Soft Self-Healing Robot Driven by New Micro Two-Way Shape Memory Alloy Spring.

Soft robotic bodies are susceptible to mechanical fatigue, punctures, electrical breakdown, and aging, which can result in the degradation of performance or unexpected failure. To overcome these challenges, a soft self-healing robot is created using a thermoplastic methyl thioglycolate-modified styrene-butadiene-styrene (MG-SBS) elastomer tube fabricated by melt-extrusion, to allow the robot to self-heal autonomously at room temperature. After repeated damage and being separated into several parts, the robot is able to heal its stiffness and elongation to break to enable almost complete recovery of robot performance after being allowed to heal at room temperature for 24 h. The self-healing capability of the robot is examined across the material scale to robot scale by detailed investigations of the healing process, healing efficiency, mechanical characterization of the robot, and assessment of dynamic performance before and after healing. The self-healing robot is driven by a new micro two-way shape-memory alloy (TWSMA) spring actuator which achieved a crawling speed of 21.6 cm/min, equivalent to 1.57 body length per minute. An analytical model of the robot is created to understand the robot dynamics and to act as an efficient tool for self-healing robot design and optimization. This work therefore provides a new methodology to create efficient, robust, and damage-tolerant soft robots.

Synthesis and Characterization of High Glycolic Acid Content Poly(glycolic acid-co-butylene adipate-co-butylene terephthalate) and Poly(glycolic acid-co-butylene succinate) Copolymers with Improved Elasticity.

Poly(glycolic acid) (PGA) is a biodegradable polymer with high gas barrier properties, mechanical strength, and heat deflection temperature. However, PGA's brittleness severely limits its application in packaging, creating a need to develop PGA-based copolymers with improved elasticity that maintain its barrier properties and hydrolytic degradability. In this work, a series of PGBAT (poly(glycolic acid-co-butylene) adipate-co-butylene terephthalate) copolymers containing 21-92% glycolic acid (nGA) with Mw values of 46,700-50,600 g mol-1 were synthesized via melt polycondensation, and the effects of altering the nGA on PGBAT's thermomechanical properties and hydrolysis rate were investigated. Poly(glycolic acid-co-butylene succinate) (PGBS) and poly(glycolic acid-co-butylene terephthalate) (PGBT) copolymers with high nGA were synthesized for comparison. DSC analysis revealed that PGBAT21 (nGA = 21%) and PGBAT92 were semicrystalline, melting between 102.8 and 163.3 °C, while PGBAT44, PGBAT86-89, PGBT80, and PGBS90 were amorphous, with Tg values from -19.0 to 23.7 °C. These high nGA copolymers showed similar rates of hydrolysis to PGA, whereas those containing <50% GA showed almost no mass loss over the testing period. Their mechanical properties were highly dependent upon their crystallinity and improved significantly after annealing. Of the high nGA copolymers, annealed PGBS90 (Mw 97,000 g mol-1) possessed excellent mechanical properties with a modulus of 588 MPa, tensile strength of 30.0 MPa, and elongation at break of 171%, a significant improvement on PGA's elongation at break of 3%. This work demonstrates the potential of enhancing PGA's flexibility by introducing minor amounts of low-cost diols and diacids into its synthesis.

Synthesis of Poly(Lactic Acid-co-Glycolic Acid) Copolymers with High Glycolide Ratio by Ring-Opening Polymerisation.

The rise in demand for biodegradable plastic packaging with high barrier properties has spurred interest in poly(lactic acid-co-glycolic acid) (PLGA) copolymers with a relatively high glycolide content. In this work, we examined how reaction conditions affect the synthesis of PLGA25 (L:G 25:75) through the ring-opening polymerisation of d-l-lactide (L) and glycolide (G), using tin 2-ethylhexanoate (Sn(Oct)2) as the catalyst and 1-dodecanol as the initiator. The effects of varying the initiator concentration, catalyst concentration, reaction time, and temperature on the molecular weight, monomer conversion, and thermal properties of PLGA25 were investigated. Increasing the reaction temperature from 130 to 205 °C significantly reduced the time required for high monomer conversions but caused greater polymer discolouration. Whilst increasing the [M]:[C] from 6500:1 to 50,000:1 reduced polymer discolouration, it also resulted in longer reaction times and higher reaction temperatures being required to achieve high conversions. High Mn and Mw values of 136,000 and 399,000 g mol-1 were achieved when polymerisations were performed in the solid state at 150 °C using low initiator concentrations. These copolymers were analysed using high temperature SEC at 80 °C, employing DMSO instead of HFIP as the eluent.

