Richard L. Andersson

Cellulose nanofibers decorated with magnetic nanoparticles – synthesis, structure and use in magnetized high toughness membranes for a prototype loudspeaker

Magnetic nanoparticles are the functional component for magnetic membranes, but they are difficult to disperse and process into tough membranes. Here, cellulose nanofibers are decorated with magnetic ferrite nanoparticles formed in situ which ensures a uniform particle distribution, thereby avoiding the traditional mixing stage with the potential risk of particle agglomeration. The attachment of the particles to the nanofibrils is achieved via aqueous in situ hydrolysis of metal precursors onto the fibrils at temperatures below 100 °C. Metal adsorption and precursor quantification were carried out using Induction Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). FE-SEM was used for high resolution characterization of the decorated nanofibers and hybrid membranes, and TEM was used for nanoparticle size distribution studies. The decorated nanofibers form a hydrocolloid. Large (200 mm diameter) hybrid cellulose/ferrite membranes were prepared by simple filtration and drying of the colloidal suspension. The low-density, flexible and permanently magnetized membranes contain as much as 60 wt% uniformly dispersed nanoparticles (thermogravimetric analysis data). Hysteresis magnetization was measured by a Vibrating Sample Magnetometer; the inorganic phase was characterized by XRD. Membrane mechanical properties were measured in uniaxial tension. An ultrathin prototype loudspeaker was made and its acoustic performance in terms of output sound pressure was characterized. A full spectrum of audible frequencies was resolved.

Electrospinning of recycled PET to generate tough mesomorphic fibre membranes for smoke filtration

Tough fibrous membranes for smoke filtration have been developed from recycled polyethylene terephthalate (PET) bottles by solution electrospinning. The fibre thicknesses were controlled from 0.4 to 4.3 μm by adjustment of the spinning conditions. The highest fibre strength and toughness were obtained for fibres with an average diameter of 1.0 μm, 62.5 MPa and 65.8 MJ m−3, respectively. The X-ray diffraction (XRD) patterns of the fibres showed a skewed amorphous halo, whereas the differential scanning calorimetry (DSC) results revealed an apparent crystallinity of 6–8% for the 0.4 and 1 μm fibres and 0.2% crystallinity for the 4.3 μm fibres. Heat shrinkage experiments were conducted by exposing the fibres to a temperature above their glass transition temperature (Tg). The test revealed a remarkable capability of the thinnest fibres to shrink by 50%, which was in contrast to the 4.3 μm fibres, which displayed only 4% shrinkage. These thinner fibres also showed a significantly higher glass transition temperature (+15 °C) than that of the 4.3 μm fibres. The results suggested an internal morphology with a high degree of molecular orientation in the amorphous segments along the thinner fibres, consistent with a constrained mesomorphic phase formed during their rapid solidification in the electric field. Air filtration was demonstrated with cigarette smoke as a model substance passed through the fibre mats. The 0.4 μm fibres showed the most effective smoke filtration and a capacity to absorb 43× its own weight in smoke residuals, whereas the 1 μm fibres showed the best combination of filtration capacity (32×) and mechanical robustness. The use of recycled PET in the form of nanofibres is a novel way of turning waste into higher-value products.

Water-based synthesis and cleaning methods for high purity ZnO nanoparticles – comparing acetate, chloride, sulphate and nitrate zinc salt precursors

A low temperature (60 °C) aqueous synthesis method of high purity ZnO nanoparticles intended as fillers for ultra-low electrical conductivity insulations is described. Particles were prepared under identical conditions from different zinc salts based on nitrate, chloride, sulphate or acetate to compare their abilities to form high yields of sub-50 nm particles with narrow size distribution. The acetate salt gave uniform 25 nm ZnO particles with a conical prism shape. The chloride and sulphate derived particles showed mixed morphologies of nanoprisms and submicron petals, whereas the nitrate salt yielded prisms assembled into well-defined flower shapes with spiky edges. The micron-sized flower shapes were confirmed by X-ray diffraction to consist of the smaller prism units. Photoluminescence spectroscopy showed emission in the blue-violet region with little variation depending on precursor salt, suggesting that the spectra were dependent on the primary nanoprism formation and rather independent of the final particle morphology. Microscopy revealed that the salt residuals after the reaction showed different affinity to the particle surfaces depending on the type of salt used, with the acetate creating ca. 20 nm thick hydrated shells; and in falling order of affinity: chloride, sulphate and nitrate. An acetate ion shielding effect during the synthesis was therefore assumed, preventing nanoparticle fusion during growth. Varying the concentrations of the counter-ions confirmed the shielding and only the acetate anions showed an ability to stabilize solitary nanoprisms formation in reaction yields from 2 to 10 g L−1. Ultrasonic particle surface cleaning was significantly more efficient than water replacement, resulting in a stable aqueous dispersion with a high zeta potential of 38.9 mV at pH 8.

