Adsorption Characteristics of Carboxymethylated Lignin on Rigid and Soft Surfaces Probed by Quartz Crystal Microbalance.

Limited information is available on the interaction of anionically charged lignin and cationic particles, despite the promising use of anionic lignin as a coagulant and dispersant for suspension systems. The main objective of this study was to discover the fate of lignin on its interaction with rigid and soft surfaces. In this work, carboxymethylated lignin (CML) with two different charge densities were produced, and their adsorption performance on gold and poly(diallydimethylammonium chloride) (PDADMAC)-coated gold surfaces was comprehensively studied. The viscoelastic properties of adsorbed CML on the gold surface were investigated by means of quartz crystal microbalance with dissipation. A higher adsorbed amount and compact layer were observed for the adsorption of CML with a lower charge density of -1.16 meq/g (CML1). CML with a higher charge density (-2.92 meq/g), CML2, yielded a lower surface excess density of 2.31 × 10-6 mol/m2 and a higher occupied area per molecule (71.84 Å2) at the interface of water and gold sensor. Below and at equilibrium, CML2 generated a bulkier adsorption layer than did CML1 on the gold sensor and on the PDADMAC-coated sensor. Studies on the layer-by-layer (LBL) assembly of CML and PDADMAC revealed that CML1 adsorbed more greatly than CML2 on PDADMAC, and it generated a thicker but less viscoelastic layer. In this system, the greater loss to storage modulus ( G″/ G') value was achieved for CML2, indicating its looser structure in the LBL system. Studies on the LBL assembly of carboxymethylated xylan/PDADMAC and CML/PDADMAC provided concrete evidence for the fate of three-dimensional structure of CML on its adsorption performance.

Production of Flocculants, Adsorbents, and Dispersants from Lignin.

Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin contains many hydroxyl groups that can participate in chemical reactions to produce value-added products. Flocculants, adsorbents, and dispersants have a wide range of applications in industry, but they are mainly oil-based chemicals and expensive. This paper reviews the pathways to produce water soluble lignin-based flocculants, adsorbents, and dispersants. It provides information on the recent progress in the possible use of these lignin-based flocculants, adsorbents, and dispersants. It also critically discusses the advantages and disadvantages of various approaches to produce such products. The challenges present in the production of lignin-based flocculants, adsorbents, and dispersants and possible scenarios to overcome these challenges for commercial use of these products in industry are discussed.

Amphiphilic Lignin Nanoparticles Made from Lignin-Acrylic Acid-Methyl Methacrylate Copolymers.

In this study, a novel amphiphilic KL-AA-MMA nanoparticle was prepared through the graft copolymerization of kraft lignin (KL) with acrylic acid (AA) and methyl methacrylate (MMA), using potassium persulfate as an initiator in a water/dimethyl sulfoxide solvent medium, which was followed by the nanoprecipitation technique using dimethylformamide as a solvent and deionized water as an antisolvent. The successful graft polymerization was verified by 1H-nuclear magnetic resonance (NMR), 31P-NMR, and Fourier transform infrared (FTIR) analyses; and the grafting yield of the generated KL-AA-MMA copolymer ranged from 68.2% to 96.5%. Transmission electron microscopy (TEM) observation revealed the formation of amorphous KL-AA-MMA nanoparticles. Additionally, KL-AA-MMA9 nanoparticles with the highest yield exhibited the minimum hydrodynamic diameter and polydispersity of 261 nm and 0.153, respectively. Moreover, the amphiphilicity of KL-AA-MMA nanoparticles was significantly improved by the grafting of MMA monomers. Finally, the adsorption performance of KL-AA-MMA nanoparticles at the xylene interface was evaluated by a quartz crystal microbalance with dissipation (QCM-D). The results demonstrated that the most amphiphilic sample, KL-AA-MMA9 nanoparticles, with the smallest hydrodynamic size displayed the highest adsorption on the oil/water interface. This product provides a wide range of applications in oil/water emulsions.

Deposition behavior of lignin on solid surfaces assessed by stagnation point adsorption reflectometry.

