Novel Hybrid Materials And Their Applications
Authors:   , Small Aaron Charles 
Published: November 2021

<p>The development of novel hybrid materials of cellulose fibres and substrates with nanoparticles, conducting polymers and quantum dots, opens up novel application for new packaging materials and paper based products for the ‘smart packaging’ and ‘functional products’ areas that are emerging in the paper and packaging industries. Examples of these materials which have been developed here include cellulose fibres and substrates functionalised with magnetic nanoparticles, electrically conducting polypyrrole, and photoluminescent zinc sulfide quantum dots.  Such materials were synthesised and then characterised using Alternating Gradient Magnetometry (AGM), Atomic Absorption Spectroscopy (AA), Cotec Profilometer Measurements, DC Conductivity Measurements, Photoluminescence Spectroscopy (PL), Scanning Electron Microscopy (SEM), SQUID Magnetometry, Transmission Electron Microscopy (TEM), Vibrational Sample Magnetometry (VSM), X-ray Diffraction (XRD), X-ray Fluorescence (XRF) and X-ray Photoelectron Spectroscopy (XPS). Ferrimagnetic magnetite nanoparticles (particle size 12-26 nm) were synthesised by a simple aqueous precipitation method and had a magnetic saturation of approximately 60 emu g⁻¹, a coercive field of approximately 12-120 Oe, and a remnant magnetisation of approximately 11 emu g⁻¹. Magnetite coated Kraft fibres (1.2 – 3.15 wt. % Fe) were synthesised by adding a colloidal suspension of magnetite nanoparticles to a suspension of Kraft fibres. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the magnetic properties of the magnetic nanoparticles. The nanoparticles remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the oxygen present in the magnetite. Newsprint, Kraft Board and Cotton fabric were coated with polypyrrole using a chemical polymerisation method. SEM shows a complete coating, whereby the fibres are completely encapsulated by the polymer, including individual fibrils. Again, bonding is facilitated through hydrogen bonding between the surface hydroxyl groups of the cellulose and the lone pairs of the nitrogen in the polypyrrole backbone. Samples were doped with p-toluenesulfonic acid to increase conductivity, of which up to 4 S cm⁻¹ was achieved. The samples were coated with magnetite nanoparticles using a starch binder, and tested for their application in EMI shielding. A maximum shielding effectiveness of 43 % in the 1-18 GHz range and 47 % in the 16-40 GHz range was obtained using cotton fabrics coated with both polypyrrole and magnetite. A synergistic effect is observed on using a polypyrrole and magnetite coating. Photoluminescent ZnS quantum dots, synthesised using an aqueous precipitation method, were doped with Mn²⁺ and Cu²⁺ to achieve emissions at approximately 600 nm (Mn²⁺) and 530 nm (Cu²⁺) on irradiation with UV light. The quantum dots had a particle size of approximately 2 nm, and were present in the zinc blende phase. Doped ZnS-coated Kraft fibres (5 – 30 wt. % Zn) were synthesised by a number of methods, the most successful being the ‘in-situ’ method, in which a uniform and complete coating was afforded. The fibres retained their inherent properties, such as tensile strength and flexibility, but inherited the photoluminescent properties of the ZnS quantum dots. The quantum dots remained unchanged on bonding - presumably through hydrogen bonding between the surface hydroxyl groups of the cellulose and the sulfur present in the ZnS quantum dots. ZnS quantum dots doped with Mn² and Cu²⁺ were successfully formulated for inkjet printing by capping with mercaptosuccinic acid. Upon irradiation with UV light, emissions at approximately 600 nm (Mn²⁺-doped) and 530 nm (Cu²⁺-doped) were observed. These were successfully inkjet printed in intricate patterns onto a number of substrates, including photographic quality inkjet paper, cotton, and wool.</p>