Morphology and properties of silica-based coatings with different functionalities for Fe3O4, ZnO and Al2O3 nanoparticles

A facile single-step method for obtaining 2–3 nm thick silsesquioxane coatings on metal oxide nanoparticles using different carbon-functional silane precursors is presented. Iron oxide nanoparticles with 8.5 nm in diameter were used as a model to evaluate the possibilities of forming different uniform carbon-functional coatings, ranging from hydrophobic to hydrophilic in character. Electron microscopy showed that all the coated nanoparticles could be described as core–shell nanoparticles with single Fe3O4 cores and carbon-functional silsesquioxane shells, without any core-free silicone oxide phase. Steric factors strongly influenced the deposited silicon oxide precursors with octyl-, methyl- or aminopropyl functionalities, resulting in coating densities ranging from 260 to 560 kg m−3. The methyl-functional coatings required several layers of silsesquioxane, 3–4, to build up the 2 nm structures, whereas only 1–2 layers were required for silsesquioxane with octyl groups. Pure silica coatings from tetraethoxysilanes were however considerably thicker due to the absence of steric hindrance during deposition, allowing the formation of 5–7 nm coatings of ca. 10 layers. The coating method developed for the iron oxide nanoparticles was generic and successfully transferred and up-scaled 30 and 325 times (by volume) to be applicable to 25 nm ZnO and 45 nm Al2O3 nanoparticles.

Micromechanics of ultra-toughened electrospun PMMA/PEO fibres as revealed by in-situ tensile testing in an electron microscope

A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra–tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt–spinning research.

Cellulose nanofibril core–shell silica coatings and their conversion into thermally stable nanotube aerogels

A facile water-based one-pot reaction protocol for obtaining 20 nm thick uniform silica coatings on cellulose nanofibrils (CNFs) is herein presented for the first time. The fully covering silica shells result in the thermal stability of the CNFs improved by ca. 70 °C and 50 °C under nitrogen and oxygen atmospheres, respectively. Heating of the core–shell hybrid fibres to 400 °C results in complete degradation/removal of the CNF cores, and demonstrates an inexpensive route to large-scale preparation of silica nanotubes with the CNFs used as templates. The key to a uniform condensation of silica (from tetraethyl orthosilicate) to cellulose is a reaction medium that permits in situ nucleation and growth of the silica phase on the fibrils, while simultaneously matching the quantity of the condensed silica with the specific surface area of the CNFs. Most coatings were applied to bundles of 2–3 associated CNFs, which could be discerned from their negative imprint that remained inside the silica nanotubes. Finally, it is demonstrated that the coated nanofibrils can be freeze-dried into highly porous silica/cellulose aerogels with a density of 0.005 g cm−3 and how these hybrid aerogels preserve their shape when extensively exposed to 400 °C in air (>6 h). The resulting material is the first reported silica nanotube aerogel obtained by using cellulose nanofibrils as templates.

Antibacterial Properties of Tough and Strong Electrospun PMMA/PEO Fiber Mats Filled with Lanasol—A Naturally Occurring Brominated Substance

A new type of antimicrobial, biocompatible and toughness enhanced ultra-thin fiber mats for biomedical applications is presented. The tough and porous fiber mats were obtained by electrospinning solution-blended poly (methyl methacrylate) (PMMA) and polyethylene oxide (PEO), filled with up to 25 wt % of Lanasol—a naturally occurring brominated cyclic compound that can be extracted from red sea algae. Antibacterial effectiveness was tested following the industrial Standard JIS L 1902 and under agitated medium (ASTM E2149). Even at the lowest concentrations of Lanasol, 4 wt %, a significant bactericidal effect was seen with a 4-log (99.99%) reduction in bacterial viability against S. aureus, which is one of the leading causes of hospital-acquired (nosocomial) infections in the world. The mechanical fiber toughness was insignificantly altered up to the maximum Lanasol concentration tested, and was for all fiber mats orders of magnitudes higher than electrospun fibers based on solely PMMA. This antimicrobial fiber system, relying on a dissolved antimicrobial agent (demonstrated by X-ray diffraction and Infrared (IR)-spectroscopy) rather than a dispersed and “mixed-in” solid antibacterial particle phase, presents a new concept which opens the door to tougher, stronger and more ductile antimicrobial fibers.