Challenges and Opportunities of Self-Healing Polymers and Devices for Extreme and Hostile Environments.

Engineering materials and devices can be damaged during their service life as a result of mechanical fatigue, punctures, electrical breakdown, and electrochemical corrosion. This damage can lead to unexpected failure during operation, which requires regular inspection, repair, and replacement of the products, resulting in additional energy consumption and cost. During operation in challenging, extreme, or harsh environments, such as those encountered in high or low temperature, nuclear, offshore, space, and deep mining environments, the robustness and stability of materials and devices are extremely important. Over recent decades, significant effort has been invested into improving the robustness and stability of materials through either structural design, the introduction of new chemistry, or improved manufacturing processes. Inspired by natural systems, the creation of self-healing materials has the potential to overcome these challenges and provide a route to achieve dynamic repair during service. Current research on self-healing polymers remains in its infancy, and self-healing behavior under harsh and extreme conditions is a particularly untapped area of research. Here, the self-healing mechanisms and performance of materials under a variety of harsh environments are discussed. An overview of polymer-based devices developed for a range of challenging environments is provided, along with areas for future research.

Dynamic Polymer Networks: A New Avenue towards Sustainable and Advanced Soft Machines.

While the fascinating field of soft machines has grown rapidly over the last two decades, the materials they are constructed from have remained largely unchanged during this time. Parallel activities have led to significant advances in the field of dynamic polymer networks, leading to the design of three-dimensionally cross-linked polymeric materials that are able to adapt and transform through stimuli-induced bond exchange. Recent work has begun to merge these two fields of research by incorporating the stimuli-responsive properties of dynamic polymer networks into soft machine components. These include dielectric elastomers, stretchable electrodes, nanogenerators, and energy storage devices. In this Minireview, we outline recent progress made in this emerging research area and discuss future directions for the field.

Isocyanate-functionalised graphene oxide and poly(vinyl alcohol) nacre-mimetic inspired freestanding films.

Nacre mimetic films based on 2-ureido-4[1H]-pyrimidinone (UPy) functionalised graphene oxide (GO) and poly(vinyl alcohol) (PVA) were readily prepared by self-assembly using a vacuum filtration method. The isocyanate (UPy) functionalisation of the PVA was confirmed from a combination of Fourier transform infrared spectroscopy (FTIR) and changes in d-spacing from X-ray diffraction (XRD) measurements and, of the GO by solid-state NMR measurements reported by the authors previously. This is the first example of nacre mimetic structures where both the nanoplatelet (GO) and polymer (PVA) components are functionalised with complimentary groups. The resulting films displayed substantial increases in Young's modulus (E) of 392% (GO1/PVA1), ultimate tensile strength (UTS, σ) of 535% (GO1/PVA1), elongation at break (ε max) of 598% (GO10/PVA5) and tensile toughness (U T) of 1789% (GO1/PVA10) compared to the un-functionalised GO analogues. The binding of UPy to both the GO and the PVA provides multiple routes by which these freestanding nacre mimetic films can dissipate applied loads.

Self-healing and mechanical performance of dynamic glycol chitosan hydrogel nanocomposites.

