Bernd Wicklein

Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide.

High-performance thermally insulating materials from renewable resources are needed to improve the energy efficiency of buildings. Traditional fossil-fuel-derived insulation materials such as expanded polystyrene and polyurethane have thermal conductivities that are too high for retrofitting or for building new, surface-efficient passive houses. Tailored materials such as aerogels and vacuum insulating panels are fragile and susceptible to perforation. Here, we show that freeze-casting suspensions of cellulose nanofibres, graphene oxide and sepiolite nanorods produces super-insulating, fire-retardant and strong anisotropic foams that perform better than traditional polymer-based insulating materials. The foams are ultralight, show excellent combustion resistance and exhibit a thermal conductivity of 15u2005mWu2005m(-1)u2005K(-1), which is about half that of expanded polystyrene. At 30u2005°C and 85% relative humidity, the foams retained more than half of their initial strength. Our results show that nanoscale engineering is a promising strategy for producing foams with excellent properties using cellulose and other renewable nanosized fibrous materials.

Bio-organoclays based on phospholipids as immobilization hosts for biological species.

A new type of hybrid biomaterials based on the clay minerals montmorillonite and sepiolite as well as phosphatidylcholine, acting as environment-friendly biomodifier, was prepared. The biohybrids were characterized by sampling of adsorption isotherms in different organic solvents. The results suggest bilayer formation both on the external sepiolite surface as well as in the intracrystalline space of the montmorillonite. The obtained supported lipid membranes were further investigated by X-ray diffraction, multinuclear solid state NMR, Fourier transformed IR spectroscopy and thermal analysis. From these results an adsorption model based on electrostatic interaction between the polar phospholipid headgroups and the silicate surface could be postulated. The versatility of bio-organoclays as immobilization host for biological species was demonstrated in a mycotoxin retention study.

Phospholipid–Sepiolite Biomimetic Interfaces for the Immobilization of Enzymes

Biomimetic interfaces based on phosphatidylcholine (PC) assembled to the natural silicate sepiolite were prepared for the stable immobilization of the urease and cholesterol oxidase enzymes. This is an important issue in practical advanced applications such as biocatalysis or biosensing. The supported lipid bilayer (BL-PC), prepared from PC adsorption, was used for immobilization of enzymes and the resulting biomimetic systems were compared to several other supported layers including a lipid monolayer (ML-PC), a mixed phosphatidylcholine/octyl-galactoside layer (PC-OGal), a cetyltrimethylammonium monolayer (CTA), and also to the bare sepiolite surface. Interfacial characteristics of these layers were investigated with a focus on layer packing density, hydrophilicity/hydrophobicity, and surface charge, which are being considered as key points for enzyme immobilization and stabilization of their biological activity. Cytoplasmic urease and membrane-bound cholesterol oxidase, which served as model enzymes, were immobilized on the different PC-based hybrid materials to probe their biomimetic character. Enzymatic activity was assessed by cyclic voltammetry and UV-vis spectrophotometry. The resulting enzyme/bio-organoclay hybrids were applied as active phase of a voltammetric urea biosensor and cholesterol bioreactor, respectively. Urease supported on sepiolite/BL-PC proved to maintain its enzymatic activity over several months while immobilized cholesterol oxidase demonstrated high reusability as biocatalyst. The results emphasize the good preservation of bioactivity due to the accommodation of the enzymatic system within the biomimetic lipid interface on sepiolite.

Functional hybrids based on biogenic nanofibrils and inorganic nanomaterials

This feature article reviews some of the recent work on the fabrication of functional hybrids based on biogenic nanofibers and inorganic nanomaterials with an emphasis on their functional properties and suggested potential applications. We also discuss some of the work oriented towards the formation of ordered materials in the pursuit of achieving a hierarchical construction. Besides the academic interest in biogenic nanomaterials, it is anticipated that the use of natural, abundant nanomaterials, e.g., cellulose, chitin, collagen, and silk, could provide affordable functional nanomaterials in developing countries.

