Lignosulfonate Research Articles

Lignosulfonate functionalized nanomaterials for enhancement of the electrochemical performance of polyaniline

The electrochemical enhancement of polyaniline (PANI) by adding nanomaterials is closely related with the dispersion state of the nanomaterials in PANI. Herein, we demonstrate the fabrication of well-mixed PANI/nanomaterials composites through solid-phase exfoliation and subsequent in-situ polymerization. Bulk molybdenum disulfide (MoS2) or carbon nanotube (CNT) bundles were firstly ball-milled in the presence of calcium lignosulphonate to provide lignosulfonate (LS) noncovalently functionalized MoS2 nanosheets or CNTs, which were then used as skeletons for in-situ polymerization of aniline. The resulted nanocomposites exhibited enhanced electrochemical properties as compared with pure PANI. Typically, the ternary composite PANI/MoS2-LS/CNT-LS delivered a specific capacitance of 458.9 F/g, a 63% improvement than PANI at 1 A/g in a three-electrode system. Furthermore, excellent cycle stability (86% capacitance retention after 10, 000 charge-discharge cycles) and high specific energy (10.9 Wh/kg at specific power of 265.3 W/kg) were obtained in a coin-type symmetric supercapacitor. The study provides an efficient and facile approach for fabrication of conductive polymer/nanomaterials composite for supercapacitors with good stability and performance.

Extreme environment-adaptable and fast self-healable eutectogel triboelectric nanogenerator for energy harvesting and self-powered sensing

Hydrogel-based triboelectric nanogenerators (H-TENGs) are emerging as an appealing platform for the wearable electronics owing to their attractive mechanical flexibilities and conductive properties. However, time- and energy-consuming polymerization process of hydrogel and inevitable freezing of water within hydrogel networks at sub-zero temperature severely limit the practical applications of H-TENGs. To address the issues, we herein report a transparent, stretchable, anti-freezing, and self-healable TENG based on the ultrafast fabricated eutectogels for energy harvesting and self-powered sensors. The eutectogel electrode is initially constructed by a dynamic oxidation and coordination system composed of sulfonated lignin (SL) and Fe3+. After immersed in deep eutectic solvent (DES), the obtained eutectogels with high stretchability (~450%), transparency (93.5%) and ionic conductivity (8.70 mS cm−1) can be retained even in extreme temperature as low as − 80 °C. Notably, the eutectogel assembled TENGs (E-TENGs) show high and stable electrical output performances including open-circuit voltage of 105 V, short-circuit current of 0.5 µA, short-circuit charge of 10 nC, and power density up to 53 mW m−2. The E-TENG with a self-charging system can easily light up 20 light-emitting diodes (LEDs) and charge up capacitors to drive commercial electronics by harvesting energy. Moreover, as a proof of concept, the flexible E-TENG can serve as a self-powered biomechanical sensor to realize the real-time monitoring of various human motions, which provide a promising and versatile platform for environment adaptable hydrogel-based TENG with reliable output performance and self-healing ability.

Facile Preparation of a 3D Porous Aligned Graphene-Based Wall Network Architecture by Confined Self-Assembly with Shape Memory for Artificial Muscle, Pressure Sensor, and Flexible Supercapacitor.

The development of a novel preparation strategy for 3D porous network structures with an aligned channel or wall is always in challenge. Herein, a 3D porous network composed of an aligned graphene-based wall is fabricated by a confined self-assembly strategy in which holey reduced graphene oxide (HrGO)/lignin sulfonate (Lig) composites are orientedly anchored on the framework of the Lig/single-wall carbon nanotube (Lig/SWCNT) hydrogel by vacuum-assisted filtration accompanied with confined self-assembly and followed with hydrothermal treatment. After freeze drying, the obtained ultralight Lig/SWCNT/HrGOal aerogel exhibits excellent shape memory properties and can roll back to the original shape even if suffering from a high compressive strain of 86.2%. Furthermore, the as-prepared aerogel used as a water-driven artificial muscle shows powerful driving force and can lift ultrahigh weight cargo that is 1030.6 times its own weight. When the prepared Lig/SWCNT/HrGOal aerogel is used as a pressure sensor, it also exhibits high sensitivity (2.28 kPa-1) and a wide detection region of 0.27-14.1 kPa. Additionally, the symmetric flexible supercapacitor assembled with as-prepared aerogel films shows superior stored energy performance that can tolerate 5000 cycles of bending. The present work not only fabricates a high-performance multifunctional material but also develops a new strategy for the preparation a wood-like 3D porous aligned wall network structure.

