Can TEMPO-Oxidized Cellulose Nanofibers Be Used as Additives in Bio-Based Building Materials? A Preliminary Study on Earth Plasters.

Interest towards cellulose nanofibers obtained from virgin and waste sources has seen a significant growth, mainly thanks to the increasing sensitivity towards the concept of circular economy and the high levels of paper recycling achieved in recent years. Inspired by the guidelines of the green building industry, this study proposes the production and characterization of TEMPO-oxidized and homogenized cellulose nanofibers (TOHO CNF) from different sources and their use as additives for earth plasters on two different raw earth samples, characterized by geotechnical laboratory tests and mineralogical analysis: a high-plasticity clay (T2) and a medium-compressibility silt (ABS). Original sources, including those derived from waste (recycled cardboard and paper mill sludge), were characterized by determining chemical content (cellulose versus ashes and lignin) and fiber morphology. TOHO CNF derived from the different sources were compared in terms of nanofibers medium diameter, crystallinity degree, thermal decomposition and oxidation degree, that is the content of carboxylic groups per gram of sample. Then, a preliminary analysis of the influence of CNF on earth plasters is examined. Adhesion and capillary absorption tests highlighted the effect of such nanofibers on blends in function of two factors, namely the cellulose original source and the oxidation degree of the fibers. In particular, for both earth samples, T2 and ABS, a significant increase in adhesion strength was observed in the presence of some TOHO CNF additives. As far as capillary sorption tests, while an undesired increase in water adsorption was detected for T2 compared to the control, in the case of ABS, a significant reduction in water content was measured by adding TOHO CNF derived from recycled sources. These results pave the way for further in-depth investigation on the role of TOHO CNF as additives for earth plasters.

Comparative Life Cycle Assessment of Cellulose Nanofibres Production Routes from Virgin and Recycled Raw Materials.

Nanocellulose-based materials are attracting an increasing interest for the positive role they could play in sustainable development; being originated from renewable resources. Moreover, cellulose has a high potential of recycling from both post-consumer waste and industrial waste. Both factors, i.e., recyclability and renewable resources; results are also extremely favourable in the perspective of circular economy. Despite all these positive aspects, an industrial production has yet to start. At the lab scale, many preparation methods of cellulose nanofibres (CNF) are available; here, the three most common are analysed: (1) enzymatic pre-treatment followed by homogenisation (ENZHO), (2) oxidative pre-treatment combined with homogenisation (TOHO) or (3) oxidative pre-treatment followed by sonication (TOSO). All three processes have been experimentally carried out starting from both virgin and recycled cellulose from industrial waste sludge. The environmental sustainability of these three routes is estimated by the Life Cycle Assessment (LCA) using experimental lab scale data. In this scenario, the comparative LCA has pointed out a superior performance of the ENZHO process, followed by TOHO and, lastly, by TOSO. The influence of energy consumption on the final results has been further investigated by a sensitivity analysis, showing that the TOHO and TOSO routes could reach similar performances by scaling-up the process from the laboratory. The different typology of CNF obtained by conducting the ENZHO process with respect to the TEMPO-mediated oxidation approach is also outlined as an additional element to be considered for the final selection of a suitable process.

PLA coated paper containing active inorganic nanoparticles: Material characterization and fate of nanoparticles in the paper recycling process.

For paper and paperboard packaging, recyclability plays an important role in conserving the resources and reducing the environmental impacts. Therefore, when it comes to the nano-enabled paper packaging material, the recyclability issue should be properly addressed. This study represents our first report on the fate of nanomaterials in paper recycling process. The packaging material of concern is a PLA (Polylactic Acid) coated paper incorporating zinc oxide nanoparticles in the coating layer. The material was characterised and assessed in a lab-scale paper recycling line. The recyclability test was based on a method adapted from ATICELCA MC501-13, which enabled to recover over 99% of the solids material. The mass balance result indicates that 86-91% zinc oxide nanoparticles ended up in the rejected material stream, mostly embedded within the polymer coating; whereas 7-16% nanoparticles ended up in the accepted material stream. Besides, the tensile strength of the recycled handsheets suggests that the nano-enabled coating had no negative impacts on the recovered fibre quality.

Contact Antimicrobial Surface Obtained by Chemical Grafting of Microfibrillated Cellulose in Aqueous Solution Limiting Antibiotic Release.

Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the ß-lactam antibiotic benzyl penicillin in aqueous medium to prepare antimicrobial films. Penicillin was grafted on the MFC surface using a suspension of these nanofilaments or directly on films. Films prepared from the penicillin-modified MFC were characterized by Fourier transform infrared spectroscopy, contact angle measurements, elemental analysis, and X-ray photoelectron spectroscopy and tested for antibacterial activity against the Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. Penicillin-grafted MFC films exhibited successful killing effect on Gram-positive bacteria with 3.5-log reduction whereas bacteriostatic efficiency was found in penicillin-grafted MFC suspension. The zone of inhibition test and leaching dynamic assay demonstrated that penicillin was not diffused into the surrounding media, thus proving that the films were indeed contact active. Thus, penicillin can be chemically bound to the modified substrate surface to produce promising nonleaching antimicrobial systems.

Hydrophobic properties conferred to Kraft pulp by a laccase-catalysed treatment with lauryl gallate.

Hydrophobic properties were conferred to a high-lignin-content Kraft pulp by a laccase-catalysed treatment in the presence of lauryl gallate (LG). The treatment resulted in a two-fold increase in contact angle and conferred water absorption resistance to the pulp. Kappa number was increased, indicating that some phenolic compounds were incorporated in the pulp. A control treatment with LG alone did not affect water absorption, demonstrating that laccase was essential to attain these new properties. The loss of hydrophobicity after an acetone Soxhlet extraction highlighted that adsorbed acetone-soluble compounds played a key role in the properties. GC-FID and HPSEC-UV analysis of the acetone extract indicated the formation of dodecanol and different phenolic oligomers. SEM images showed the treatment-induced changes in the fibre network. Additional experiments with various reaction times and reactant concentrations highlighted the role of LG oxidation products in the introduction of absorption resistance.

Structural characterization and antioxidant activity evaluation of lignins from rice husk.

In recent years, lignin and extractives from herbaceous plants and crops are receiving increasing attention for their renewability and large annual biomass stock. It is worth noting that only a few studies deal with the chemical characterization of rice husk, a side product of one of the most important crops with regard to human nutrition. Thus, in this study lignin from rice husk was isolated and characterized. Two different extraction procedures were optimized and tested: acidolysis and alkaline enzymatic (AE). The different lignins isolated were fully characterized by means of gravimetric, chromatographic (GPC), and spectroscopic (31P NMR, 2D-HSQC-NMR) analyses with the aim to compare yields, sample purity, and chemical properties, recognized as key parameters for future development. Notwithstanding the extraction procedure, the results highlighted that rice husk lignin is mainly formed by guaiacyl and p-hydroxyphenyl units. The acidolytic approach showed an appreciable lignin recovery and high purity, whereas the AE lignin sample was found to be rich in residual polysaccharides and oxidized functionalities. Moreover, different rice husk extracts, along with acidolysis lignin and AE lignin specimens, were assayed for their antioxidant activity by means of a DPPH radical scavenging test.