The application of functional self-healing and mechanically robust hydrogels in bioengineering, drug delivery, soft robotics, etc., is continuously growing. However, fabricating hydrogels that simultaneously possess good mechanical and self-healing properties remains a challenge. Developing robust hydrogel formulations for the encapsulation and release of hydrophobic substances is a major challenge especially in some pharmaceutical treatments where the many of drugs show incompatibility with the hydrophilic hydrogel matrices. Schiff base hydrogels have been developed using a benzaldehyde multifunctional amphiphilic polyacrylamide crosslinker in conjunction with glycol chitosan. The polymeric crosslinker was synthesized by a two-step reaction using aqueous Cu-RDRP to give an ABA telechelic copolymer of N,N-dimethyl acrylamide (DMAc) and N-hydroxyethyl acrylamide (HEAm) from a bifunctional PEG. The polymer was then modified by post functionalization leading to a multifunctional benzaldehyde crosslinker that was shown to be capable of self-assembly into aggregates in aqueous media serving as a possible candidate for the entrapment of hydrophobic substances. Aqueous solutions of the crosslinker spontaneously formed hydrogels when mixed with glycol chitosan due to the in situ formation of imine bonds. Hydrogels were characterized while additional comparisons were made with a commonly used bifunctional PEG crosslinker. The effect of introducing partially reduced graphene oxide (GO) nanosheets was also examined and led to enhancements in both mechanical properties (2.0 fold increase in modulus and 1.4 fold increase in strain) and self-healing efficiencies (>99% from 60% by rheology) relative to the pristine polymer hydrogels.

Coupling Dynamic Covalent Bonds and Ionic Crosslinking Network to Promote Shape Memory Properties of Ethylene-vinyl Acetate Copolymers.

Dynamic crosslinking networks based on Diels-Alder (DA) chemistry and ionic interactions were introduced to maleic anhydride modified ethylene-vinyl acetate copolymer (mEVA) via in situ melt processing. The dual dynamic crosslinking networks were characterized by temperature-dependent FTIR, and the effects on the shape memory properties of mEVA were evaluated with dynamic mechanical thermal analysis and cyclic tensile testing. A crosslinking density was achieved at 2.36 × 10-4 mol·cm-3 for DA-crosslinked mEVA; as a result, the stress at 100% extension was increased from 3.8 to 5.6 MPa, and tensile strength and elongation at break were kept as high as 30.3 MPa and 486%, respectively. The further introduction of 10 wt % zinc methacrylate increased the dynamic crosslinking density to 3.74 × 10-4 mol·cm-3 and the stress at 100% extension to 9.0 MPa, while providing a tensile strength of 28.4 MPa and strain at break of 308%. The combination of reversible DA covalent crosslinking and ionic network in mEVA enabled a fixing ratio of 76.4% and recovery ratio of 99.4%, exhibiting an enhanced shape memory performance, especially at higher temperatures. The enhanced shape memory and mechanical performance of the dual crosslinked mEVA showed promising reprocessing and recycling abilities of the end-of-life products in comparison to traditional peroxide initiated covalent crosslinked counterparts.

Self-Healing Dielectric Elastomers for Damage-Tolerant Actuation and Energy Harvesting.

The actuation and energy-harvesting performance of dielectric elastomers are strongly related to their intrinsic electrical and mechanical properties. For future resilient smart transducers, a fast actuation response, efficient energy-harvesting performance, and mechanical robustness are key requirements. In this work, we demonstrate that poly(styrene-butadiene-styrene) (SBS) can be converted into a self-healing dielectric elastomer with high permittivity and low dielectric loss, which can be deformed to large mechanical strains; these are key requirements for actuation and energy-harvesting applications. Using a one-step click reaction at room temperature for 20 min, methyl-3-mercaptopropionate (M3M) was grafted to SBS and reached 95.2% of grafting ratios. The resultant M3M-SBS can be deformed to a high mechanical strain of 1000%, with a relative permittivity of εr = 7.5 and a low tan δ = 0.03. When used in a dielectric actuator, it can provide 9.2% strain at an electric field of 39.5 MV m-1 and can also generate an energy density of 11 mJ g-1 from energy harvesting. After being subjected to mechanical damage, the self-healed elastomer can recover 44% of its breakdown strength during energy harvesting. This work demonstrates a facile route to produce self-healing, high permittivity, and low dielectric loss elastomers for both actuation and energy harvesting, which is applicable to a wide range of diene elastomer systems.

Interface design for high energy density polymer nanocomposites.

