A new way to nanostructure hydrogels : electrospun thermo-responsive islands-in-the-sea nanofibres

Islands-in-the-sea nanofibres are a very interesting system: one polymer (islands) is distributed in fibrillar domains within a second polymer (sea). This fibre geometry is often used in microfiber technologies to obtain very fine fibers, by removing the “sea” polymer. This geometry also allows to combine two polymers with very different properties. In this work this geometry is introduced applied to electrospun hydrogel nanofibers, in a novel fashion, and as a way to improve and stabilize the hydrogel nanofibers. Thermo-responsive islands-in-the-sea nanofibers are here produced by electrospinning solutions of a hydrogel-forming thermo-responsive polymer (crosslinked poly(N-isopropylacrylamide), PNIPAM) and a reinforcing polymer (polyetherketone cardo, PEK-c). The two polymers are thermodynamically incompatible in solution and phase separation takes place, which allows the instant formation of islands-in-the-sea nanofibers upon electrospinning. PNIPAM was then crosslinked post-spinning using an oligomeric silsesquioxane. The formed nanocomposite nanofibers showed intrinsic nanostructure, where the fibril-like PNIPAM domains are intimately adjacent to the strong PEK-c domains. Upon contacting with water, the hydrogel domains became instantly highly swollen, while the PEK-c domains did not. As a result, very wrinkly, swollen fibers were obtained, with increased capillary action, as demonstrated through confocal microscopy. The composite nanofibers in water showed excellent swelling ratios and very fast responses to temperature variations (of the order of 1 second) with morphological and optical effects: variations in fiber-diameter were accompanied by optical transitions: transparent-opaque. The produced hydrogel nanofibers also presented improved mechanical properties (even with small amounts of PEK-c), when compared to their crosslinked-PNIPAM-only nanofibers. It will be also shown how these materials can be used as optical actuators and smart hydrogel platforms with tuneable contact angle and morphology. In brief, this work aims to demonstrate a new platform technology which can be applied to several hydrogel systems, to achieve hydrogel-based composites with new and improved properties, while retaining (and improving) the main properties of the hydrogel. Here this was demonstrated by showing that the composite materials showed thermo-responsiveness, and enhanced transition kinetics.

Toughening epoxy thermosets and their carbon fibre reinforced composites with electrospun nanofibres

Electrospun nanofibres have emerged as important fibrous materials for diverse applications. They have been shown excellent toughening results when they are applied as interlayer materials between carbon/epoxy laminas in the structural carbon fibre reinforced epoxy matrix composites. They also exhibit synergistic modification effects when they are combined with carbon nanofibres in the thermosetting polymer matrix. In this study, electrospun polyetherketone cardo (PEK-C) nanofibres were used in two ways: directly electrospun onto the surface of carbon fabric [1], and blended with epoxy resin in the form of PEK-C/VGCNF (vapour grown carbon nanofibre) composite nanofibres[2].The interlaminar fracture toughness, flexural properties and thermal mechanical properties of the modified systems were investigated.

Electrospun nanofibres

This book deals with an emerging nanofibre-making technology, electrospinning, the functionalities of electrospun nanofibres and their wound healing application. An important fundamental issue, fibre morphological evolution during electrospinning, is clarified. Effective techniques to improve the fibre toughness and control the surface wettability of nanofibre membrane have been developed. These functional nanofibre membranes have been used as dressing materials for healing skin wounds, and shown promising results. This work makes electrospun nanofibre membrane an ideal candidate for wound healing application.

Electrospinning of nanofibres with parallel line surface texture for improvement of nerve cell growth