The deposition behavior of lignin on a solid surface was studied using stagnation point adsorption reflectometry (SPAR) comprehensively. In this study, the light absorption coefficient of lignin (τ = 20 476 m-1) at 633 nm wavelength was considered to define a new imaginary refractive index (k) used in the SPAR technique for adsorption analysis. The inclusion of k in the adsorption model yielded an adsorbed amount (Γ) of 1.11 mg m-2, leading to the quality factor (Q f) of 31.71 mg m-2. At a lower concentration, the deposition of lignin on the surface was increased, and it generated a maximum sticking coefficient of ß = 0.71 at 25 mg L-1 on the surface. At the concentration range of 35 and 45 mg L-1, lignin formed clusters and its deposition dropped. The use of Quartz crystal microbalance (QCM) and SPAR techniques also confirmed that the proportion of water in the deposited lignin adlayer was greater when a lower concentration (5-25 mg L-1) of lignin solution was used for adsorption. The findings of this study revealed the potential use of the SPAR technique for evaluating the deposition performance of lignin-based materials on varied surfaces, which would facilitate the development of coating and composite applications for lignin.

Dual lignin-derived polymeric systems for hazardous ion removals.

The functionalization of lignin derivatives for ion removals is a promising method to expedite their use in treating industrial wastewater. In this work, kraft lignin (KL) was polymerized with [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate (METAM) or acrylic acid (AA) in an acidic aqueous suspension system to produce cationic and anionic water-soluble lignin polymers with high molecular weights. Then, the interaction of soluble ions and KL-METAM and KL-AA was investigated using a Quartz crystal microbalance (QCM) and a vertical scan analyzer (VSA). The QCM, X-ray photoelectron spectroscopy (XPS) and contact angle measurement results showed that the adsorption efficiency of KL-AA was better than KL-METAM for ions due to the stronger electrostatic interaction, cationic π-interaction, and chelation between ions and KL-AA. Based on adsorption, sedimentation, and aggregate size analyses, the dual polymer systems of KL-AA/KL-METAM were more effective than KL-METAM/KL-AA in removing ions. Among Zn2+, Cu2+, and K+; Zn2+ interacted more effectively with polymers in all scenarios because it has higher reactivity for interacting with other elements. As the efficiency of ion removals was more remarkable than past reported findings, the system of KL-AA/KL-METAM may be a promising alternative for the removal of dissolved ions from solutions.

Production and Application of Triblock Hydrolysis Lignin-Based Anionic Copolymers in Aqueous Systems.

Although lignin is currently an under-utilized biopolymer, it has the potential to be valorized through different modification pathways to yield alternative products to petroleum-based ones. In this work, hydrolysis lignin (HL) was copolymerized with acrylamide (AM) and acrylic acid (AA) under acidic conditions to generate the lignin/AM polymer (HM), lignin/AA polymer (HA), and lignin/AM/AA copolymer (HAM) with different negative charge densities and molecular weights. Lignin-based polymers characterized by advanced tools, such as proton nuclear magnetic resonance (1H NMR), gel permission chromatography (GPC), and elemental analysis confirmed the successful polymerization of HL with AM, AA, or AM/AA monomers. The adsorption analysis using a quartz crystal microbalance (QCM) revealed that compared to diblock HM and HA, the triblock copolymers of HAM adsorbed more on the Al2O3 surface and generated a bulkier adsorbed layer, which is important for lignin-based coating formulation. HAM1 with a lower charge density yielded a higher surface excess density, while HAM2 with a larger R h occupied more space (153.7 Å2) at the interface of water and Al2O3. In suspension systems, because of the higher M w, R h, and adsorption affinity, the bridging performance of HAM2 was more remarkable than that of the other lignin derivatives for Al2O3 particles via forming stronger flocs (with a deflocculation parameter, T df, of 80.6 s). However, the diblock lignin-AA (HA1) polymer showed the fastest floc regrowth capability after reducing the shear forces (with a reflocculation parameter, T rf, of 62.5 s). The high thermal stability, T g, and rheological characteristics of the HAM copolymer proved that it can be an excellent material for coating formulations and flocculants for wastewater treatment systems.

