Électrofilage de complexes de polymères

Ce travail a permis de démontrer que l’électrofilage, ainsi que l’électronébulisation, sont des méthodes faciles et efficaces de préparation de complexes entre des polymères et des petites molécules. En effet, la plupart des méthodes de préparation de complexes donnent des mélanges inhomogènes à cause de la cristallisation cinétiquement favorisée des petites molécules. Or, un mélange inhomogène peut être très difficile à caractériser. Dans ce travail, l’électrofilage a été utilisé pour la première fois avec succès pour obtenir des nanofils de complexe entre le poly(oxyde d’éthylène) (PEO) et le NaSCN (PEO-NaSCN) ainsi qu’entre le PEO et l’hydroquinone. L’électronébulisation a été utilisée pour obtenir du complexe entre la polycaprolactone (PCL) et l’urée. L’électrofilage n’était pas possible pour le système PCL-urée parce que la solubilité n’était pas suffisante pour atteindre la viscosité minimale requise pour l’électrofilage. L’électronébulisation peut donc complémenter l’électrofilage et rendre la technique applicable à encore plus de systèmes. Les systèmes ont été caractérisés par spectroscopie infrarouge (FT-IR), par diffraction de rayons X (XRD), par calorimétrie différentielle à balayage (DSC) et par microscopies optique et électronique à balayage.

Electrospinning and characterization of supramolecular poly(4-vinyl pyridine)-small molecule complexes

La chimie supramoléculaire est basée sur l'assemblage non covalent de blocs simples, des petites molécules aux polymères, pour synthétiser des matériaux fonctionnels ou complexes. La poly(4-vinylpyridine) (P4VP) est l'une des composantes supramoléculaires les plus utilisées en raison de sa chaîne latérale composée d’une pyridine pouvant interagir avec de nombreuses espèces, telles que les petites molécules monofonctionnelles et bifonctionnelles, grâce à divers types d'interactions. Dans cette thèse, des assemblages supramoléculaires de P4VP interagissant par liaisons hydrogène avec de petites molécules sont étudiés, en ayant comme objectifs de faciliter l'électrofilage de polymères et de mieux comprendre et d'optimiser la photoréponse des matériaux contenant des dérivés d'azobenzène. Une nouvelle approche est proposée afin d'élargir l'applicabilité de l'électrofilage, une technique courante pour produire des nanofibres. À cet effet, un complexe entre la P4VP et un agent de réticulation bifonctionnel capable de former deux liaisons hydrogène, le 4,4'-biphénol (BiOH), a été préparé pour faciliter le processus d’électrofilage des solutions de P4VP. Pour mieux comprendre ce complexe, une nouvelle méthode de spectroscopie infrarouge (IR) a d'abord été développée pour quantifier l'étendue de la complexation. Elle permet de déterminer un paramètre clé, le rapport du coefficient d'absorption d'une paire de bandes attribuées aux groupements pyridines libres et liées par liaisons hydrogène, en utilisant la 4-éthylpyridine comme composé modèle à l’état liquide. Cette méthode a été appliquée à de nombreux complexes de P4VP impliquant des liaisons hydrogène et devrait être généralement applicable à d'autres complexes polymères. La microscopie électronique à balayage (SEM) a révélé l'effet significatif du BiOH sur la facilité du processus d’électrofilage de P4VP de masses molaires élevées et faibles. La concentration minimale pour former des fibres présentant des perles diminue dans le N, N'-diméthylformamide (DMF) et diminue encore plus lorsque le nitrométhane, un mauvais solvant pour la P4VP et un non-solvant pour le BiOH, est ajouté pour diminuer l'effet de rupture des liaisons hydrogène causé par le DMF. Les liaisons hydrogène dans les solutions et les fibres de P4VP-BiOH ont été quantifiées par spectroscopie IR et les résultats de rhéologie ont démontré la capacité de points de réticulation effectifs, analogues aux enchevêtrements physiques, à augmenter la viscoélasticité de solutions de P4VP pour mieux résister à la formation de gouttelettes. Cette réticulation effective fonctionne en raison d'interactions entre le BiOH bifonctionnel et deux chaînes de P4VP, et entre les groupements hydroxyles du BiOH complexé de manière monofonctionnelle. Des études sur d’autres agents de réticulation de faible masse molaire ont montré que la plus forte réticulation effective est introduite par des groupes d’acide carboxylique et des ions de zinc (II) qui facilitent le processus d’électrofilage par rapport aux groupements hydroxyles du BiOH. De plus, la sublimation est efficace pour éliminer le BiOH contenu dans les fibres sans affecter leur morphologie, fournissant ainsi une méthode élégante pour préparer des fibres de polymères purs dont le processus d’électrofilage est habituellement difficile. Deux complexes entre la P4VP et des azobenzènes photoactifs portant le même groupement tête hydroxyle et différents groupes queue, soit cyano (ACN) ou hydrogène (AH), ont été étudiés par spectroscopie infrarouge d’absorbance structurale par modulation de la polarisation (PM-IRSAS) pour évaluer l'impact des groupements queue sur leur performance lors de l'irradiation avec de la lumière polarisée linéairement. Nous avons constaté que ACN mène à la photo-orientation des chaînes latérales de la P4VP et des azobenzènes, tandis que AH mène seulement à une orientation plus faible des chromophores. La photo-orientation des azobenzènes diminue pour les complexes avec une teneur croissante en chromophore, mais l'orientation de la P4VP augmente. D'autre part, l'orientation résiduelle après la relaxation thermique augmente avec la teneur en ACN, à la fois pour le ACN et la P4VP, mais la tendance opposée est constatée pour AH. Ces différences suggèrent que le moment dipolaire a un impact sur la diffusion rotationnelle des chromophores. Ces résultats contribueront à orienter la conception de matériaux polymères contenant des azobenzène efficaces.

