Microfibrillated celluloses (MFCs) with diameters predominantly in the range of 10-100 nm liberated from larger plant-based fibers have garnered much attention for the use in composites, coatings, and films due to large specific surface areas, renewability, and unique mechanical properties. Energy consumption during production is an important aspect in the determination of the ''green'' nature of these MFC-based materials. Bleached and unbleached hardwood pulp samples were processed by homogenization, microfluidization, and micro-grinding, to determine the effect of processing on microfibril and film properties, relative to energy consumption. Processing with these different methods affected the specific surface area of the MFCs, and the film characteristics such as opacity, roughness, density, water interaction properties, and tensile properties. Apparent film densities were approximately 900 kg/ m 3 for all samples and the specific surface area of the processed materials ranged from approximately 30 to 70 m 2 /g for bleached hardwood and 50 to 110 m 2 /g for unbleached hardwood. The microfluidizer resulted in films with higher tensile indices than both micro-grinding and homogenization (148 Nm/g vs. 105 Nm/g and 109 Nm/g, respectively for unbleached hardwood). Microfluidization and micro-grinding resulted in films with higher toughness values than homogenization and required less energy to obtain these properties, offering promise for producing MFC materials with lower energy input. It was also determined that a refining pretreatment required for microfluidization or homogenization can be reduced or eliminated when producing MFCs with the micro-grinder. A summary of the fiber and mechanical energy costs for different fibers and processing conditions with economic potential is presented.
Cellulose nanocrystals (CN) were used to reinforce nanofibers in composite mats produced via electrospinning of poly(vinyl alcohol) (PVA) with two different concentrations of acetyl groups. Ultrathin cross-sections of the obtained nanocomposites consisted of fibers with maximum diameters of about 290 nm for all the CN loads investigated (from 0 to 15% CN loading). The electrospinning process did not affect the structure of the PVA polymer matrix, but its degree of crystallinity increased significantly together with a slight increase in the corresponding melting temperature. These effects were explained as being the result of alignment and enhanced crystallization of PVA chains within the individual nanofibers that were subjected to high shear stresses during electrospinning. The strong interaction of the PVA matrix with the dispersed CN phase, mainly via hydrogen bonding or bond network, was reduced with the presence of acetyl groups in PVA. Most importantly, the elastic modulus of the nanocomposite mats increased significantly as a consequence of the reinforcing effect of CNs via the percolation network held by hydrogen bonds. However, this organization-driven crystallization was limited as observed by the reduction in the degree of crystallinity of the CN-loaded composite fibers. Finally, efficient stress transfer and strong interactions were demonstrated to occur between the reinforcing CN and the fully hydrolyzed PVA electrospun fibers.
There is significant
interest in biodegradable and transparent
UV protection films from renewable resources for many different applications.
Herein, the preparation and characterization of semitransparent flexible
cellulose films containing low amounts of covalently bonded lignin
with UV-blocking properties are described. Azide modified cellulose
dissolved in dimethylacetamide/lithium chloride (DMAc/LiCl) was reacted
with propargylated lignin to produce 0.5%, 1%, and 2% by weight lignin
containing materials. Cellulose-lignin films were prepared by regeneration
in acetone. These covalently bonded cellulose-lignin films were homogeneous,
unlike the simple blends of cellulose and lignin. Prepared films showed
high UV protection ability. Cellulose film containing 2% lignin showed
100% protection of UV-B (280–320 nm) and more than 90% of UV-A
(320–400 nm). The UV protection of prepared films was persistent
when exposed to thermal treatment at 120 °C and UV irradiation.
Thermogravimetric analysis of the films showed minimal mass loss up
to 275 °C. The tensile strength of the neat cellulose film was
around 120 MPa with about a 10% strain to break. Treated cellulose
films with 2% lignin showed lower tensile strength (90 MPa). The described
methods demonstrate a straightforward procedure to produce renewable
based cellulose-lignin UV-light-blocking films.
The interactions with water and the physical properties of microfibrillated celluloses (MFCs) and associated films generated from wood pulps of different yields (containing extractives, lignin, and hemicelluloses) have been investigated. MFCs were produced by combining mechanical refining and a high pressure treatment using a homogenizer. The produced MFCs were characterized by morphology analysis, water retention, hard-to-remove water content, and specific surface area. Regardless of chemical composition, processing to convert macrofibrils to microfibrils resulted in a decrease in water adsorption and water vapor transmission rate, both important properties for food packaging applications. After homogenization, MFCs with high lignin content had a higher water vapor transmission rate, even with a higher initial contact angle, hypothesized to be due to large hydrophobic pores in the film. A small amount of paraffin wax, less than 10%, reduced the WVTR to a similar value as low density polyethylene. Hard-toremove water content correlated with specific surface area up to approximately 50 m 2 /g, but not with water retention value. The drying rate of the MFCs increased with the specific surface area. Hornified fibers from recycled paper also have the potential to be used as starting materials for MFC production as the physical and optical properties of the films were similar to the films from virgin fibers. In summary, the utilization of lignin containing MFCs resulted in unique properties and should reduce MFC production costs by reducing wood, chemical, and energy requirements.
Ultrathin films of aligned cellulose nanocrystals (CNCs)
were assembled
on mica supports by using electric field-assisted shear. The relationship
between polarization gradients and strain mechanics of the obtained
films was examined by monitoring their deflection with an atomic force
microscope operated in contact mode. The piezoelectric response of
the films was ascribed to the collective contribution of the asymmetric
crystalline structure of the cellulose crystals. The magnitude of
the effective shear piezoelectric constant (d
25) of highly ordered CNC films was determined to be 2.1 Å/V,
which is comparable to that of a reference film of a piezoelectric
metal oxide.
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