Application of Chitosan-Lignosulfonate Composite Coating Film in Grape Preservation and Study on the Difference in Metabolites in Fruit Wine

In order to solve the global problem of fruit rotting due to microbial infection and water loss after harvest, which leads to a large amount of food waste, this experiment uses degradable biological composite coating to prolong the preservation period of grapes. Chitosan (CH) and Lignosulfonate (LS) were used as Bio-based film materials, CH films, 1% CH/LS films and 2% CH/LS biomass composite films were synthesized by the classical casting method and applied to grape preservation packaging. Its preservation effect was tested by grape spoilage rate, water loss rate, hardness, soluble solids, titratable acid, and compared with plastic packaging material PE film. At the same time, 1H NMR technology combined with pattern recognition analysis (PCA) and partial least squares discriminant analysis (PLS-DA) was used to determine the nuclear magnetic resonance (NMR) of Cabernet Sauvignon, Chardonnay and Italian Riesling wines from the eastern foothills of Helan Mountain to explore the differences in metabolites of wine. The results of preservation showed that the grapes quality of CH films and 2% CH/LS coating package is better than the control group, the decay rates decreased from 37.71% to 21.63% and 18.36%, respectively, the hardness increased from 6.83 to 10.4 and 12.78 and the soluble solids increased from 2.1 in the control group to 3.0 and 3.2. In terms of wine metabolites, there are similar types of metabolites between cabernet Sauvignon dry red wine and Chardonnay and Italian Riesling dry white wine, but there are significant differences in content. The study found that 2% CH/LS coating package could not only reduce the spoilage rate of grapes, inhibit the consumption of soluble solids and titratable acids, but also effectively extend the shelf life of grapes by 6 days.

Effect of sodium lignosulfonate on the anti-redeposition ability of cotton cloth in a SDBS-Na2C2O4-CMC formulation

Abstract Sodium oxalate (Na2C2O4) is an excellent phosphorus-free agent, but in sodium oxalate-containing detergents with sodium dodecylbenzene sulfonate (SDBS) and sodium carboxymethyl cellulose (CMC), significant ash deposition occurs on cotton fabrics. SDBS is the main anionic surfactant in modern detergents and cotton fiber is the most commonly used textile fiber. In this study, sodium lignosulfonate (LS) was investigated for its ability to prevent redeposition in SDBS-Na2C2O4-CMC-LS formulations. The effects of LS on ash content, whiteness, optimum washing temperature, calcium oxalate morphology, zeta potential and surface tension were carefully analyzed. The results showed that the addition of LS significantly improved the prevention of ash deposits on cotton fibers. The ash content was less than 0.46% and a small amount of particles were scattered on the cotton fibers. LS showed good dispersibility but had little effect on the washing power and zeta-potential.

Mixed Ionic and Electronic Conducting Eutectogels for 3D‐Printable Wearable Sensors and Bioelectrodes

AbstractEutectogels are a new class of soft ion conductive materials that are attracting attention as an alternative to conventional hydrogels and costly ionic liquid gels to build wearable sensors and bioelectrodes. Herein, the first example of mixed ionic and electronic conductive eutectogels showing high adhesion, flexibility, nonvolatility, and reversible low‐temperature gel transition for 3D printing manufacturing is reporting. The eutectogels consist of choline chloride/glycerol deep eutectic solvent, poly(3,4‐ethylenedioxythiophene): lignin sulfonate, and gelatin as the biocompatible polymer matrix. These soft materials are flexible and stretchable, show high ionic and electronic conductivities of 7.3 and 8.7 mS cm−1, respectively, and have high adhesion energy. Due to this unique combination of properties, they could be applied as strain sensors to precisely detect physical movements. Furthermore, these soft mixed ionic electronic conductors possess excellent capacity as conformal electrodes to record epidermal physiological signals, such as electrocardiograms and electromyograms, over a long time.