The charge effect of cationic surfactants on the elimination of fibre beads in the electrospinning of polystyrene

Polystyrene nanofibres were electrospun with the inclusion of cationic surfactants, dodecyltrimethylammonium bromide (DTAB) or tetrabutylammonium chloride (TBAC), in the polymer solution. A small amount of cationic surfactant effectively stopped the formation of beaded fibres during the electrospinning. The cationic surfactants were also found to improve the solution conductivity, but had no effect on the viscosity. Only DTAB had an effect on the surface tension of the polymer solution, the surface tension decreasing slightly with an increase in the concentration of DTAB.

The formation of beaded fibres was attributed to an insufficient stretch of the filaments during the whipping of the jet, due to a low charge density. Adding the cationic surfactants improved the net charge density that enhanced the whipping instability. The jet was stretched under stronger charge repulsion and at a higher speed, resulting in an exhaustion of the bead structure. In addition, a polymer/surfactant interaction was found in the polystyrene–DTAB solution system, while this interaction was not found in the polystyrene–TBAC system. The polymer/surfactant interaction led to the formation of thinner fibres than those formed in the absence of the interaction.

The effects of a non-ionic surfactant, Triton X-405, on the electrospun fibres were also studied. The addition of Triton X-405 did not eliminate the fibre beads, but reduced the bead numbers and changed the morphology. Triton X-405 slightly improved the solution conductivity, and had a minor effect on the surface tension, but no effect on the viscosity.

Using chitosan as a thickener for electrospinning dilute PVA solutions to improve fibre uniformity

Chitosan was added to PVA aqueous solutions as a thickener to improve the electrospinning process. The presence of a small amount of chitosan considerably improved the uniformity of as-spun nanofibres. This improvement is attributed to its significant effect on the solution viscosity and conductivity, with only a slight impact on the surface tension. The concentration of the PVA required to produce bead-free and uniform nanofibres was reduced with the increase in chitosan concentration. The chitosan thickener suppressed the jet break-up and facilitated the jet stretching so that fine and uniform fibres could be electrospun even from a dilute PVA solution.

Toughened electrospun nanofibers from crosslinked elastomer-thermoplastic blends

A crosslink-able elastomeric polyester urethane (PEU) was blended with a thermoplastic, polyacrylonitrile (PAN), and electrospun into nanofibres. The effects of the PEU/PAN ratio and the crosslinking reaction on the morphology and the tensile properties of the as-spun fibre mats were investigated. With the same overall polymer concentration (9 wt %), the nanofibre containing higher composition of PEU shows a slight decrease in the average fibre diameter, but the tensile strength, the elongation at break and tensile modulus of the nanofibre mats are all improved. These tensile properties are further enhanced by slight crosslinking of the PEU component within the nanofibres.

Polypyrrole-coated electrospun nanofibre membranes for recovery of Au(III) from aqueous solution

In this paper, for the first time, polypyrrole-coated electrospun nanofibre mats have been used as separation membranes to electrolessly recover Au from aqueous [Au(III)Cl₄]− solutions, based on a continuous-flow membrane separation process. With a [Au(III)Cl₄]− solution passing through the nanofibre membrane, the Au(III) ions were converted into elemental Au. The gold recovered was deposited on the nanofibre membranes in the form of Au particles, as confirmed by EDX and XPS measurements. It has been found that the polypyrrole-coated electrospun nanofibres are good candidate membrane material for the recovery of Au, and the recovery efficiency is affected by the membrane thickness, the permeate flux rate and the initial [Au(III)Cl₄]− concentration.