This review provides a detailed overview on the latest developments in the design and control of the interface in polymer based composite dielectrics for energy storage applications. The methods employed for interface design in composite systems are described for a variety of filler types and morphologies, along with novel approaches employed to build hierarchical interfaces for multi-scale control of properties. Efforts to achieve a close control of interfacial properties and geometry are then described, which includes the creation of either flexible or rigid polymer interfaces, the use of liquid crystals and developing ceramic and carbon-based interfaces with tailored electrical properties. The impact of the variety of interface structures on composite polarization and energy storage capability are described, along with an overview of existing models to understand the polarization mechanisms and quantitatively assess the potential benefits of different structures for energy storage. The applications and properties of such interface-controlled materials are then explored, along with an overview of existing challenges and practical limitations. Finally, a summary and future perspectives are provided to highlight future directions of research in this growing and important area.

Mechanically Enhanced Electrical Conductivity of Polydimethylsiloxane-Based Composites by a Hot Embossing Process.

Electrically conductive polymer composites are in high demand for modern technologies, however, the intrinsic brittleness of conducting conjugated polymers and the moderate electrical conductivity of engineering polymer/carbon composites have highly constrained their applications. In this work, super high electrical conductive polymer composites were produced by a novel hot embossing design. The polydimethylsiloxane (PDMS) composites containing short carbon fiber (SCF) exhibited an electrical percolation threshold at 0.45 wt % and reached a saturated electrical conductivity of 49 S/m at 8 wt % of SCF. When reducing the sample thickness from 1.0 to 0.1 mm by the hot embossing process, a compression-induced percolation threshold occurred at 0.3 wt %, while the electrical conductivity was further enhanced to 378 S/m at 8 wt % SCF. Furthermore, the addition of a second nanofiller of 1 wt %, such as carbon nanotube or conducting carbon black, further increased the electrical conductivity of the PDMS/SCF (8 wt %) composites to 909 S/m and 657 S/m, respectively. The synergy of the densified conducting filler network by the mechanical compression and the hierarchical micro-/nano-scale filler approach has realized super high electrically conductive, yet mechanically flexible, polymer composites for modern flexible electronics applications.

Stress-oscillation behaviour of semi-crystalline polymers: the case of poly(butylene succinate).

Stress oscillation has been observed in a number of linear thermoplastic polymers during the cold-drawing process, where the polymers exhibit periodic self-excited oscillatory neck propagation. However, the origin of the mechanical stress oscillation process and its relationship with the crystalline morphology of the polymer are still under debate. In this work, we revisit the stress oscillation behavior by studying a semi-crystalline polyester, poly(butylene succinate) (PBS), a biodegradable polymer suitable for biomedical and packaging applications. Stress oscillation of PBS is observed when deformed at a range of elongation rates from 10 to 200 mm min-1, and the fluctuation magnitude decays as the deformation temperature increases from 23 to 100 °C. Periodic transparent/opaque bands form during necking of PBS, which consists of alternating regions of highly oriented crystalline zones and microcavities due to crazing and voiding, although the degree of crystallinity did not change significantly in the bands. Simultaneous small- and wide-angle X-ray scattering confirms that the alternating stress increases, as shown in the stress-strain curves, correspond to the appearance of the transparent bands in the sample, and the abrupt drop of the stress is the result of voiding during the neck propagation. The voiding and cavitation are ultimately responsible for the stress oscillation process in PBS. The in-depth analysis of this work is important in understanding and controlling the occurrence of instabilities/cavitation during polymer processing such as film blowing, biaxial stretching and injection moulding of biodegradable polymer materials.

2D boron nitride nanosheets (BNNS) prepared by high-pressure homogenisation: structure and morphology.