Investigation on the interaction between the lipophilic structure of anionic dispersants and Shenhua non-caking coal in coal water slurry

Three anionic dispersants with different lipophilic structures and hydrophilic ends of sulfonic acid, including sodium lignin sulfonate (SLS), sulfonated acetone formaldehyde condensate (SAF) and naphthalene sulfonate formaldehyde condensate (NSF), were selected to study the effect of different lipophilic structures on the adsorption properties and dispersion mechanism. The results show that NSF and SAF are adsorbed on the surface of Shenhua non-caking coal (SNC) by single-molecular layer while SLS is adsorbed by multi-molecular layers. Through molecular dynamics simulation, the negative value of interaction energy indicates that all three dispersants can be spontaneously adsorbed on the surface of SNC. The dispersant with simple lipophilic structure has small steric hindrance during the adsorption process, which facilitate to rapidly adsorb on the coal surface with a thin layer and more adsorption sites. On the contrary, dispersants with more side chains and complex structure are adsorbed with a relatively thick layer and less adsorption sites. A dispersion mechanism of anionic dispersant on SNC surface has been proposed in this paper.

Enhancing the mechanical properties and hydrophobicity of heat-treated wood by migrating and relocating sulfonated lignin

Abstract Heat-treated wood (HTW) has better dimensional stability but worse mechanical strength than untreated wood. This study aimed to overcome this shortcoming by sulfonating lignin in Balfour spruce (Picea likiangensis var. balfouriana) wood with sulfurous acid and Na2SO3 followed by heat treatment. The mass loss of as-prepared HTW decreased while the crystallinity index increased slightly compared with those of HTW without sulfonation pretreatment. The cellulose structure of the as-prepared HTW was not damaged by the sulfonation pretreatment. The as-prepared HTW showed a higher MOE, MOR, and compressive strength (CS) of 34, 32, and 22%, respectively, compared with the HTW without sulfonation treatment. The improved mechanical properties were attributed to the increase of the relative mass fraction of lignin in the secondary walls of wood, as sulfonated lignin could migrate with water from the compound middle lamellae into the secondary wall under the combined driving forces of a concentration difference and steam pressure. These findings provide a way to enhance the mechanical properties of HTW while gaining better hydrophobicity.

Recycling of paper/wood industry waste for hydromechanical stability of expansive soils: A novel approach

This article presents a sustainable solution to repurpose paper/wood industry waste as a geotechnical construction material. A novel lignosulphonate (LS)-based composite admixture (CA) was used in this study to cope with construction problems pertaining to expansive soils. Surface water infiltration in terms of rainfall and surface water irrigation are the prime factors that cause volumetric change behavior and a drastic reduction in shear strength due to loss in suction that eventually causes failure in expansive soils. Such failures are comprised of complex hydromechanical phenomena and their remediation requires special attention. In this context, this study for the first time deals with the use of LS-based CA as a remedy to such failures in expansive soils considering the hydromechanical properties. To better understand the hydraulic response, the specially designed soil-column model tests (SCMTs) were conducted. Besides, different geotechnical experiments and microstructural analyses were carried out to analyze the hydromechanical behavior of CA treatment against the varying degree of saturation (Sr). The results showed that LS-based CA treatment increases the water holding capacity over a suction range of 78.4 kPa and air entry value (AEV) by 33%. Also, the SCMT showed that the wetting-front depth (WFD) at full saturation in CA treated expansive soil was 4–10% quicker than untreated expansive soil. In addition, for the increase in Sr from optimum to 100%, the decrease in cohesion (c) value for untreated and treated soil was found to be 88% and 39.8%, and the increase in compressibility was 37% and 17%, respectively, highlighting better resistance against Sr. Whereas, the swelling potential was completely eradicated with a significant reduction in volumetric shrinkage by 43% compared to untreated soil. The microstructural analyses showed the development of apparent aggregation with the Sr in untreated expansive soil, whereas the CA treatment-induced better structure with bigger size particles with disrupted inter and intra assemblage pore spaces. The results showed that LS-based CA manifests substantial hydromechanical stability against variation in Sr. Overall, this study provides the scientific basis to the practitioners for the pragmatic use of LS-based CA in treating expansive soil problems.