Strong and Moldable Cellulose Magnets with High Ferrite Nanoparticle Content

A major limitation in the development of highly functional hybrid nanocomposites is brittleness and low tensile strength at high inorganic nanoparticle content. Herein, cellulose nanofibers were extracted from wood and individually decorated with cobalt-ferrite nanoparticles and then for the first time molded at low temperature (<120 °C) into magnetic nanocomposites with up to 93 wt % inorganic content. The material structure was characterized by TEM and FE-SEM and mechanically tested as compression molded samples. The obtained porous magnetic sheets were further impregnated with a thermosetting epoxy resin, which improved the load-bearing functions of ferrite and cellulose material. A nanocomposite with 70 wt % ferrite, 20 wt % cellulose nanofibers, and 10 wt % epoxy showed a modulus of 12.6 GPa, a tensile strength of 97 MPa, and a strain at failure of ca. 4%. Magnetic characterization was performed in a vibrating sample magnetometer, which showed that the coercivity was unaffected and that the saturation magnetization was in proportion with the ferrite content. The used ferrite, CoFe2O4, is a magnetically hard material, demonstrated by that the composite material behaved as a traditional permanent magnet. The presented processing route is easily adaptable to prepare millimeter-thick and moldable magnetic objects. This suggests that the processing method has the potential to be scaled-up for industrial use for the preparation of a new subcategory of magnetic, low-cost, and moldable objects based on cellulose nanofibers.

Tailoring dielectric properties using designed polymer-grafted ZnO nanoparticles in silicone rubber

Polymer grafts were used to tailor the interphases between ZnO nanoparticles (NPs) and silicone matrices. The final electrical properties of the nanocomposites were tuned by the grafted interphases, by controlling the inter-particle distance and the NP-morphology. The nanocomposites can be used in electrical applications where control of the resistivity is desired. Hansens solubility parameters were used to select a semi-compatible polymer for grafting to obtain anisotropic NP morphologies in silicone, and the grafted NPs self-assembled into various morphologies inside the silicone matrices. The morphologies in the semi-compatible nanocomposites could be tuned by steering the graft length of poly(n-butyl methacrylate) via entropic matrix-graft wetting using surface-initiated atom-transfer radical polymerization. Image analysis models were developed to calculate the radius of primary NPs, the fraction of aggregates, the dispersion, and the face-to-face distance of NPs. The dielectric properties of the nanocomposites were related to the morphology and the face-to-face distance of the NPs. The dielectric losses, above 100 Hz, for nanocomposites with grafted NPs were approximately one decade lower than those of pristine NPs. The isotropic nanocomposites increased the resistivity up to 100 times compared to that of neat silicone rubber, due to the trapping of charge carriers by the interphase of dispersed NPs and nanoclusters. On the other hand, the resistivity of anisotropic nanocomposites decreased 10–100 times when the inter-particle distance in continuous agglomerates was close to the hopping distance of charge carriers. The electrical breakdown strength increased for compatible isotropic nanocomposites, and the temperature dependence of the resistivity and the activation energy were ∼50% lower in the nanocomposites with grafted NPs. These flexible dielectric nanocomposites are promising candidates for low-loss high-voltage transmission cable accessories, mobile electronic devices, wearables and sensors.

Reduced and Surface‐Modified Graphene Oxide with Nonlinear Resistivity

Field-grading materials (FGMs) are used to reduce the probability for electrical breakdowns in critical regions of electrical components and are therefore of great importance. Usually, FGMs are heavily filled (40 vol.%) with semi-conducting or conducting particles. Here, polymer-grafted reduced graphene oxide (rGO) is used as a filler to accomplish percolated networks at very low filling ratios (<2 vol.%) in a semi-crystalline polymer matrix: poly(ethylene-co-butyl acrylate) (EBA). Various simulation models are used to predict the percolation threshold and the flake-to-flake distances, to complement the experimental results. A substantial increase in thermal stability of rGO is observed after surface modification, either by silanization or subsequent polymerizations. The non-linear DC resistivity of neat and silanized rGO and its trapping of charge-carriers in semi-crystalline EBA are demonstrated for the first time. It is shown that the polymer-grafted rGO improve the dispersibility in the EBA-matrix and that the graft length controls the inter-flake distances (i.e. charge-carrier hopping distances). By the appropriate selection of graft lengths, both highly resistive materials at 10 kV mm-1 and FGMs with a large and distinct drop in resistivity (six decades) are obtained, followed by saturation. The nonlinear drop in resistivity is attributed to narrow inter-flake distance distributions of grafted rGO.