2D Boron Nitride Nano-sheets (BNNS) were prepared using a high-pressure homogenisation process to exfoliate bulk hexagonal boron nitride (h-BN). The effectiveness of this process was studied by characterising bulk h-BN and BNNS post-processing using numerous techniques. The BNNS produced was composed of a mixture of sheets having lengths on the nanometre (nm) scale, but lateral thicknesses on the micron (µm) length scale. The product was a macro-porous material containing slit-like pores with a surface area of 170 m2 g-1. It had a polycrystalline structure with d002 = 0.335 nm and L002 = 2 nm. From the sharp E2g peak in the Raman spectrum at 1360 cm-1 (FWHM = 12.5 cm-1), the sheets had a low defect density and were highly exfoliated. X-Ray photoelectron spectroscopy (XPS) studies detected B-OH and N-H groups on the BNNS surface and the presence of residual surfactant. Contact angle measurements (60°± 3° (0 s); 40°± 2° (10 s)) confirmed a hydrophilic surface. The BNNS was thermally stable under oxidative conditions up to 323 °C.

Intrinsic Tuning of Poly(styrene-butadiene-styrene)-Based Self-Healing Dielectric Elastomer Actuators with Enhanced Electromechanical Properties.

The electromechanical properties of a thermoplastic styrene-butadiene-styrene (SBS) dielectric elastomer was intrinsically tuned by chemical grafting with polar organic groups. Methyl thioglycolate (MG) reacted with the butadiene block via a one-step thiol-ene "click" reaction under UV at 25 °C. The MG grafting ratio reached 98.5 mol % (with respect to the butadiene alkenes present) within 20 min and increased the relative permittivity to 11.4 at 103 Hz, with a low tan δ. The actuation strain of the MG-grafted SBS dielectric elastomer actuator was 10 times larger than the SBS-based actuator, and the actuation force was 4 times greater than SBS. The MG-grafted SBS demonstrated an ability to achieve both mechanical and electrical self-healing. The electrical breakdown strength recovered to 15% of its original value, and the strength and elongation at break recovered by 25 and 21%, respectively, after 3 days. The self-healing behavior was explained by the introduction of polar MG groups that reduce viscous loss and strain relaxation. The weak CH/π bonds through the partially charged (δ+) groups adjacent to the ester of MG and the δ- center of styrene enable polymer chains to reunite and recover properties. Intrinsic tuning can therefore enhance the electromechanical properties of dielectric elastomers and provides new actuator materials with self-healing mechanical and dielectric properties.

Intrinsically Tuning the Electromechanical Properties of Elastomeric Dielectrics: A Chemistry Perspective.

Dielectric elastomers have the capability to be used as transducers for actuation and energy harvesting applications due to their excellent combination of large strain capability (100-400%), rapid response (10-3  s), high energy density (10-150 kJ m-3 ), low noise, and lightweight nature. However, the dielectric properties of non-polar elastomers such as dielectric permittivity εr , breakdown strength Eb , and dielectric loss ε ″, need to be enhanced for real world applications. The introduction of polar groups or structures into dielectric elastomers through covalently bonding is an attractive approach to 'intrinsically' induce a permanent polarity to the elastomers, and can eliminate the poor post-processing issues and breakdown strength of extrinsically modified materials, which have often been prepared by incorporation of fillers. This review discusses the chemical methods for modification of dielectric elastomers, such as hydrosilylation, thiol-ene click chemistry, azide click chemistry, and atom transfer radical polymerization. The effects of the type and concentration of polar groups on the dielectric and mechanical properties of the elastomers and their performance in actuation and harvesting systems are discussed. State-of-the-art developments and perspectives of modified dielectric elastomers for deformable energy generators and transducers are provided.

Vegetable derived-oil facilitating carbon black migration from waste tire rubbers and its reinforcement effect.

Three dimensional chemically cross-linked polymer networks present a great challenge for recycling and reutilization of waste tire rubber. In this work, the covalently cross-linked networks of ground tire rubber (GTR) were degraded heterogeneously under 150 °C due to the synergistic effects of the soybean oil and controlled oxidation. The degradation mechanism was discussed using Horikx theory and Fourier transformation infrared spectroscopy (FTIR). The results showed that the structural evolution of sol and gel parts, which indicated that the sols consisted of degraded GTR chains with low molecular weight, while the gels were mainly composed of bound rubber coated carbon black, which are separated from the cross-linked network of GTR in a high degradation degree. The degraded GTR compound demonstrated an excellent reinforcing effect on solution styrene-butadiene rubber (SSBR), due to the presence of core-shell structured carbon black. This work provide an efficient and economic approach to degrade GTR and transform it into useful products.