Slurryability and Influencing Mechanism of Hydrophobic Structures in Additive-Coal-Water Ternary System.

This study investigates the effects of additive adsorption onto coal particles on surface properties, hydrophobic groups on the slurryability, and the moisture occurrence form on the performance of coal water slurry (CWS). Mechanisms related to the different hydrophobic structures of the additives are proposed. The adsorption method of sulfonated acetone formaldehyde enhances the adsorption capacity of coal surfaces but is not conducive to slurrying. Sodium lignin sulfonate has hydrophobic ends with nonpolar aromatic groups, three-dimensional macromolecular structures, and complex branched chains, which provide CWS with good stability and slurryability. Naphthalenesulfonate formaldehyde has a double benzene ring structure and provides the thick but nonuniform adsorption layers on coal surfaces. The many amorphous structures and low molecular weights of sodium humic sulfonate lead to nonuniform hydration films and poor slurryability. The results of this paper provide guidance for improving synergism in coal–water–additive systems and enhancing slurry performance.

Facile fabrication of lignin containing cellulose films using water as green solvent

Sodium lignin sulfonate (SLS) containing α-cellulose film with high compatibility was fabricated via crosslinking process using water as green solvent. FTIR analysis showed that intramolecular/intermolecular hydrogen bonds were formed after water treatment. In addition, physicochemical and antibacterial properties were analyzed comprehensively and results presented that the crosslinked film showed stronger tensile strength, higher water and heat resistance as compared to the pure sample. Better UV blocking capacity and antibacterial performance were derived from the addition of SLS. After water treatment, antibacterial performance was deteriorated with the consumption of sulfonate groups to form intermolecular hydrogen bonds.

Double-Interpenetrating-Network Lignin-based Epoxy Resin Adhesives for Resistance to Extreme Environment.

The gradually depleting fossil resources and the biosafety of bisphenol A have always restricted the green development of the traditional epoxy resin field. In this Article, biomass macromolecule lignin sulfonates are selected as the raw material instead of traditional bisphenol A to prepare lignin-based epoxy resin adhesives. Lignin sulfonates are chemically modified and combined with a cross-linking agent to form lignin-based epoxy resin adhesives with double-interpenetrating-network structures. The resulting lignin-based epoxy adhesive exhibits a maximum tensile shear strength of 11.29 MPa, which is 213% higher than the strength before chemical modification. The tensile shear strength of the adhesive is still 10.13 MPa after 12 h of immersion in water (20 °C), and its tensile shear strength is 9.30 MPa after 12 h of immersion in boiling water (100 °C). The high-temperature and high-humidity environment has no significant effect on the properties of the resulting lignin-based epoxy adhesive.

High lignin containing hydrogels with excellent conducting, self-healing, antibacterial, dye adsorbing, sensing, moist-induced power generating and supercapacitance properties

Herein, we design a dynamic redox system of using high contents of lignosulfonate (LS) and Al3+ to prepare poly acrylic acid (PAA) (LS-g-PAA-Al) hydrogels. The presence of high LS and Al3+ contents, in combination with the effective Al3+ complexes formed, renders the resultant hydrogel with some unique attributes, including excellent ionic conductivity (as high as 7.38 S·m−1) and antibacterial activity; furthermore, a very fast gelation (in 1 min) was obtained. As a flexible strain sensor, the LS-g-PAA-Al hydrogel with high conductivity demonstrates superior sensitivity in human movement detection. In addition, the rich anionic hydrophilic groups, such as sulfonic groups, phenolic hydroxyl groups, in the hydrogels impart the resultant hydrogels with excellent adsorption capacity for cationic dyes: when using Rhodamine B (RB) as a model cationic dye, the adsorption capacity of the resultant hydrogel reaches 334.64 mg·g−1; as a moist-induced power generator, it generates maximum 150.5 mV open circuit voltage with moist air flow. When the hydrogel electrolyte is assembled into a supercapacitor assembly, it shows high specific capacitance of 245.4 F·g−1, with the maximum energy density of 21.8 Wh·kg−1, power density of 2.37 kW·kg−1, and capacitance retention of 95.1% after 5000 consecutive charge-discharge cycles.

