Influence of microstructural alterations of liquid metal and its interfacial interactions with rubber on multifunctional properties of soft composite materials.

Liquid metal (LM)-based polymer composites are currently new breakthrough and emerging classes of soft multifunctional materials (SMMs) having immense transformative potential for soft technological applications. Currently, room-temperature LMs, mostly eutectic gallium­indium and Galinstan alloys are used to integrate with soft polymer due to their outstanding properties such as high conductivity, fluidity, low adhesion, high surface tension, low cytotoxicity, etc. The microstructural alterations and interfacial interactions controlling the efficient integration of LMs with rubber are the most critical aspects for successful implementation of multifunctionality in the resulting material. In this review article, a fundamental understanding of microstructural alterations of LMs to the formation of well-defined percolating networks inside an insulating rubber matrix has been established by exploiting several existing theoretical and experimental studies. Furthermore, effects of the chemical modifications of an LM surface and its interfacial interactions on the compatibility between solid rubber and fluid filler phase have been discussed. The presence of thin oxide layer on the LM surface and the effects and challenges it poses to the adequate functionalization of these materials have been discussed. Plausible applications of SMMs in different soft matter technologies, like soft robotics, flexible electronics, soft actuators, sensors, etc. have been provided. Finally, the current technical challenges and further prospective to the development of SMMs using non­silicone rubbers have been critically discussed. This review is anticipated to infuse a new impetus to the associated research communities for the development of next generation SMMs.

Designing Supertough and Ultrastretchable Liquid Metal-Embedded Natural Rubber Composites for Soft-Matter Engineering.

Functional elastomers with incredible toughness and stretchability are indispensable for applications in soft robotics and wearable electronics. Furthermore, coupled with excellent electrical and thermal properties, these materials are at the forefront of recent efforts toward widespread use in cutting-edge electronics and devices. Herein, we introduce a highly deformable eutectic-GaIn liquid metal alloy-embedded natural rubber (NR) architecture employing, for the first time, industrially viable solid-state mixing and vulcanization. Standard methods of rubber processing and vulcanization allow us to fragment and disperse liquid metals into submicron-sized droplets in cross-linked NR without compromising the elastic properties of the base matrix. In addition to substantial boosts in mechanical (strain at failure of up to ∼650%) and elastic (negligible hysteresis loss) performances, the tearing energy of the composite was enhanced up to 6 times, and a fourfold reduction in the crack growth rate was achieved over a control vulcanizate. Moreover, we demonstrate improved thermal conductivity and dielectric properties for the resulting composites. Therefore, this work provides a facile and scalable pathway to develop liquid metal-embedded soft elastomeric composites that could be instrumental toward potential applications in soft-matter engineering.

Morphology and Physico-Mechanical Threshold of α-Cellulose as Filler in an E-SBR Composite.

In the current context of green mobility and sustainability, the use of new generation natural fillers, namely, α-cellulose, has gained significant recognition. The presence of hydroxyl groups on α-cellulose has generated immense eagerness to map its potency as filler in an elastomeric composite. In the present work, α-cellulose-emulsion-grade styrene butadiene rubber (E-SBR) composite is prepared by conventional rubber processing method by using variable proportions of α-cellulose (1 to 40 phr) to assess its reinforce ability. Rheological, physical, visco-elastic and dynamic-mechanical behavior have clearly established that 10 phr loading of α-cellulose can be considered as an optimized dosage in terms of performance parameters. Morphological characterization with the aid of scanning electron microscope (SEM) and transmission electron microscopy (TEM) also substantiated that composite with 10 phr loading of α-cellulose has achieved the morphological threshold. With this background, synthetic filler (silica) is substituted by green filler (α-cellulose) in an E-SBR-based composite. Characterization of the compound has clearly established the reinforcement ability of α-cellulose.

Fabrication of Flexible Polymer Molds for Polymer Microstructuring by Roll-to-Roll Hot Embossing.

Roll-to-roll hot embossing could revolutionize the manufacturing of multifunctional polymer films with the ability to process large area at a high rate with reduced cost. The continuous hot embossing of the films, however, has been hindered due to the lack of durable and flexible molds, which can replicate micro and nanofeatures with reliability over several embossing cycles. In this work, we demonstrate for the first time the fabrication of a flexible polymer (polyimide) mold from the commercially available sheet by a maskless photolithography approach combined with inductively coupled plasma etching and its potential application to the roll-to-roll hot embossing process. The flexible polyimide mold consisted of holes with controlled dimensions: diameter: 14 µm, spacing: 16.5 µm, and depth: 6.8 µm. The reliability of flexible polyimide mold was tested and implemented by embossing micron-sized features on a commercial thermoplastic polymer, polyamide, and thermoplastic elastomer (TPE) sheet. The polyimide mold replicated micron-sized features on polymer substrates (polyamide and TPE) with excellent fidelity and was durable even after numerous embossing cycles.

