Modification and characterization of a novel and fluorine-free cellulose nanofiber with hydrophobic and oleophobic properties.

In this study, a brand-new, easy, and environmentally friendly approach for chemically functionalizing 2,2,6,6-tetramethylpiperidinyloxyl radical (TEMPO)-oxidized cellulose nanofiber (TOCNF) to produce modified cellulose nanofiber (octadecylamine-citric acid-CNF) was proposed. Effects of octadecylamine (ODA)/TOCNF mass ratio on the chemical structure, morphology, surface hydrophobicity and oleophobicity were studied. According to Fourier transform infrared spectroscopy (FTIR) analysis, ODA was successfully grafted onto the TOCNF by simple citric acid (CA) esterification and amidation reactions. Scanning electron microscopy (SEM) showed that a new rough structure was formed on the ODA-CA-CNF surface. The water contact angle (WCA) and the castor oil contact angle (OCA) of the ODA-CA-CNF reached 139.6° and 130.6°, respectively. The high-grafting-amount ODA-CA-CNF was sprayed onto paper, and the OCA reached 118.4°, which indicated good oil-resistance performance. The low-grafting-amount ODA-CNF was applied in a pH-responsive indicator film, exhibiting a colour change in response to the pH level, which can be applied in smart food packaging. The ODA-CA-CNF with excellent water/oil-resistance properties and fluorine-free properties can replace petrochemical materials and can be used in the fields of fluorine-free oil-proof paper.

Multi-site sulfonation of lignin for the synthesis of a high-performance dye dispersant.

Sulfonated lignin-based dye dispersants have intensively attracted attention due to their low cost, renewability and abundant sources. However, their utilization is limited by the low content of sulfonic groups and high content of hydroxyl groups in their complex lignin structure, which results in various problems such as high reducing rate of dye, severe staining of the fibers and uneven dyeing. Here, the multi-site sulfonated lignin-based dispersants were prepared with high sulfonic group content (2.20 mmol/g) and low hydroxyl content (2.43 mmol/g). When using it as the dispersant, the dye uptake rate was improved from 69.23 % to 98.55 %, the reducing rate was decreased from 20.82 % to 2.03 %, the K/S value was reduced from 0.69 to 0.02, and the particle sizes in dye system before and after high temperature treatment were stabilized below 0.5 µm. Besides, the dispersion effect was significantly improved because no obvious separation between dye and water was observed even if without the assistance of grinding process. In short, the multi-site sulfonation method proposed in this work could remarkably improve the performances of the lignin-based dye dispersants, which would facilitate the development of the dye dispersion and the high value utilization of lignin.

Development of novel paper-based supercapacitor electrode material by combining copper-cellulose fibers with polyaniline.

Along with the developing of flexible electronics, there is a strong interest in high performance flexible energy storage materials. As natural carbohydrate polymer, cellulose fibers have potential applications in the area due to their biodegradability and flexibility. However, their conductive and electrochemical properties are impossible to meet the demands of practical applications. In this study, cellulose fibers were combined with polyaniline to develop novel paper-based supercapacitor electrode material. Cellulose fibers were firstly coordinated to Cu(II) and subsequently involved in polymerization of polyaniline. Not only the mass loading of polyaniline was significantly increased, but also an impressive area specific capacitance (2767 mF/cm2 at 1 mA/cm2) was achieved. The developed strategy is efficient, environmentally friendly, and has implications for the development of cellulosic paper-based advanced functional materials.

Innovative modification of cellulose fibers for paper-based electrode materials using metal-organic coordination polymers.

Cellulosic paper-based electrode materials have attracted increasing attention in the field of flexible supercapacitor. As a conductive polymer, polyaniline exhibits high theoretical pseudocapacitive capacitance and has been applied in paper-based electrode materials along with cellulose fibers. However, the stacking of polyaniline usually leads to poor performance of electrodes. In this study, metal-organic coordination polymers of zirconium-alizarin red S and zirconium-phytic acid are applied to modulate the polyaniline layer to obtain high-performance cellulosic paper-based electrode materials. Zirconium hydroxide is firstly loaded on cellulose fibers while alizarin red S and phytic acid are introduced to regulate the morphology of polyaniline through doping and coordination processes. The results show that the introduction of dual coordination polymers is effective to regulate the morphology of polyaniline on cellulose fibers. The performances of the paper-based electrode materials, including electrical conductivity and electrochemistry, are apparently improved. It provides a promising strategy for the potential development of economical and green electrode materials in the conventional paper-making process.