Cyclic undrained properties of stabilised expansive clay with lignosulfonate

ABSTRACT In this work, the influence of lignosulfonate (LS), which is a by-product of timber and paper industries, on the cyclic characteristics of expansive clay was investigated by conducting cyclic triaxial tests. Test findings showed that cyclic stress ratio (CSR) substantially influenced liquefaction resistance of treated soil samples such that, at CSR = 0.2, none of the specimens were liquefied, whereas, at CSR = 0.4, all of the specimens were liquefied. Furthermore, liqueaction resistance was enhanced by decreasing the sample moisture content. Due to a stabilisation effect, the secant shear modulus increased by up to about 64%, and the damping ratio decreased by up to about 22%.

Remediation Analysis of Azo and Anthraquinone Dye by Modified Low Sulphonated Lignin

Industrial wastes mostly consist of dyes and pigments which are known to cause detrimental effects on environmental and human health. Various techniques can be used for the removal of dyes, among them adsorption is by far the simplest and inexpensive one. Lignocellulosic biomass which consists of the second most abundant lignin is now increasingly being explored as an adsorbent due to its structural properties. In this study, the commercial low sulfonated lignin was modified by Mannich reaction i.e. amination and was employed in the adsorption of Reactive Blue 19 and Acid orange 10. Structural characterization like FTIR, SEM, TGA substantiates the presence of the amine group. From batch adsorption studies, almost >80% removal efficiency was found for the azo dye. Docking analysis was done to understand the active site interactions.

Facile preparation of self-assembled high-performance cellulose based composite

The huge accumulation of plastic wastes is emerging as a serious threat to the ecological environment and human health. Herein, inspired by the reinforcement principle of lignin-carbohydrate complexes (LCC) in the natural trees, we design a green, highly efficient, and eco-friendly method to prepare cellulose composites with excellent performances. Cationic Guar Gum (CGG) and Lignosulfonate (LS), which are derived from biomass, are employed as raw materials to form LS-CGG complexes (LGC) acted as LCC analogs to improve the performance of the cellulose framework. Based on the principle of electrostatic interactions, a self-assembled and facile infiltrated strategy has been applied in the preparation of the LGC-filter paper complex (LGC-FP), which can be industrial-scale manufactured employing established and mature processes from pulping and papermaking industry. This work provides an eco-friendly, low-cost, and scalable route to prepare bioplastics, which is a promising alternative to address the “white pollution” and reach the carbon neutrality goal to a certain extent.

Lignin-Mediated Silver Nanoparticle Synthesis for Photocatalytic Degradation of Reactive Yellow 4G and In Vitro Assessment of Antioxidant, Antidiabetic, and Antibacterial Activities.

This study explored the potential of abundantly available sodium lignosulfonate (LS) as a reducer and fabricating agent in preparing silver nanoparticles (LS–Ag NPs). The operational conditions were optimized to make the synthesis process simpler, rapid, and eco-friendly. The prepared LS–Ag NPs were analyzed via UV–Vis spectroscopy, X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and high-resolution transmission electron microscopy. Results demonstrated that LS–Ag NPs were of crystalline structure, capped with LS constituents, and spherical in shape with a size of approximately 20 nm. Under optimized conditions, LS–Ag NPs exhibited significant photocatalytic activity in Reactive Yellow 4G degradation. The effects of photocatalyst (LS–Ag NPs) dosage, dye concentration, and its reusability for dye degradation were studied to make the process practically applicable in textile wastewater treatment. Additionally, the synthesized LS–Ag NPs displayed significant free radical scavenging against 2-diphenyl-1-picrylhydrazyl (DPPH) with an IC50 value of (50.2 ± 0.70 µg/mL) and also exhibited antidiabetic activity in terms of inhibition in the activity of carbohydrate-degrading marker enzyme α-glucosidase with an IC50 value of (58.1 ± 0.65 µg/mL). LS–Ag NPs showed substantial antibacterial potential against pathogenic strains, namely E. coli and S. aureus. In conclusion, LS–Ag NPs can be a reliable and eco-friendly material for their possible application in the treatment of dye-containing wastewater and have a great perspective in the biomedical and pharmaceutical sectors.