Water-Responsive and Mechanically Adaptive Natural Rubber Composites by in Situ Modification of Mineral Filler Structures.

A new biomimetic stimuli-responsive adaptive elastomeric material, whose mechanical properties are altered by a water treatment is reported in this paper. This material is a calcium sulphate (CaSO4) filled composite with an epoxidized natural rubber (ENR) matrix. By exploiting various phase transformation processes that arise when CaSO4 is hydrated, several different crystal structures of CaSO4· xH2O can be developed in the cross-linked ENR matrix. Significant improvements in the mechanical and thermal properties are then observed in the water-treated composites. When compared with the untreated sample, there is approximately 100% increase in the dynamic modulus. The thermal stability of the composites is also improved by increasing the maximum degradation rate temperature by about 20 °C. This change in behavior results from an in situ development of hydrated crystal structures of the nanosized CaSO4 particles in the ENR matrix, which has been verified using Raman spectroscopy, transmission electron microscopy, atomic force microscopy, and X-ray scattering. This work provides a promising and relatively simple pathway for the development of next generation of mechanically adaptive elastomeric materials by an eco-friendly route, which may eventually also be developed into an innovative biodegradable and biocompatible smart polymeric material.

3D-Printable PP/SEBS Thermoplastic Elastomeric Blends: Preparation and Properties.

Currently, material extrusion 3D printing (ME3DP) based on fused deposition modeling (FDM) is considered a highly adaptable and efficient additive manufacturing technique to develop components with complex geometries using computer-aided design. While the 3D printing process for a number of thermoplastic materials using FDM technology has been well demonstrated, there still exists a significant challenge to develop new polymeric materials compatible with ME3DP. The present work reports the development of ME3DP compatible thermoplastic elastomeric (TPE) materials from polypropylene (PP) and styrene-(ethylene-butylene)-styrene (SEBS) block copolymers using a straightforward blending approach, which enables the creation of tailorable materials. Properties of the 3D printed TPEs were compared with traditional injection molded samples. The tensile strength and Young's modulus of the 3D printed sample were lower than the injection molded samples. However, no significant differences could be found in the melt rheological properties at higher frequency ranges or in the dynamic mechanical behavior. The phase morphologies of the 3D printed and injection molded TPEs were correlated with their respective properties. Reinforcing carbon black was used to increase the mechanical performance of the 3D printed TPE, and the balancing of thermoplastic elastomeric and mechanical properties were achieved at a lower carbon black loading. The preferential location of carbon black in the blend phases was theoretically predicted from wetting parameters. This study was made in order to get an insight to the relationship between morphology and properties of the ME3DP compatible PP/SEBS blends.

DNA-melamine hybrid molecules: from self-assembly to nanostructures.

Single-stranded DNA-melamine hybrid molecular building blocks were synthesized using a phosphoramidation cross-coupling reaction with a zero linker approach. The self-assembly of the DNA-organic hybrid molecules was achieved by DNA hybridization. Following self-assembly, two distinct types of nanostructures in the form of linear chains and network arrays were observed. The morphology of the self-assembled nanostructures was found to depend on the number of DNA strands that were attached to a single melamine molecule.

Processing of abasic site damaged lesions by APE1 enzyme on DNA adsorbed over normal and organomodified clay.

The efficiency of the apurinic/apyrimidinic endonuclease (APE1) DNA repair enzyme in the processing of abasic site DNA damage lesions at precise location in DNA oligomer duplexes that are adsorbed on clay surfaces was evaluated. Three different forms of clay namely montmorillonite, quaternary ammonium salt modified montmorillonite and its boiled counterpart i.e. partially devoid of organic moiety were used for a comparative study of adsorption, desorption and DNA repair efficiency on their surfaces. The interaction between the DNA and the clay was analysed by X-ray diffraction, Atomic force microscopy, UV-Vis spectroscopy and Infrared spectroscopy. The abasic site cleavage efficiency of APE1 enzyme was quantitatively evaluated by polyacrylamide gel electrophoresis. Apart from the difference in the DNA adsorption or desorption capacity of the various forms of clay, substantial variation in the repair efficiency of abasic sites initiated by the APE1 enzyme on the clay surfaces was observed. The incision efficiency of APE1 enzyme at abasic sites was found to be greatly diminished, when the DNA was adsorbed over organomodified montmorillonite. The reduced repair activity indicates an important role of the pendant surfactant groups on the clay surfaces in directing APE1 mediated cleavage of abasic site DNA damage lesions.