Multi-functional polyvinyl alcohol/tannin acid composite films incorporated with lignin nanoparticles loaded by potassium sorbate.

The biocompatible, biodegradable and strong polyvinyl alcohol-based films have been widely investigated and used in the field of active packaging. To endow with diverse function, this paper firstly prepared lignin nanoparticles loaded with potassium sorbate (LNP@PS) as additives to exploit additional antibacterial, UV blocking, oxygen barrier, and water barrier properties. Besides, tannin acid (TA) was incorporated for compensating and further enhancing mechanical properties. Results showed that the PVA-based composite films containing 3 % LNP@PS and 5 % TA could achieve the optimal tensile strength at 74.51 MPa, water vapor permeability at 7.015·10-13·g·cm/cm2·s·Pa and oxygen permeability at 1.93 cm3/m2·24 h MPa, which was an 165 % of increase, 47 % and 112 % of reduction respectively compared to pure PVA films. Additionally, the composite films exhibited apparently superior bacteria and oxygen resistance properties evidenced by microbial infection and free radical scavenging performance. In addition, the slow-release effect of PS assisted the strawberry preservation with an extension of 3 days, which provided a promising novel route to prepare active food packaging material.

One-step fabrication of eco-friendly multi-functional amphiphobic coatings for cellulose-based food packaging.

Plastic and fluorine-containing oil and water resistant packaging materials have been gradually replaced by non-toxic and harmless bio-based materials because of their hazard to environment and human health. In this study, chitosan/carnauba wax emulsions (CS/CWs) were firstly prepared by one-step and used as oil and water resistant coating for cellulose-based food packaging paper. The impacts of emulsion components on stability of the emulsions and barrier performance of the coated paper were investigated. The results showed that the viscosity, particle size and polydispersity index of the emulsions were greatly dependent on the concentration of CS and CW, and the coated paper had the best comprehensive performance in water and oil resistance when the concentration of CS was 3 % and the amount of CW was 90 % of the total solid content (CS3/CW90). The particle size of CS3/CW90 was in the range of 0.5-0.7 µm, and the Cobb60 value, water contact angle and the kit ratings of paper coated with CS3/CW90 achieved 7.5 g/m2, 130.9° and 12/12, respectively, and the coated paper also exhibited excellent thermal stability and high antibacterial rate of 99.1 %, demonstrating its great potential for application in multi-functional food packaging.

Chitosan-graft-poly(lactic acid)/CD-MOFs degradable composite microspheres for sustained release of curcumin.

The solubility of cyclodextrin metal-organic frameworks (CD-MOFs) in aqueous media making it not suitable as sustained-release drug carrier. Here, curcumin-loaded CD-MOFs (CD-MOFs-Cur) was embedded in chitosan-graft-poly(lactic acid) (CS-LA) via a solid-in-oil-in-oil (s/o/o) emulsifying solvent evaporation method forming the sustained-release composite microspheres. At CS-LA concentration of 20 mg/mL, the composite microspheres showed good sphericity. The average particle size of CS-LA/CD-MOFs-Cur (2:1), CS-LA/CD-MOFs-Cur (4:1) and CS-LA/CD-MOFs-Cur (6:1) composite microspheres was about 9.3, 12.3 and 13.5 µm, respectively. The above composite microspheres exhibited various degradation rates and curcumin release rates. Treating in HCl solution (pH 1.2) for 120 min, the average particle size of above microspheres reduced 28.19 %, 24.34 % and 6.19 %, and curcumin released 86.23 %, 78.37 % and 52.57 %, respectively. Treating in PBS (pH 7.4) for 12 h, the average particle size of above microspheres reduced 30.56 %, 26.56 % and 10.66 %, and curcumin released 68.54 %, 54.32 % and 31.25 %, respectively. Moreover, the composite microspheres had a favorable cytocompatibility, with cell viability of higher than 90 %. These composite microspheres open novel opportunity for sustained drug release of CD-MOFs.

