Cyclomatrix polyphosphazenes frameworks (Cyclo-POPs) and the related nanomaterials : synthesis, assembly and functionalisation

Poly (organophosphazene) (POP) is one of the most important inorganic polymers along with polysiloxane. The versatile phosphazene chemistry enables a wealth of functional inorganic-organic hybrid polymers with −P = N structures ranging from covalently crosslinked cyclomatrix phosphazene to linear POP copolymers. Cyclomatrix phosphazene framework materials (Cyclo-POPs) represent a novel type of molecular composites, and can be facilely formed via a rapid one-step polycondenzation and simultaneous self-assembly process under ambient conditions, and the stereoscopic morphologies are tuneable from zero-dimension (0D) to 3D depending on the compositions and reaction conditions. The novel cyclo-POPs have shown distinctive advantages over boron-containing covalent organic framework (COFs) materials in terms of the facile and rapid synthesis and integrated functionalities. Moreover, the highly crosslinked −P = N- backbone structures are readily to be transformed into porous carbon nanomaterials with intrinsically doped heteroatoms (P, N, S, O, B, depending on the framework skeletons), which are desirable for catalysis, sensors and energy storage applications. In this article, we critically overview the rational design, synthesis and functionalisation of the cyclo-POPs materials, and their emerging applications in optoelectronics, catalysis and energy storage devices, along with the technical challenges and development perspectives

Structure and dielectric properties of electroactive tetraaniline grafted non-polar elastomers

Intrinsic modification of polybutadiene and block copolymer styrene–butadiene–styrene with the electrically conducting emeraldine salt of tetraaniline (TANI) via a three-step grafting method, is reported in this work. Whilst the TANI oligomer grafted at a similar rate to both polybutadiene and styrene–butadiene–styrene under the same conditions, the resulting elastomers exhibited vastly different properties. 1 mol% TANI-PB exhibited an increased relative permittivity of 5.9, and a high strain at break of 156%, whilst 25 mol% TANI-SBS demonstrated a relative permittivity of 6.2 and a strain at break of 186%. The difference in the behaviour of the two polymers was due to the compatibilisation of TANI by styrene in SBS through π-π stacking, which prevented the formation of a conducting TANI network in SBS at. Without the styrene group, TANI-PB formed a phase separated structure with high levels of TANI grafting. Overall, it was concluded that the polymer chain structure, the morphology of the modified elastomers, and the degree of grafting of TANI, had the greatest effect on the mechanical and dielectric properties of the resultant elastomers. This work paves the way for an alternative approach to the extrinsic incorporation of conducting groups into unsaturated elastomers, and demonstrates dielectric elastomers with enhanced electrical properties for use in actuation devices and energy harvesting applications

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

Functionalization of BaTiO3 nanoparticles with electron insulating and conducting organophosphazene-based hybrid materials

Novel core–shell structured organophosphazene (OPZ) coated BaTiO3 nanoparticles (OPZ@BaTiO3) were produced via a facile and rapid one-step nucleophilic substitution reaction in ambient conditions. The morphology, structure and textural properties of the core–shell nanoparticles were analysed via electron microscopy, spectroscopy, thermogravimetry and porosimetry, and the dielectric properties were evaluated by impedance spectroscopy. The thickness of the cross-linked OPZ shell was readily tailored by varying the weight ratio of the OPZ monomers to BaTiO3, which in turn affected the relative permittivity and the frequency dependence of the OPZ/BaTiO3 particles. A subsequent carbonisation treatment of the OPZ@BaTiO3 at 700 °C transformed the polymeric OPZ shell to a microporous carbonaceous shell, which dramatically increased the electrical conductivity of the particles. Organophosphazene chemistry offers a facile route to functionalise BaTiO3 nanoparticles without any pre-treatment, and generate a range of core–shell BaTiO3 nanoparticles with tailored dielectric and electrically conductive properties that can be used as active fillers for polymer based nanocomposites and energy storage applications. The effectiveness and advantages of OPZ chemistry over other reported methods in forming core–shell particles are demonstrated

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

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

Intrinsic tuning of poly (styrene-butadiene-styrene) (SBS) 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 minutes 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 ten times larger than the SBS-based actuator, and the actuation force was four 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 three days. The self-healing behaviour 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- centre 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

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

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

Structural and electrical properties of CuAlMo thin films prepared by magnetron sputtering

The structural and electrical properties of a low resistivity CuAlMo thin film resistor material were investigated. The thin films were grown on Al2O3 and glass substrates by direct current (dc) magnetron sputtering. The key electrical properties of sheet resistance, temperature coefficient of resistance (TCR) and resistance stability were investigated as a function of sputtering pressure and post-deposition heat treatment time and temperature. A low sputtering pressure range of 0.13 to 0.40 Pa produced CuAlMo films with sheet resistance in the range 0.1 to 0.2 Ω/□ and resistance stability of 0.45 to 0.65% with a TCR of − 90 ppm/°C which could be shifted to zero following annealing in air at 425 °C. Films grown at higher sputtering pressures of 0.53 to 0.80 Pa had increased sheet resistance in the range 0.4 to 0.6 Ω/□ and inferior stability of 0.8 to 1.7% with a more negative TCR of − 110 to − 180 ppm/°C which could not be shifted to zero following annealing. The stability of the films grown at 0.13 and 0.40 Pa could be further improved to < 0.25% with heat treatment, due to the formation of a protective aluminium oxide layer. A minimum dwell time of 3 h at 425 °C was required to stabilise the films and set the electrical properties