Omnidispersible poly(ionic liquid)-functionalized cellulose nanofibrils: surface grafting and polymer membrane reinforcement

We report a facile one-step route to graft poly(ionic liquid)s (PILs) onto cellulose nanofibrils (CNFs). The dispersibility of the PIL-functionalized CNFs in water and various organic solvents could be tuned by the choice of the PIL-binding anion. We demonstrate that such omnidispersible PIL@CNF hybrids can be used to reinforce porous poly(ionic liquid) membranes.

Stabilizing nanocellulose-nonionic surfactant composite foams by delayed Ca-induced gelation

Aggregation of dispersed rod-like particles like nanocellulose can improve the strength and rigidity of percolated networks but may also have a detrimental effect on the foamability. However, it should be possible to improve the strength of nanocellulose foams by multivalent ion-induced aggregation if the aggregation occurs after the foam has been formed. Lightweight and highly porous foams based on TEMPO-mediated oxidized cellulose nanofibrils (CNF) were formulated with the addition of a non-ionic surfactant, pluronic P123, and CaCO3 nanoparticles. Foam volume measurements show that addition of the non-ionic surfactant generates wet CNF/P123 foams with a high foamability. Foam bubble size studies show that delayed Ca-induced aggregation of CNF by gluconic acid-triggered dissolution of the CaCO3 nanoparticles significantly improves the long-term stability of the wet composite foams. Drying the Ca-reinforced foam at 60 °C results in a moderate shrinkage and electron microscopy and X-ray tomography studies show that the pores became slightly oblate after drying but the overall microstructure and pore/foam bubble size distribution is preserved after drying. The elastic modulus (0.9-1.4 MPa) of Ca-reinforced composite foams with a density of 9-15 kg/m(3) is significantly higher than commercially available polyurethane foams used for thermal insulation.

Recent Advances on Fibrous Clay-Based Nanocomposites

This review critically introduces recent results on nanocomposite materials derived from the fibrous clay silicates sepiolite and palygorskite and combined with diverse types of polymers, from typical thermoplastics to biopolymers such as polysaccharides, proteins, lipids, and nucleic acids. First, the main features of both silicates are described, emphasizing the structural and textural characteristics that determine the interaction mechanisms with organic compounds and particularly with polymers, which define the final properties of the resulting materials. The crucial role of the clay–silicate interface governing the terminal properties of the nanocomposites is especially considered. Second, this work reports and discusses different experimental approaches and preparative procedures adopted for the nanofabrication and conformation (powders, films, monoliths, foams, etc.) of nanocomposites, comparing in certain cases with analogous materials derived from layered clays instead of sepiolite or palygorskite. Selected examples of fibrous clay-based nanocomposites are discussed to show the broad versatility of these materials in application fields as diverse as structural materials, conducting nanocomposites, biomaterials, environmental remediation, and sensor devices.

CHAPTER 1:Functional Nanocomposites Based on Fibrous Clays

This chapter is focused on functional nanocomposites based on the use of the microfibrous clays sepiolite and palygorskite as efficient fillers for diverse types of polymer matrices, from typical thermoplastics to biopolymers. The main features that govern the interaction between the silicates and the polymer matrix are discussed. The introduction addresses the structural and textural features of the fibrous silicates, as well as the possible synthetic approaches to increase the compatibility of these nanofillers with the polymeric matrix. Additionally, these clays can be easily functionalized through their surface silanol groups based on chemical reactions or by anchoring of nanoparticles. This allows for the preparation of a wide variety of functional polymer–clay nanocomposites. Thereafter, some relevant examples of nanocomposites derived from conventional polymers are reported, as well as of those based on polymers that exhibit electrical conductivity. Lastly, selected works employing sepiolite or palygorskite as fillers in polymeric matrixes of natural origin are discussed, showing the wide application of these resulting nanocomposites as bioplastics, as well as in biomedicine, environmental remediation and the development of sensor devices.