High mass loading paper-based electrode material with cellulose fibers under coordination of zirconium oxyhydroxide nanoparticles and sulfosalicylic acid.

With the rapid expansion of the flexible electronics market, it is critical to develop high-performance flexible energy storage electrode materials. Cellulose fibers, which are sustainable, low cost, and flexible, fully meet the requirements of flexible electrode materials, but they are electrically insulating and cause a decrease in energy density. In this study, high-performance paper-based flexible electrode materials (PANI:SSA/Zr-CFs) were prepared with cellulose fibers and polyaniline. A high mass loading of polyaniline was wrapped on zirconia hydroxide-modified cellulose fibers under metal-organic acid coordination through a facile in situ chemical polymerization process. The increase in mass loading of PANI on cellulose fibers not only improves the electrical conductivity but also enhances the area-specific capacitance of the flexible electrodes. The results of electrochemical tests show that the area specific capacitance of the PANI:SSA/Zr-CFs electrode is 4181 mF/cm2 at 1 mA/cm2, which is more than two times higher than that of the electrode with PANI on pristine CFs. This work provides a new strategy for the design and manufacture of high-performance flexible electronic electrodes based on cellulose fibers.

Evaluation of oxy-organosolv pretreatment on lignin extraction from wheat straw.

To develop a characteristic "Lignin-first" strategy, the oxy-organosolv delignification processes under mild conditions were comprehensively investigated. Results showed that lignin yield could achieve about 50 % under the optimum process conditions of ethanol concentration 80 %, temperature 90 °C, liquid to wheat straw ratio 25:1 for powdery-scale substrates, which was 65.0 % higher than that for rod-scale substrates under the same conditions. The lignin structural and carbohydrate component results demonstrated the employment of oxygen induced great quantities of lignin dissolving out on the premise of little carbohydrate component (<1 %) and lignin structural (mainly ß-O-4 units) changes. Moreover, based on the molecular weight and polydiversity comparison results, the aqueous oxygen could transfer homogeneously in mild organosolv system and result in lignin degradation uniformly. Besides, the employment of oxygen assisted in not only extending the massive lignin removal stage to 30 min and 50 min for P-OEEL and R-OEEL respectively, but also boost the delignification rate with comparison to P-EL and R-EL. Lastly, the excellent anti-oxidant properties of lignin from oxy-organosolv process were demonstrated by scavenging DPPH and ABTS radicals. The economic calculations showed that the cost for lignin production were about 1.58USD/g lignin from powdery-scale wheat straw, providing a competitive route for high-value utilize waste biomass.

Multiphasic lignocellulose-based suspension for oil-water interfacial stabilization: Synergistic adsorption and phase behavior.

This study described the multiphasic and multi-sized lignocellulose-based suspension (LBS) prepared by green method and its adsorption and phase behavior at O/W interface. The LBS consisting of lignin containing microfibrils (LMFs), lignin containing cellulose nanofibers (LCNFs), and lignin nanoparticles (LNPs), was obtained by mechanical fibrillation and high-shear treatments. They had different functions in emulsion stabilization: (1) synergistic irreversible adsorption of LCNFs and LNPs limited the coalescence of droplets and formed micro-sized droplets; (2) droplets filled in the LMFs network creating a strong fiber-droplet network structure. The fluorescent micrographs confirmed the synergistic irreversible adsorption of LCNFs and LNPs on the surface of the droplets, which was conductive to the high interfacial stability. The droplets were deformed rather than being destroyed under the high flow speed. The increasing viscosity, improving gel-like behavior, decreasing creep compliance and increasing yield stress demonstrated that the internal droplets can support the fiber network to delay the destruction under shear force. And the fiber-droplet network can automatically regenerate in situ after completed destruction.

Enhanced paper sludge dewatering and in-depth mechanism by oxalic acid/Fe2+/persulfate process.

