enhanced mechanical properties

In this study, a series of cementitious composites with high toughness and flexural strength was obtained by melt-dispersing ultra-high molecular weight polyethylene (UHMWPE) into a cement matrix followed by water immersion. The structure and chemical composition of the composites were characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Three point bending tests showed that the flexural strengths of the composites were improved from 5.5 MPa to 18.2 MPa with the presence of 25 wt% UHMWPE, and could be further enhanced to 28.1 MPa with the addition of only 0.1 vol% oriented thermotropic liquid crystalline copolyester (TLCP) fibers. An adhesive test revealed that the interfacial binding force between polymer and fiber was much stronger than that between cement and fiber. Our findings provide a simple way for utilizing polymer to improve the interface between the fibers and cement matrix, consequently achieving a dramatic increase in the flexural strength and toughness.

Thermal Conductivity in the Radial Direction of Deformed Polymer Fibers.

Thermal conductivity of polymer fibers in the axial direction has been extensively studied while thermal conductivity in the radial direction Λ remains unknown. In this work, polymer fibers with different molecular arrangements (crystalline, liquid crystalline, and amorphous) were plastically deformed. Λ was measured at engineering strains ε = 0.2-2.3 using time-domain thermoreflectance. Λ decreases with increasing strains for polyethylene (PE) and poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibers and is independent of strain for poly(methyl methacrylate) (PMMA) fibers. The extrapolated thermal conductivity at zero strain is Λ0 ≈ 0.27 Wm-1 K-1 for crystalline PE, Λ0 ≈ 0.29 Wm-1 K-1 for liquid crystalline PBO, and Λ0 ≈ 0.18 Wm-1 K-1 for amorphous PMMA. Λ of PE drops to Λ ≈ 0.14 Wm-1 K-1 at ε = 1.9; Λ of PBO drops to Λ ≈ 0.12 Wm-1 K-1 at ε = 2.1. We attribute the decrease of Λ with ε in crystalline and liquid crystalline fibers to structural disorder induced by plastic deformation. The combination of structural disorder and phonon focusing effects produces a thermal conductivity in deformed PE and PBO fibers that is lower than amorphous PMMA.

Scalable One‐Step Wet‐Spinning of Graphene Fibers and Yarns from Liquid Crystalline Dispersions of Graphene Oxide: Towards Multifunctional Textiles

AbstractKey points in the formation of liquid crystalline (LC) dispersions of graphene oxide (GO) and their processability via wet‐spinning to produce long lengths of micrometer‐dimensional fibers and yarns are addressed. Based on rheological and polarized optical microscopy investigations, a rational relation between GO sheet size and polydispersity, concentration, liquid crystallinity, and spinnability is proposed, leading to an understanding of lyotropic LC behavior and fiber spinnability. The knowledge gained from the straightforward formulation of LC GO “inks” in a range of processable concentrations enables the spinning of continuous conducting, strong, and robust fibers at concentrations as low as 0.075 wt%, eliminating the need for relatively concentrated spinning dope dispersions. The dilute LC GO dispersion is proven to be suitable for fiber spinning using a number of coagulation strategies, including non‐solvent precipitation, dispersion destabilization, ionic cross‐linking, and polyelectrolyte complexation. One‐step continuous spinning of graphene fibers and yarns is introduced for the first time by in situ spinning of LC GO in basic coagulation baths (i.e., NaOH or KOH), eliminating the need for post‐treatment processes. The thermal conductivity of these graphene fibers is found to be much higher than polycrystalline graphite and other types of 3D carbon based materials.