Houssine Sehaqui

Strong and Tough Cellulose Nanopaper with High Specific Surface Area and Porosity

In order to better understand nanostructured fiber networks, effects from high specific surface area of nanofibers are important to explore. For cellulose networks, this has so far only been achieved in nonfibrous regenerated cellulose aerogels. Here, nanofibrillated cellulose (NFC) is used to prepare high surface area nanopaper structures, and the mechanical properties are measured in tensile tests. The water in NFC hydrogels is exchanged to liquid CO2, supercritical CO2, and tert-butanol, followed by evaporation, supercritical drying, and sublimation, respectively. The porosity range is 40-86%. The nanofiber network structure in nanopaper is characterized by FE-SEM and nitrogen adsorption, and specific surface area is determined. High-porosity TEMPO-oxidized NFC nanopaper (56% porosity) prepared by critical point drying has a specific surface area as high as 482 m(2) g(-1). The mechanical properties of this nanopaper structure are better than for many thermoplastics, but at a significantly lower density of only 640 kg m(-3). The modulus is 1.4 GPa, tensile strength 84 MPa, and strain-to-failure 17%. Compared with water-dried nanopaper, the material is softer with substantiallly different deformation behavior.

Mechanical performance tailoring of tough ultra-high porosity foams prepared from cellulose I nanofiber suspensions

Low-density structures of mechanical function in plants, arthropods and other organisms, are often based on high-strength cellulose or chitin nanofibers and show an interesting combination of flexibility and toughness. Here, a series of plant-inspired tough and mechanically very robust cellular biopolymer foams with porosities as high as 99.5% (porosity range 93.1–99.5%) were therefore prepared by solvent-free freeze-drying from cellulose I wood nanofiber water suspensions. A wide range of mechanical properties was obtained by controlling density and nanofiber interaction in the foams, and density–property relationships were modeled and compared with those for inorganic aerogels. Inspired by cellulose–xyloglucan (XG) interaction in plant cell walls, XG was added during preparation of the toughest foams. For the cellulose–XG nanocomposite foams in particular, the mechanical properties at comparable densities were superior to those reported in the literature for clay aerogel/cellulose whisker nanocomposites, epoxy/clay aerogels, polymer/clay/nanotube aerogels, and polymer/silica aerogels. The foam structure was characterized by high-resolution field-emission scanning electron microscopy and the specific surface area was measured by nitrogen physisorption. Dynamic mechanical thermal analysis and uniaxial compression tests were performed. The foam was thermally stable up to 275 °C where cellulose started to degrade.

Cellulose Nanofiber Orientation in Nanopaper and Nanocomposites by Cold Drawing

To exploit the mechanical potential of native cellulose fibrils, we report on the preparation of nanopaper with preferred orientation of nanofibrillated cellulose (TEMPO-NFC) by cold drawing. The preparation route is papermaking-like and includes vacuum filtering of a TEMPO-oxidated NFC water dispersion, drawing in wet state and drying. The orientation of the fibrils in the nanopaper was assessed by AFM and wide-angle X-ray diffraction analysis, and the effect on mechanical properties of the resulting nanopaper structure was investigated by tensile tests. At high draw ratio, the degree of orientation is as high as 82 and 89% in-the-plane and cross-sectional planes of the nanopaper, respectively, and the Youngs modulus is 33 GPa. This is much higher than mechanical properties of isotropic nanopaper. The cold drawing method can be also applied to NFC nanocomposites as demonstrated by preparation of TEMPO-NFC/hydroxyethyl cellulose (HEC) nanocomposites. The introduction of the soft HEC matrix allows further tailoring of the mechanical properties.

Stretchable and strong cellulose nanopaper structures based on polymer-coated nanofiber networks: an alternative to nonwoven porous membranes from electrospinning.

Nonwoven membranes based on electrospun fibers are of great interest in applications such as biomedical, filtering, and protective clothing. The poor mechanical performance is a limitation, as is some of the electrospinning solvents. To address these problems, porous nonwoven membranes based on nanofibrillated cellulose (NFC) modified by a hydroxyethyl cellulose (HEC) polymer coating are prepared. NFC/HEC aqueous suspensions are subjected to simple vacuum filtration in a paper-making fashion, followed by supercritical CO(2) drying. These nonwoven nanocomposite membranes are truly nanostructured and exhibit a nanoporous network structure with high specific surface area, as analyzed by nitrogen adsorption and FE-SEM. Mechanical properties evaluated by tensile tests show high strength combined with remarkably high strain to failure of up to 55%. XRD analysis revealed significant fibril realignment during tensile stretching. After postdrawing of the random mats, the modulus and strength are strongly increased. The present preparation route uses components from renewable resources, is environmentally friendly, and results in permeable membranes of exceptional mechanical performance.