As a typical advanced oxidation process, Fe2+-persulfate (PDS) oxidation technology has been widely and efficiently reported for enhancing sludge dewaterability. However, higher dosage of Fe2+ must be added, which will restrain the oxidation efficiency of Fe2+-PDS process. In this work, the oxalic acid (OA)/Fe2+-PDS process was studied to improve paper sludge dewatering. With the OA dosage of 6 µmol (g total solid (TS))-1, Fe2+ dosage of 0.3 mmol (g TS)-1, and PDS dosage of 0.6 mmol (g TS)-1, sludge dewaterability was improved more efficiently. The specific resistance to filtration and water content of sludge cake were decreased by 70.7% and 8.0%, respectively. In comparison with Fe2+-PDS process, the viscosities of sludge suspension and supernatant were further reduced by 3.73% and 51.77%, respectively, and the contents of extracellular polymeric substances fractions were increased. The improved sludge dewaterability in OA/Fe2+-PDS process was mainly contributed by the synergistic effect of oxidative disintegration by free radicals and flocs re-flocculation, the contributions of which were the orders: metal cations > sulfate radical > hydroxyl radical. OA enhanced the efficient disintegration of sludge flocs, released more bound water, generated more Fe3+-oxalate complexes, and finally increased the sludge particle size significantly, forming a larger aggregation and obvious cracks. Additionally, the stabilization of several heavy metals was improved due to the chelating capacity of OA. These works will provide a novel approach for sludge dewatering in the PDS oxidation process.

Green and Efficient Preparation of Tailed Lignin Nanoparticles and UV Shielding Composite Films.

Lignin nanoparticles (LNP) with various morphologies could be prepared with solvent-antisolvent methods. However, the employed toxic chemicals limited its large-scale application. In this study, an extremely green method using only ethanol and water as solvent and antisolvent was reported. Besides, with the syringaldehyde (SA) addition and its anchoring action on the lignin particles, a forming process of the tailed structure was observed and resulted. Moreover, the improved electronegativity originating from the phenolic hydroxyl groups enhanced the size distribution uniformity, and the new absorption peaks at 1190 cm-1 demonstrated the involvement of SA in the LNP formation. Lastly, the tailed lignin nanoparticles (T-LNP) composited with, respectively, polyvinyl alcohol, chitosan, cellulose nanofibers, cationic etherified starch, and sodium alginate were successfully prepared. The outstanding UV-shielding and free radical scavenging properties in the above composites showed their great potential in wide applications in packaging materials.

Preparation and properties of chitosan/guar gum/nanocrystalline cellulose nanocomposite films.

Nanocrystalline cellulose (NCC) has shown great potential for reinforcing nanocomposite systems, particularly in biopolymer-based nanocomposites. In the present work, transparent and biodegradable chitosan (CH)/guar gum (GG)/NCC nanocomposite films were designed and prepared. The effect of NCC loadings on the rheological behavior of the as-prepared nanocomposite suspensions was investigated, the overall properties of the resultant nanocomposite films as a function of various amounts of NCC were determined, and the surface morphology of various nanocomposite films was characterized by scanning electron microscopy (SEM). Results indicated that the increased NCC loadings increased the shear viscosity of the nanocomposite suspensions. Moreover, as expected, the obtained CH/GG/NCC nanocomposite films were found to exhibit improved tensile strength and reduced air permeability in comparison to pure CH/GG films. This work supported the conclusion that NCC was effective in reinforcing the CH/GG composite films, which may be a promising material for food packaging applications.

Chitosan/titanium dioxide nanocomposite coatings: Rheological behavior and surface application to cellulosic paper.

Incorporation of nanofillers into a polymeric matrix has received much attention as a route to reinforced polymer nanocomposites. In the present work, an environmentally friendly chitosan (CTS)/titanium dioxide (TiO2) nanocomposite coating was designed/prepared and subsequently employed for imparting antibacterium and improved mechanical properties to cellulosic paper via surface coating. Effect of TiO2 nanoparticle loadings on the rheological behavior of nanocomposite coatings was investigated. Surface application of CTS/TiO2 nanocomposite coatings to cellulosic paper was performed, and the antibacterial activity and mechanical properties of surface-coated cellulosic paper were examined. Results showed that the increased TiO2 nanoparticle loadings decreased the viscosity and dynamic viscoelasticity of the as-prepared coatings, and improved the antibacterial activity and mechanical properties of surface-coated cellulosic paper. The optimum loading of TiO2 nanoparticles was identified at 10%. This work suggested that CTS/TiO2 nanocomposite coatings may have the potential to be used as a promising antibacterial protective coating for paper packaging.

