Molecular modeling of interfaces between cellulose crystals and surrounding molecules: Effects of caprolactone surface grafting

A technical problem in cellulosic nanocomposite materials is the weak interaction between hydrophilic cellulose and hydrophobic polymer matrices. One approach to solve this difficulty is to chemically graft monomers of the matrix polymer onto the cellulose surface. An important question is to understand the effect such surface modification has on the interfacial properties. Semi-empirical approaches to estimate work of adhesion based on surface energies do not provide information on specific molecular interactions. Details about these interactions were obtained using molecular dynamics (MD) simulation. Cellulose interfaces with water and caprolactone medium were modeled with different amounts of grafted caprolactone. The modification lead to an increased work of adhesion between the surface and its surrounding medium. Furthermore, the MD simulations showed that the interaction between cellulose, both modified and non-modified, and surrounding medium is dominated by Coulomb interactions, predominantly as hydrogen bonds.     

Extraction of cellulose and preparation of nanocellulose from sisal fibers

In this work a study on the feasibility of extracting cellulose from sisal fiber, by means of two different procedures was carried out. These processes included usual chemical procedures such as acid hydrolysis, chlorination, alkaline extraction, and bleaching. The final products were characterized by means of Thermogravimetric Analysis (TGA), Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC) and Scanning Electronic Microscopy (SEM). The extraction procedures that were used led to purified cellulose. Advantages and disadvantages of both procedures were also analyzed. Finally, nanocellulose was produced by the acid hydrolysis of obtained cellulose and characterized by Atomic Force Microscopy (AFM).     

Toughness enhancement of cellulose nanocomposites by alkali treatment of the reinforcing cellulose nanofibers

Nanocomposites were produced with NaOH aqueous solution-treated microfibrillated cellulose (MFC) and phenolic resin, and the mechanical properties were compared with their microcomposite counterparts based on pulp fiber. Tensile tests showed that strong alkali-treated MFC nanocomposites with resin content around 20 wt.% achieved strain at fracture values two times higher than those of untreated MFC nanocomposites and five times higher than those of untreated pulp microcomposites. The improvement in work of fracture of alkali-treated MFC nanocomposites was attributed to the ductility of the nanofibers caused by transformations in the amorphous regions along the cellulose microfibrils.     

Dissolution and forming of cellulose with ionic liquids

The dissolution of cellulose in different ionic liquids will be described as a very recent subject for a direct dissolving process, which was used to prepare regenerated cellulose fibres. The preparation of the dopes was arranged starting from slurry of cellulose in the aqueous ionic liquid by removing the water at elevated temperature, vacuum and high shearing rates. As ionic liquids, the 1-N-Butyl-3-methylimidazolium chloride, the 1-Ethyl-3-methylimidazolium chloride, the 1-N-Butyl-2,3-dimethylimidazolium chloride, the 1-N-Butyl-3-methylimidazolium acetate and the 1-Ethyl-3-methylimidazolium acetate were investigated. The cellulose solutions in ionic liquids were characterised by means of light microscopy, cone-plate rheometry and particle analysis. In addition these results were compared with cellulose solutions in N-methyl-morpholine-N-oxide monohydrate. Finally the cellulose dopes were shaped by a dry-wet spinning process to manufacture cellulose fibres. The properties of the resulted fibre had been determined and will be discussed.     

硅烷化磁铁粉固定胰蛋白酶的研究

分别以硅烷化磁铁粉、硅烷磁化脱乙酰几丁质及脱乙酰几丁质作载体,甲醛或戊二醛为交联剂,对胰蛋白酶的固定化条件及所制备的固定化酶的性质进行了研究．研究了载体种类、交联剂和ｐＨ值以及载体与酶比例等因素对胰蛋白酶固定化的影响．研究了不同载体固定胰蛋白酶的特点,证明以硅烷化试剂和甲醛作交联剂的硅烷化磁铁粉作胰蛋白酶固定化的载体具有明显优点,所制备的硅烷化磁铁粉固定化胰蛋白酶酶学性质明显优于可溶性胰蛋白酶     

UV-cured polymer electrolyte membranes for Li-cells: Improved mechanical properties by a novel cellulose reinforcement

One of the main drawbacks that restricts the practical application of gel-polymer electrolytes is the inferior mechanical performance compared to other available systems. In this work, we have reinforced UV-cured methacrylic membranes with cellulose. To enhance its compatibility with the polymer matrix, cellulose is modified by UV-grafting poly(ethylene glycol) methyl ether methacrylate on it. Excellent mechanical properties are obtained and good ionic conductivity values are observed, enlightening that this kind of membrane is an interesting candidate for future applications as thin gel-polymer electrolyte in flexible lithium batteries.     

Liquid crystalline cellulose derivative elastomer films under uniaxial strain

Mesogenic cellulose derivative chains cross-linked into free-standing thin films were prepared by a shear-casting technique from anisotropic precursor solutions of thermotropic (acetoxypropyl)cellulose. After shear cessation a macroscopically oriented serpentine structure with the director in average along the shear direction is locked resulting in anisotropic optical and mechanical properties of the material. These films were submitted to an external uniaxial mechanical field perpendicular and parallel to the shear direction. Stretching perpendicular to the shear direction produced significant director rotations and a reset of order of the director order parameter for a deformation in the range 2–3 as detected by X-rays and optical microscopy. The different response found for strains imposed parallel and perpendicular to the initial average director orientation indicates that even though our system shows a serpentine director modulation that is either attenuated or reinforced by deformations parallel or perpendicular to the shear direction, its behaviour is similar to theoretical predictions for monodomain nematic elastomers described in the literature.     

A new bio-based nanocomposite: fibrillated TEMPO-oxidized celluloses in hydroxypropylcellulose matrix

Utilization of TEMPO-oxidized celluloses in bio-based nanocomposites is reported for the first time. TEMPO-oxidized wood pulps (net carboxylate content 1.1 mmol/g cellulose) were fibrillated to varying degrees using a high intensity ultrasonic processor. The degree of fibrillation was controlled by varying sonication time from 1 to 20 min. The sonication products were then characterized independently and as fillers (5 wt% loading) in hydroxypropyl cellulose nanocomposite films. Nanofibril yields ranging from 11 to 98 wt% (on fiber weight basis) were obtained over the range of sonication times used. Suspension viscosities increased initially with sonication time, peaked with gel-like behavior at 10 min of sonication and then decreased with further sonication. The thermal degradation temperature of unfibrillated oxidized pulps was only minimally affected (6 °C decrease) by the fibrillation process. Dynamic mechanical analysis of the nanocomposites revealed strong fibril-matrix interactions as evidenced by remarkable storage modulus retention at high temperatures and a suppression of matrix glass transition at “high” (~5 wt%) nanofibril loadings. Creep properties likewise exhibited significant (order of magnitude) suppression of matrix flow at high temperatures. It was also believed, based on morphologies of freeze-fracture surfaces that the nanocomposites may be characterized by high fracture toughness. Direct fracture testing will however be necessary to verify this suspicion.