Multifunctional Nanoclay Hybrids of High Toughness, Thermal, and Barrier Performances

To address brittleness of nanoclay hybrids of high inorganic content, ductile polymers (polyethylene oxide and hydroxyethyl cellulose) and montmorillonite (MTM) have been assembled into hybrid films using a water-based filtration process. Nacre-mimetic layered films resulted and were characterized by FE-SEM and XRD. Mechanical properties at ambient condition were studied by tensile test, while performance at elevated temperature and moisture conditions were evaluated by TGA, dynamic vapor sorption, and dynamic thermomechanical and hygromechanical analyses. Antiflammability and barrier properties against oxygen and water vapor were also investigated. Despite their high MTM content in the 60-85 wt % range, the hybrids exhibit remarkable ductility and a storage modulus above 2 GPa even in severe conditions (300°C or 94% RH). Moreover, they present fire-shielding property and are amongst the best oxygen and water vapor barrier hybrids reported in the literature. This study thus demonstrates nanostructure property advantages for synergistic effects in hybrids combining inexpensive, available, and environmentally benign constituents.

Fast and Reversible Direct CO2 Capture from Air onto All-Polymer Nanofibrillated Cellulose—Polyethylenimine Foams

Fully polymeric and biobased CO2 sorbents composed of oxidized nanofibrillated cellulose (NFC) and a high molar mass polyethylenimine (PEI) have been prepared via a freeze-drying process. This resulted in NFC/PEI foams displaying a sheet structure with porosity above 97% and specific surface area in the range 2.7-8.3 m(2)·g(-1). Systematic studies on the impact of both PEI content and relative humidity on the CO2 capture capacity of the amine functionalized sorbents have been conducted under atmospheric conditions (moist air with ∼400 ppm of CO2). At 80% RH and an optimum PEI content of 44 wt %, a CO2 capacity of 2.22 mmol·g(-1), a stability over five cycles, and an exceptionally low adsorption half time of 10.6 min were achieved. In the 20-80% RH range studied, the increase in relative humidity increased CO2 capacity of NFC/PEI foams at the expense of a high H2O uptake in the range 3.8-28 mmol·g(-1).

Tamarind seed xyloglucan – a thermostable high-performance biopolymer from non-food feedstock

Polysaccharide biopolymers from renewable resources are of great interest as replacements for petroleum-based polymers since they have lower cradle-to-grave non-renewable energy use and greenhouse gas emissions. Starch is widely used as a packaging material but is based on food resources such as potato or corn, and suffers from high sensitivity to water vapor even under ambient conditions. For the first time, xyloglucan (XG) from tamarind seed waste is explored as an alternative high-performance biopolymer from non-food feedstock. XG is purified, and dissolved in water to cast films. Moisture sorption isotherms, tensile tests and dynamic mechanical thermal analysis are performed. Glycerol plasticization toughening and enzymatic modification (partial removal of galactose in side chains of XG) are attempted as means of modification. XG films show much lower moisture sorption than the amylose component in starches. Stiffness and strength are very high, with considerable ductility and toughness. The thermal stability is exceptionally high and is approaching 250 °C. Glycerol plasticization is effective already at 10% glycerol. These observations point towards the potential of XG as a “new” biopolymer from renewable non-food plant resources for replacement of petroleum-based polymers.

Highly Carboxylated Cellulose Nanofibers via Succinic Anhydride Esterification of Wheat Fibers and Facile Mechanical Disintegration

We report herein the preparation of 4-6 nm wide carboxyl-functionalized cellulose nanofibers (CNF) via the esterification of wheat fibers with cyclic anhydrides (maleic, phtalic, and succinic) followed by an energy-efficient mechanical disintegration process. Remarkable results were achieved via succinic anhydride esterification that enabled CNF isolation by a single pass through the microfluidizer yielding a transparent and thick gel. These CNF carry the highest content of carboxyl groups ever reported for native cellulose nanofibers (3.8 mmol g-1). Compared to conventional carboxylated cellulose nanofibers prepared via Tempo-mediated oxidation of wheat fibers, the present esterified CNF display a higher molar-mass and a better thermal stability. Moreover, highly carboxylated CNF from succinic anhydride esterification were effectively integrated into paper filters for the removal of lead from aqueous solution and are potentially of interest as carrier of active molecules or as transparent films for packaging, biomedical or electronic applications.

Mechanosorptive creep in nanocellulose materials

The creep behavior of nanocellulose films and aerogels are studied in a dynamic moisture environment, which is crucial to their performance in packaging applications. For these materials, the creep rate under cyclic humidity conditions exceeds any constant humidity creep rate within the cycling range, a phenomenon known as mechanosorptive creep. By varying the sample thickness and relative humidity ramp rate, it is shown that mechanosorptive creep is not significantly affected by the through-thickness moisture gradient. It is also shown that cellulose nanofibril aerogels with high porosity display the same accelerated creep as films. Microstructures larger than the fibril diameter thus appear to be of secondary importance to mechanosorptive creep in nanocellulose materials, suggesting that the governing mechanism is found between molecular scales and the length-scales of the fibril diameter.