Preparation of nanofibre yarns from electrospun nonwoven strips

From ancient to modern time, humans have been trying to use finer fibres to make fibrous products for various purposes and believing that finer fibres have better aesthetic qualities. So far, the commercial fibres have been reduced to microns in diameter, but it seems difficult to further reduce the fibre fineness to submicrons using conventional fibre-making techniques.
Electrospinning is a promising technique to produce continuous fibres with diameters on nanometre scales. This technique involves stretching a polymer fluid under a strong electric field into fine filaments, which are deposited randomly on the electrode collector forming a nonwoven nanofibre mat in most cases. Despite considerable efforts in exploring the applications of electrospun nanofibres in non-fibrous fields [1], very limited work has been conducted on using this material to process mechanically robust nanofibre yarns [2,3].

Nano related research in fibres and textiles

With the increasing hype surrounding what nanotechnology can actually deliver, research emphasis in this area needs to be placed on how nanotechnology can bring tangible benefits to existing industries and ordinary consumers. This paper gives selected examples of real world applications of nano-structured materials, including nano fibrous and particulate materials. It reviews recent research into nano-structured surface coating of textile substrates for enhanced functionalities, and the development of fine and uniform nanofibres for advanced applications. Emphasis has been placed on relevant research activities in the Centre for Material and Fibre Innovation at Deakin University, Australia. In the nano-structured surface coating area, several examples of enhancing fabric performance and functionality are provided, including silica coating for photochromic textiles, superhydrophobic surface coating and transparent ZnO coating to reduce colour fading of textiles exposed to UV radiation. In the nanofibre area, these activities include: elimination of beaded fibres without increasing the average diameter of the electrospun nanofibres, electrospinning of side-by-side bi-component nanofibres, new insight into the evolution of fibre morphology in electrospinning and the electrospinning technology itself.

ELECTROSTATIC SPINNING ASSEMBLY

A spinneret for producing nanofibres from a viscous liquid using electrostatic spinning in an electric field is described. The spinneret includes one or more narrow annular bodies radially centred about and axially spaced along a central axis. The annular bodies may be discs, rings, or coils.

Needleless electrospinning of nanofibrous structures

In this study, different wire coils have been used as electrodes for needless electrospinning. Very thin and uniform nanofibres have been produced, and the fibre productivity is much higher than existing electrospinning systems.

Properties of a carbon-fibre composite modified by electrospun poly (vinylidene fluoride)

The interlaminar toughening of a carbon-fibre reinforced composite by incorporation of electrospun polyvinylidene fluoride (PVDF) nanofibrous membranes was explored in this work. The nanofibres were electrospun directly onto commercial pre-impregnated carbon fibre materials under optimised conditions and PVDF was found to primarily crystallise in its β phase polymorphic form. There is strong evidence from DMTA analysis to suggest that a partial miscibility between the amorphous phases of the PVDF nanofibres and the epoxy exists. The improved plastic deformation at the crack tip after inclusion of the nanofibres was directly translated to a 57% increase in the mode II interlaminar fracture toughness (in-plane shear failure). Conversely, the fracture toughness in mode I (opening failure) was slightly lower than the reference by approximately 20%, and the results were interpreted from the complex micromechanisms of failure arising from the changes in polymorphism of the PVDF.

Electrostatic spinning assembly

A spinneret for producing nanofibres from a viscous liquid using electrostatic spinning in an electric field is described. The spinneret includes one or more narrow annular bodies radially centred about and axially spaced along a central axis. The annular bodies may be discs, rings, or coils.

Electrostatic spinning assembly

A spinneret for producing nanofibres from a viscous liquid using electrostatic spinning in an electric field is described. The spinneret includes one or more narrow annular bodies radially centred about and axially spaced along a central axis. The annular bodies may be discs, rings, or coils.

Production and characterisation of nanofibre yarns and composites

This thesis propsed a novel method to produce and characterise nanofibre yarns and composites.  It contributed to the fundamental research in the field of nanofibre yarns.

Needleless electrospinning : influences of fibre generator geometry

The fibre generator shape and dimension are key factors affecting the needleless electrospinning process and fibre fineness. In this work, cylinder with rounded rim, disc and ball were used as spinnerets to electrospin polyvinyl alcohol and polyacrylonitrile solutions. A finite element method was used to analyse how the spinneret geometry affected the electric field generated during electrospinning and the associated changes in fibre diameter and productivity. For cylinder spinnerets, increasing the rim radius reduced the discrepancy of electric field intensity between the cylinder end and middle area, which affected the fibre productivity. The electrospinning failed to operate when the rim radius was over 20 mm. With decreasing cylinder diameter, the electric field intensity in the middle area increased, improving the fibre productivity. Thinner disc spinnerets increased the electric field intensity, resulting in finer nanofibres and higher productivities. Ball spinnerets produced evenly distributed electric field, but failed to electrospin fibres when the diameters were below 60 mm. It has been found that strong and narrowly distributed electric field in the fibre-generating area can significantly facilitate the mass production of quality nanofibres.