A renewable membrane with high ionic conductivity and thermal stability for Li-ion batteries

Traditional polyolefin membrane for lithium ion batteries (LIBs) is not renewable and it has poor thermal stability and wettability. Here, we designed a porous membrane based on the hydrogen bonding effect between the renewable cellulose nanofibers (CNF) and lignosulphonates (LS). In the membrane, the CNF endows it with good flexibility, and the functional groups can improve its wettability with the electrolyte. The LS plays the role of dispersing the CNF to form uniform porous structure. Moreover, the sulfonate groups in LS can also enhance the ionic conductivity. Under the synergistic effect of CNF and LS, the membrane exhibits high ion conductivity of 1.99 mS cm-1, high electrolyte uptake of 213% and high thermal stability up to 270 °C, which is much higher than those of commercial Celgard 2325. The LIBs with the designed separators display high capacity of 188 mAh g−1 and high voltage of 4.8 V. This research provided an efficient strategy for fabricating the membrane with low cost and high performance for LIBs.

Sulfonated lignin intercalated graphene oxide membranes for efficient proton conduction

Graphene oxide (GO) membrane has triggered great attention in proton conduction, benefitting from the well-aligned interlayer nanochannels and oxygen-containing groups. However, GO membrane exhibited a relatively low proton conductivity because of the deficiency of proton-conducting groups on basal plane. Herein, sulfonated lignin (SL) was explored as a multifunctional intercalator to prepare highly conductive GO/SL membranes. The resultant GO/SL membrane with the SL mass fraction of 100% exhibits the highest proton conductivity of 346 mS cm−1 at 80 °C, 100% RH and 7.5 mS cm−1 at 80 °C, 40% RH, which are 3 times and 13 times higher than that of pristine GO membrane, respectively. Bearing abundant sulfonic acid groups and ether bonds, SL acts as both proton donors and acceptors, affording additional proton hopping sites and forming continuous hydrogen bond network for proton transfer. The continuous interlayer nanochannels along with the low-energy-barrier proton hopping pathways render GO/SL membranes highly elevated proton conductivity. Moreover, the GO/SL membrane with the SL mass fraction of 100% achieves a significantly increased maximum power density by 162.7% up to 169.2 mW cm−2 at 60 °C, 100% RH.

Production of Urea/Acetylated-lignin Sulfonate Matrix as SRFs and an Investigation on the Effect of Hydrodynamic Conditions on Release Rate Using the Biot Number

Background: This study aimed to investigate the effect of hydrodynamic conditions on the release rate of urea/acetylated lignin sulfonate (Ac-LS) matrix as slow-release fertilizers (SRFs). Therefore, two models were developed using the mass transfer balance for the determination of finite/infinite volume of fluids and solving finite integral transformation/separation of a variable. The Biot number, validating the hydrodynamic condition, was found in these models. Methods: In this study, the urea/Ac-LS matrix fertilizer was prepared. The morphological, thermal, chemical, and mechanical properties of the LS, Ac-LS, urea, and urea/Ac-LS matrix were analyzed using Fe-SEM, TGA, XRD, and SANTAM. Finally, the nitrogen release of the matrix fertilizer was investigated at 25°C for different impeller speeds. The models were also validated using the experimental data. Results: The results showed that the thermal and mechanical resistance of urea/Ac-LS due to strong interaction increased compared to pure urea or Ac-LS. The results further showed that the external resistance on the mass transfer decreased as the impeller speed increased, and the nitrogen release rate increased as the Biot number increased in both the states, i.e., finite and infinite. Conclusion: It was also observed that the release rate in the finite environment was less than that of the infinite one in the given hydrodynamic condition initially; however, the type of environment did not affect the release rate after a while.