Enhancing cycling durability of Li-ion batteries with hierarchical structured silicon-graphene hybrid anodes.

Hybrid anode materials consisting of micro-sized silicon (Si) particles interconnected with few-layer graphene (FLG) nanoplatelets and sodium-neutralized poly(acrylic acid) as a binder were evaluated for Li-ion batteries. The hybrid film has demonstrated a reversible discharge capacity of ∼1800 mA h g-1 with a capacity retention of 97% after 200 cycles. The superior electrochemical properties of the hybrid anodes are attributed to a durable, hierarchical conductive network formed between Si particles and the multi-scale carbon additives, with enhanced cohesion by the functional polymer binder. Furthermore, improved solid electrolyte interphase (SEI) stability is achieved from the electrolyte additives, due to the formation of a kinetically stable film on the surface of the Si.

Heteroatom Doped-Carbon Nanospheres as Anodes in Lithium Ion Batteries.

Long cycle performance is a crucial requirement in energy storage devices. New formulations and/or improvement of "conventional" materials have been investigated in order to achieve this target. Here we explore the performance of a novel type of carbon nanospheres (CNSs) with three heteroatom co-doped (nitrogen, phosphorous and sulfur) and high specific surface area as anode materials for lithium ion batteries. The CNSs were obtained from carbonization of highly-crosslinked organo (phosphazene) nanospheres (OPZs) of 300 nm diameter. The OPZs were synthesized via a single and facile step of polycondensation reaction between hexachlorocyclotriphosphazene (HCCP) and 4,4'-sulphonyldiphenol (BPS). The X-ray Photoelectron Spectroscopy (XPS) analysis showed a high heteroatom-doping content in the structure of CNSs while the textural evaluation from the N2 sorption isotherms revealed the presence of micro- and mesopores and a high specific surface area of 875 m²/g. The CNSs anode showed remarkable stability and coulombic efficiency in a long charge-discharge cycling up to 1000 cycles at 1C rate, delivering about 130 mA·h·g-1. This study represents a step toward smart engineering of inexpensive materials with practical applications for energy devices.

Exceptional oxygen barrier performance of pullulan nanocomposites with ultra-low loading of graphene oxide.

Polymer nanocomposites are increasingly important in food packaging sectors. Biopolymer pullulan is promising in manufacturing packaging films or coatings due to its excellent optical clarity, mechanical strength, and high water-solubility as compared to other biopolymers. This work aims to enhance its oxygen barrier properties and overcome its intrinsic brittleness by utilizing two-dimensional planar graphene oxide (GO) nanoplatelets. It has been found that the addition of only 0.2 wt% of GO enhanced the tensile strength, Young's modulus, and elongation at break of pullulan films by about 40, 44 and 52%, respectively. The light transmittance at 550 nm of the pullulan/GO films was 92.3% and haze values were within 3.0% threshold, which meets the general requirement for food packaging materials. In particular, the oxygen permeability coefficient of pullulan was reduced from 6337 to 2614 mL µm m(-2) (24 h(-1)) atm(-1) with as low as 0.05 wt% of GO loading and further to 1357 mL µm m(-2) (24 h(-1)) atm(-1) when GO concentration reached 0.3 wt%. The simultaneous improvement of the mechanical and oxygen barrier properties of pullulan was ascribed to the homogeneous distribution and prevalent unidirectional alignment of GO nanosheets, as determined from the characterization and theoretical modelling results. The exceptional oxygen barrier properties of pullulan/GO nanocomposites with enhanced mechanical flexibility and good optical clarity will add new values to high performance food packaging materials.

Efficient oxygen reduction catalysts formed of cobalt phosphide nanoparticle decorated heteroatom-doped mesoporous carbon nanotubes.

Oxygen reduction catalysts based on heteroatom-doped mesoporous carbon nanotubes loaded with Co2P nanoparticles were skilfully fabricated. The electronic interaction between the embedded Co2P nanoparticles and the heteroatom-doped carbon structures could strongly promote the ORR catalytic performance of the heteroatom-doped carbon nanotubes.