Highly Ordered Thermoplastic Polyurethane/Aramid Nanofiber Conductive Foams Modulated by Kevlar Polyanion for Piezoresistive Sensing and Electromagnetic Interference Shielding.

Highly ordered and uniformly porous structure of conductive foams is a vital issue for various functional purposes such as piezoresistive sensing and electromagnetic interference (EMI) shielding. With the aids of Kevlar polyanionic chains, thermoplastic polyurethane (TPU) foams reinforced by aramid nanofibers (ANF) with adjustable pore-size distribution were successfully obtained via a non-solvent-induced phase separation. In this regard, the most outstanding result is the in situ formation of ANF in TPU foams after protonation of Kevlar polyanion during the NIPS process. Furthermore, in situ growth of copper nanoparticles (Cu NPs) on TPU/ANF foams was performed according to the electroless deposition by using the tiny amount of pre-blended Ti3C2Tx MXene as reducing agents. Particularly, the existence of Cu NPs layers significantly promoted the storage modulus in 2,932% increments, and the well-designed TPU/ANF/Ti3C2Tx MXene (PAM-Cu) composite foams showed distinguished compressive cycle stability. Taking virtues of the highly ordered and elastic porous architectures, the PAM-Cu foams were utilized as piezoresistive sensor exhibiting board compressive interval of 0-344.5 kPa (50% strain) with good sensitivity at 0.46 kPa-1. Meanwhile, the PAM-Cu foams displayed remarkable EMI shielding effectiveness at 79.09 dB in X band. This work provides an ideal strategy to fabricate highly ordered TPU foams with outstanding elastic recovery and excellent EMI shielding performance, which can be used as a promising candidate in integration of satisfactory piezoresistive sensor and EMI shielding applications for human-machine interfaces.

Highly thermally conductive Ti3C2Tx/h-BN hybrid films via coulombic assembly for electromagnetic interference shielding.

With the development of electronic equipment, heat problem and electromagnetic pollution severely affect both their functions and human health, which leads to great interests in developing materials synchronously with outstanding thermal conductivity and electromagnetic interference (EMI) shielding performance. Here, ultrathin Ti3C2Tx/h-BN two-dimensional (2D) heterostructure films were prepared via coulombic assembly between Ti3C2Tx MXene and h-BN nanosheet through ultrasonic blending. After the addition of h-BN nanosheet as thermal conductive nanofillers, the hybrid films achieved a higher value of thermal conductivity, compared to Ti3C2Tx composite film without h-BN. The higher thermal conductivity offered by h-BN enables the Ti3C2Tx/h-BN films have good potential for EMI shielding applications on wearable and portable electronic devices. When the mass ratio of Ti3C2Tx/h-BN is 7:3, the hybrid film with the thickness of 47.60 µm exhibited electrical conductivity of 57.67 S/cm and the maximum EMI shielding effectiveness of 37.29 dB.

Doubly crosslinked microgel-colloidosomes: a versatile method for pH-responsive capsule assembly using microgels as macro-crosslinkers.

A new family of pH-responsive microgel-colloidosomes was prepared using microgel particles as the building blocks and macro-crosslinker. Our simple and versatile method used covalent inter-linking of vinyl-functionalised microgel particles adsorbed to oil droplets to form shells of doubly crosslinked microgels (DX MGs) and was demonstrated using two different microgel types.

Effects of crosslinker on the morphology and properties of microgels containing N-vinylformamide, glycidylmethacrylate and vinylamine.

Microgels are swollen crosslinked polymer colloid particles. We used non-aqueous dispersion polymerisation to prepare new water-swellable microgels containing N-vinylformamide (NVF), glycidylmethacrylate (GMA) and an alkali-stable crosslinker, 2-(N-vinylformamido)ethyl ether (NVE). The microgel particles had a core that was rich in NVF. The shell contained GMA and NVF. In order to expose the amine functionality, alkaline hydrolysis was used, transforming the NVF groups in the shell to vinylamine (VAM) while leaving most NVF in the core untouched. The hydrolysed microgels (H-NVF-GMA-NVE) were cationic at low pH and were shown to have polyampholyte behaviour. Inclusion of NVE had the beneficial effects of preventing microphase separation at the microgel surface and stabilising the polyampholyte structure against excessive fragmentation during hydrolysis. These new water-swellable core-shell microgels were prepared using scalable methods and may enable future preparation of functionalised core-shell microgels and composites.