Nanofibres having a parallel line surface texture were electrospun from cellulose acetate butyrate solutions using a solvent mixture of acetone and N,N'-dimethylacetamide. The formation mechanism of the unusual surface feature was explored and attributed to the formation of voids on the jet surface at the early stage of electrospinning and subsequent elongation and solidification of the voids into a line surface structure. The fast evaporation of a highly volatile solvent, acetone, from the polymer solution was found to play a key role in the formation of surface voids, while the high viscosity of the residual solution after the solvent evaporation ensured the line surface to be maintained after the solidification. Based on this principle, nanofibres having a similar surface texture were also electrospun successfully from other polymers, such as cellulose acetate, polyvinylidene fluoride, poly(methyl methacrylate), polystyrene and poly(vinylidene fluoride-co-hexafluoropropene), either from the same or from different solvent systems. Polarized Fourier transform infrared spectroscopy was used to measure the polymer molecular orientation within nanofibres. Schwann cells were grown on both aligned and randomly oriented nanofibre mats. The parallel line surface texture assisted in the growth of Schwann cells especially at the early stage of cell culture regardless of the fibre orientation. In contrast, the molecular orientation within nanofibres showed little impact on the cell growth.

Actuating individual electrospun hydrogel nanofibres

The actuation of a single hydrogel nanofibre is measured for the first time by AFM. The actuation stress generated was comparable to that produced by skeletal muscle and the actuation rate was significantly increased by the nanoscale dimensions of the fibre.

Crosslinking neat ultrathin films and nanofibres of pH-responsive poly(acrylic acid) by UV radiation

Electrospun polyelectrolyte hydrogel nanofibres are being developed for many applications including artificial muscles, scaffolds for tissue engineering, wound dressings and controlled drug release. For electrospun polyelectrolytes, a post-spinning crosslinking process is necessary for producing a hydrogel. Typically, radiation or thermal crosslinking routines are employed that require multifunctional crosslinking molecules and crosslink reaction initiators (free radical producers). Here, ultraviolet subtype-C (UVC) radiation was employed to crosslink neat poly(acrylic acid) (PAA) nanofibres and films to different crosslink densities. Specific crosslink initiators or crosslinking molecules are not necessary in this fast and simple process providing an advantage for biological applications. Scanning probe microscopy was used for the first time to measure the dry and wet dimensions of hydrogel nanofibres. The diameters of the swollen fibres decrease monotonically with increasing UVC radiation time. The fibres could be reversibly swollen/contracted by treatment with solutions of varying pH, demonstrating their potential as artificial muscles. The surprising success of UVC radiation exposure to achieve chemical crosslinks without a specific initiator molecule exploits the ultrathin dimensions of the PAA samples and will not work with relatively thick samples.

Fabrication and characterisation of carbon nanofibres from cellulose nanofibres

Carbon nanofibers were fabricated by pyrolysis of plant-based cellulose nanofibers. The findings demonstrate the possibility of obtaining strong and commercially competitive carbon nanofibers that are used in many industries including aerospace, automobile and electronics.

Thermo-responsive PNIPAM nanofibres crosslinked by OpePOSS

Stable and re-usable thermo-responsive hydrogel nanofibres were roduced by electrospinning poly(Nisopropylacrylamide) (PNIPAM) in presence of a polyhedral oligomeric silsesquioxane (POSS) possessing eight epoxide groups, and of a 2-ethyl-4-methylimidazole (EMI) as a catalyst, followed by a heat curing treatment. The roles of the organic-base catalyst in the formation of crosslinked polymer network, fibre morphologies, and hydrogel properties were examined in this paper.

Improving the toughness and electrical conductivity of epoxy nanocomposites by using aligned carbon nanofibres

There is an increasing demand for high performance composites with enhanced mechanical and electrical properties. Carbon nanofibres offer a promising solution but their effectiveness has been limited by difficulty in achieving directional alignment. Here we report the use of an alternating current (AC) electric field to align carbon nanofibres in an epoxy. During the cure process of an epoxy resin, carbon nanofibres (CNFs) are observed to rotate and align with the applied electric field, forming a chain-like structure. The fracture energies of the resultant epoxy nanocomposites containing different concentrations of CNFs (up to 1.6wt%) are measured using double cantilever beam specimens. The results show that the addition of 1.6wt% of aligned CNFs increases the electrical conductivity of such nanocomposites by about seven orders of magnitudes to 10^-2S/m and increases the fracture energy, G<inf>Ic</inf>, by about 1600% from 134 to 2345J/m². A modelling technique is presented to quantify this major increase in the fracture energy with aligned CNFs. The results of this research open up new opportunities to create multi-scale composites with greatly enhanced multifunctional properties.