Functional Lignin Nanoparticles with Tunable Size and Surface Properties: Fabrication, Characterization, and Use in Layer-by-Layer Assembly.

Lignin is the richest source of renewable aromatics and has immense potential for replacing synthetic chemicals. The limited functionality of lignin is, however, challenging for its potential use, which motivates research for creating advanced functional lignin-derived materials. Here, we present an aqueous-based acid precipitation method for preparing functional lignin nanoparticles (LNPs) from carboxymethylated or carboxypentylated lignin. We observe that the longer grafted side chains of carboxypentylated lignin allow for the formation of larger LNPs. The functional nanoparticles have high tolerance against salt and aging time and well-controlled size distribution with Rh ≤ 60 nm over a pH range of 5-11. We further investigate the layer-by-layer (LbL) assembly of the LNPs and poly(allylamine hydrochloride) (PAH) using a stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). Results demonstrate that LNPs made of carboxypentylated lignin (i.e., PLNPs with the adsorbed mass of 3.02 mg/m2) form a more packed and thicker adlayer onto the PAH surface compared to those made of carboxymethylated lignin (i.e., CLNPs with the adsorbed mass of 2.51 mg/m2). The theoretical flux, J, and initial rate of adsorption, (dΓ/dt)0, analyses confirm that 22% of PLNPs and 20% of CLNPs arriving at the PAH surface are adsorbed. The present study provides a feasible platform for engineering LNPs with a tunable size and adsorption behavior, which can be adapted in bionanomaterial production.

Interaction Mechanism of Anionic Lignin and Cationic Soft Surface in Saline Systems.

Lignin has a complicated three-dimensional structure that is different from other synthetic and bio-based materials. In this work, we first examined the physicochemical behavior, i.e., apparent hydrodynamic radius (Rh) and ζ-potential, of carboxymethylated lignin (CM) in a saline system. Then, the detailed interaction and adsorption behavior of CM on a cationic poly(diallyldimethylammonium chloride) (PDADMAC)-coated surface were investigated in a saline system by a quartz crystal microbalance with dissipation. The theoretical and experimental adsorption data revealed that CM made limited surface coverage at a low salt concentration via charge neutralization following an intrinsic compensation mechanism. At a higher salt concentration, the adsorption of CM was improved significantly following the extrinsic compensation mechanism and nonionic interaction (e.g., hydrophobic interaction). The adsorption affinity of CM in the urea environment revealed the contribution (10-30%) of hydrogen bonding in the adsorption of CM on the PDADMAC surface. Contrary to what was found for the CM, the adsorption of a linear poly(acrylic acid-acrylamide) (PAM) on the PDADMAC surface exhibited a dramatic decrease at higher salinity, possibly due to the absence of nonionic and hydrophobic interactions between PAM and the surface. The findings of this study showed the superior adsorption performance of the lignin-based polyelectrolytes to the synthetic ones in salt-containing systems.

Preparation and characterization of novel bionanocomposite based on soluble soybean polysaccharide and halloysite nanoclay.

In this research, casting method was used to prepare novel polysaccharide-based bio-nanocomposite films with halloysite nanoclay (HNC). HNC was incorporated into soluble soybean polysaccharide (SSPS) at different concentrations (e.g., 1, 3, and 5%, w/w). Functional properties of SSPS films were evaluated following by ASTM standards. Incorporating HNC to SSPS matrix decreased water vapor permeability from 7.41 × 10(-11) to 3.27 × 10(-11) (gm(-1) s(-1) Pa(-1)) and oxygen permeability from 202 to 84 cm(3)(µm m(-2) day(-1) atm(-1)). By addition of HNC to SSPS films, glass transition temperature, tensile strength, and heat seal strength was increased and elongation at break was decreased. Uniform and smooth surface morphology revealed by scanning electron microscopy and shows no sign of phase separation among the film constitutes. In summary, HNC has the potential to be a filler in SSPS-based films for use in food and non-food packaging industries.