Effect of Microwave Treatment of Graphite on the Electrical Conductivity and Electrochemical Properties of Polyaniline/Graphene Oxide Composites.

Polyaniline (PANI)/graphene oxide (GO) composites were synthesized via in situ polymerization of aniline in the presence of GO. The effect of microwave treatment of graphite on the electrical conductivity and electrochemical properties of PANI/GO composites was highlighted, and the morphology and microstructure were subsequently characterized using transmission electron microscopy, scanning electron microscopy, Fourier-transformed infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. The results demonstrated that microwave treatment of graphite imparted a well-dispersed, highly ordered layered structure to the as-prepared GO, and in turn facilitated strong bonding between the GO and PANI nanosheets, which may be responsible for the improved electrical conductivity and electrochemical properties of the resulting PANI/GO composites. The desired PANI/GO composites possessed an electrical conductivity of 508 S/m, an areal capacitance of 172.8 mF/cm², and a retained capacitance of 87.4% after cycling, representing percentage increases of 102, 232, and 112, respectively, as a result of the microwave treatment of graphite. The resulting composites are promising electrode materials for high-performance and ecofriendly electrical energy storage devices.

Extraction of cellulose nano-crystals from old corrugated container fiber using phosphoric acid and enzymatic hydrolysis followed by sonication.

Due to its amazing physicochemical properties and high environmental compatibility, cellulose nano-crystals (CNC) hold great promise for serving as a strategic platform for sustainable development. Now, there has been growing interest in the development of processes using waste or residual biomass as CNC source for addressing economic and environmental concerns. In the present work, a combined process involving phosphoric acid hydrolysis, enzymatic hydrolysis and sonication was proposed aiming to efficiently exact CNC from low-cost old corrugated container (OCC) pulp fiber. The effect of enzymatic hydrolysis on the yield and microstructure of resulting CNC was highlighted. Results showed that the enzymatic hydrolysis was effective in enhancing CNC yield after phosphoric acid hydrolysis. CNC was obtained with a yield of 23.98 wt% via the combined process with phosphoric acid concentration of 60 wt%, cellulase dosage of 2 mL (84 EGU) per 2g fiber and sonication intensity of 200 W. Moreover, the presence of enzymatic hydrolysis imparted the obtained CNC with improved dispersion, increased crystallinity and thermal stability.

Effects of chemical form of sodium on the product characteristics of alkali lignin pyrolysis.

The effects of Na as organic bound form or as inorganic salts form on the pyrolysis products characteristics of alkali lignin were investigated by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR), tube furnace and thermo-gravimetric analyzer (TGA). Results of TG-FTIR and tube furnace indicated that the two chemical forms Na reduced the releasing peak temperature of CO and phenols leading to the peak temperature of the maximum mass loss rate shifted to low temperature zone. Furthermore, organic bound Na obviously improved the elimination of alkyl substituent leading to the yields of phenol and guaiacol increased, while inorganic Na increased the elimination of phenolic hydroxyl groups promoting the formation of ethers. It was also found the two chemical forms Na had different effects on the gasification reactivity of chars. For inorganic Na, the char conversion decreased with increasing the char forming temperature, while organic bound Na was opposite.

Thermogravimetric-Fourier transform infrared spectrometric analysis of CO2 gasification of reed (Phragmites australis) kraft black liquor.

CO(2) gasification of the reed (Phragmites australis) kraft black liquor (KBL) and its water-soluble lignin (WSL) was analyzed by thermogravimetry coupled with Fourier transform infrared spectrometry (TG-FTIR). In KBL gasification, major mass loss of KBL occurred between 150 and 1000°C, followed by a further slow mass loss until the heating was stopped and the TG curve leveled off. The TG profiles of the WSL and the KBL were similar during gasification; however, the differential thermogravimetry (DTG) curves and mass decrease from 300°C of the TG curves of the WSL and the KBL were different because of their dissimilar ingredients. The CO formation mechanism was the same and independent of structural types of lignins between reed and wood in their KBL CO(2) gasification.