Doubly crosslinked poly(vinyl amine) microgels: hydrogels of covalently inter-linked cationic microgel particles.

Doubly crosslinked (DX) microgels are macroscopic hydrogels comprised of covalently inter-linked singly crosslinked (colloidal) microgel particles. In this study we demonstrate for the first time that DX microgels can be prepared from concentrated dispersions of singly crosslinked (SX) poly(vinyl amine) (PVAM) microgel particles. The latter were of micrometer size, cationic and contained high primary amine contents. The DX PVAM morphologies contained extensive inter-connected porosity as determined by optical microscopy and SEM. The effective porosity ranged from 76 to 93 vol% and was tuneable through microgel particle concentration. The mechanical properties of the DX PVAM microgels were investigated using dynamic rheology. The best DX PVAM microgel had a storage modulus (G') of 41 kPa and yield strain of 46%, which are a good combination of elasticity and ductility. This gel had an internal porosity of 76 vol%. The dependence of G' on the effective volume fraction (ϕeff) for the DX PVAM microgels was tuneable and followed the equation: G'∼ exp(bϕeff), with b = 16.4. The latter value indicated low particle softness. The DX PVAM gels were also injectable and could be prepared at 37 °C. Furthermore, the gel mechanical properties after swelling for 3 days at physiological pH and ionic strength were similar to those before swelling. Because these injectable DX PVAM microgels have high primary amine contents they are well suited to functionalisation and should have potential applications in areas including catalysis, composite hydrogels and biomaterials.

Hollow colloidosomes prepared using accelerated solvent evaporation.

We demonstrate a new, scalable, simple, and generally applicable two-step method to prepare hollow colloidosomes. First, a high volume fraction oil-in-water emulsion was prepared. The oil phase consisted of CH2Cl2 containing a hydrophobic structural polymer, such as polycaprolactone (PCL) or polystyrene (PS), which was fed into the water phase. The water phase contained poly(vinylalcohol), poly(N-isopropylacrylamide), or a range of cationic graft copolymer surfactants. The emulsion was rotary evaporated to rapidly remove CH2Cl2. This caused precipitation of PCL or PS particles which became kinetically trapped at the periphery of the droplets and formed the shell of the hollow colloidosomes. Interestingly, the PCL colloidosomes were birefringent. The colloidosome yield increased and the polydispersity decreased when the preparation scale was increased. One example colloidosome system consisted of hollow PCL colloidosomes stabilized by PVA. This system should have potential biomaterial applications due to the known biocompatibility of PCL and PVA.

One-step preparation of uniform cane-ball shaped water-swellable microgels containing poly(N-vinyl formamide).

In this study we report the preparation of a new family of core-shell microgels that are water-swellable and have a morphology that is controllable by particle composition. Here, nearly monodisperse core-shell PNVF-xGMA [poly(N-vinylformamide-co-glycidyl methacrylate)] particles (where x is the weight fraction of GMA used) were prepared via nonaqueous dispersion (NAD) polymerization in one step. The shells were PGMA-rich and were cross-linked by reaction of epoxide groups (from GMA) with amide groups (from NVF). The core of the particles was PNVF-rich. A bifunctional cross-linking monomer was not required to prepare these new microgels. The particles had a remarkable "cane-ball"-like morphology with interconnected ridges, and this could be controlled by the value for x. The particle size was tunable over the range 0.8-1.8 µm. Alkaline hydrolysis was used to hydrolyze the PNVF segments to poly(vinylamine), PVAM. The high swelling pressure of the cationic cores caused shell fragmentation and release of some of the core polymer when the hydrolyzed particles were dispersed in pure water. The extent to which this occurred was controllable by x. Remarkably, the PGMA-rich shells could be detached from the hydrolyzed particles by dispersion in water followed by drying. The hydrolyzed PNVF-0.4GMA particles contained both positively and negatively charged regions and the dispersions appeared to exhibit charge-patch aggregation at low ionic strengths. The new cross-linking strategy used here to prepare the PNVF-xGMA particles should be generally applicable for amide-containing monomers and may enable the preparation of a range of new water-swellable microgels.