Synthesis of lignin-based carbon/graphene oxide foam and its application as sensors for ammonia gas detection.

The present study highlights the integration of lignin with graphene oxide (GO) and its reduced form (rGO) as a significant advancement within the bio-based products industry. Lignin-phenol-formaldehyde (LPF) resin is used as a carbon source in polyurethane foams, with the addition of 1 %, 2 %, and 4 % of GO and rGO to produce carbon structures thus producing carbon foams (CFs). Two conversion routes are assessed: (i) direct addition with rGO solution, and (ii) GO reduction by heat treatment. Carbon foams are characterized by thermal, structural, and morphological analysis, alongside an assessment of their electrochemical behavior. The thermal decomposition of samples with GO is like those having rGO, indicating the effective removal of oxygen groups in GO by carbonization. The addition of GO and rGO significantly improved the electrochemical properties of CF, with the GO2% sensors displaying 39 % and 62 % larger electroactive area than control and rGO2% sensors, respectively. Furthermore, there is a significant electron transfer improvement in GO sensors, demonstrating a promising potential for ammonia detection. Detailed structural and performance analysis highlights the significant enhancement in electrochemical properties, paving the way for the development of advanced sensors for gas detection, particularly ammonia, with the prospective market demands for durable, simple, cost-effective, and efficient devices.

Selected Kraft lignin fractions as precursor for carbon foam: Structure-performance correlation and electrochemical applications.

The rapid exhaustion of fossil fuels brings to the fore the need to search for energy efficient strategies. The conversion of lignin into advanced functional carbon-based materials is considered one of the most promising solutions for environmental protection and the use of renewable resources. This study analyzed the structure-performance correlation of carbon foams (CF) when lignin-phenol-formaldehyde (LPF) resins produced with different fractions of kraft lignin (KL) were employed as carbon source, and polyurethane foam (PU) as sacrificial mold. The lignin fractions employed were KL, fraction of KL insoluble in ethyl acetate (LFIns) and fraction of KL soluble in ethyl acetate (LFSol). The produced CFs were characterized by thermogravimetric analysis (TGA), X-ray diffractometry (XRD), Raman spectroscopy, 2D HSQC Nuclear magnetic resonance (NMR) analysis, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and electrochemical measurements. The results showed that when LFSol was employed as a partial substitute for phenol in LPF resin synthesis, the final performance of the produced CF was infinitely higher. The improved solubility parameters of LFSol along with the higher S/G ratio and ß-O-4/α-OH content after fractionation were the key to produce CF with better carbon yields (54 %). The electrochemical measurements showed that LFSol presented the highest current density (2.11 × 10-4 mA.cm-2) and the lowest value of resistance to charge transfer (0.26 KΩ) in relation to the other samples, indicating that the process of electron transfer was faster in the sensor produced with LFSol. LFSol's potential for application as an electrochemical sensor was tested as a proof of concept and demonstrated excellent selectivity for the detection of hydroquinone in water.

Improvement of UV stability of thermoplastic starch matrix by addition of selected lignin fraction - Photooxidative degradation.

This paper examines the additivation of thermoplastic starch (TPS) matrix by selected fractions of kraft lignin (KL) and correlates its structure-performance when exposed to photooxidative degradation. KL from Eucalyptus urograndis wood was refined by a sequential fractionation process in ethyl acetate (EtOAc). Films were prepared by mixing lignin fractions as additive in TPS matrix by casting and pressing. The lignin employed were KL, fraction of KL insoluble in EtOAc (INS) and fraction of KL soluble in EtOAc (SOL). The samples were exposed to accelerated aging with Ultraviolet-C light (UV-C) for 432 h. Structural changes were measured by FTIR (Fourier-Transform Infrared) spectra. Thermal properties, such as melting enthalpy, glass transition temperature and thermal decomposition, were evaluated by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetry). Morphology of the films was obtained by SEM (Scanning Electron Microscopy). Surface property of wettability was measured by contact angle. Mechanical properties were explored before and after exposure to UV-C light. It was observed that the least photodegraded films were those resulting from the addition of the lignin fraction with higher phenolic hydroxyl group content. According to structural and morphological observations, the soluble fraction (TSOL) presented the highest photoprotection and stabilizing effect as an UV-C light blocker additive on TPS matrix.

Improvements in thermal and mechanical properties of composites based on thermoplastic starch and Kraft Lignin.

Thermoplastic starch (TPS) is a widely studied biopolymer as an alternative to the use of conventional polymers. In this sense, the incorporation of fillers or reinforcements coming preferably from other substances of natural origin, can be an alternative to try to improve some mechanical and thermal properties of starch polymers. Thus, Kraft Lignin (KL), can be an excellent filler to be incorporated, since it presents mechanical and thermal properties and reduces the cost and weight of the final compounds. TPS films were prepared by casting using dimethyl sulfoxide (DMSO) as solvent and additives with 2, 4 and 8% KL. Characterization of TPS films and compositions with KL were carried out by Fourier-Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM), Thermogravimetric Analysis (TGA), Dynamic Thermomechanical Analysis (DMTA), tensile testing and contact angle. Samples were also analyzed for biodegradation and for the ability to remove contaminants in water, Metil Orange (MO), by Ultraviolet-Visible Spectroscopy (UV-Vis). The FT-IR spectra of the films showed bands typical of functional groups derived from starch and lignin, with the intensity of these bands varying among the samples studied. Micrographs revealed slightly different morphologies among the films, but all showed irregular shapes with structures that appeared as plots. Increasing the percentage of KL led to an increase in contact angle values, showing a more hydrophobic behavior. In the TGA analysis, it was possible to observe a change in the main degradation event of the films for lower temperatures, especially of TPS - 4 and 8% KL compared to the TPS film. Films with KL had the peak of maximum degradation shifted to temperatures below the starch film, where the decrease in intensity of the main peak in the TPS - 4% KL and TPS - 8% KL samples demonstrates that there was less mass loss in the event. There was also in the percentage of residue as the addition of KL was increased The DMTA analyses allowed for the conclusion that presence of KL in TPS film allowed for an increase in its energy storage property, and that the loss modulus followed a decreasing order of storage modulus values to TPS - 8% KL from TPS. For the tensile strength property only TPS - 4% KL has significant improvement, and the elongation at break showed an increase for TPS - 4 and 8% KL compared to TPS. Samples showed a continuous and progressive biodegradation process, being completely biodegraded within 10 days. The monitoring of the ability to remove contaminants from water by UV-Vis, also showed promising results of compounds for this application. The best results were obtained, in most tests, for the TPS- 4% KL films.

Forward Black Liquor Acid Precipitation: Lignin Fractionation by Ultrafiltration.

Lignin recovery from black liquor is an important task for producing valuable chemical products. Acidification processes are currently applied by pulp and paper industries for black liquor treatment, in which two main streams are produced: the precipitated lignin fraction and a lignin-lean black liquor. Membrane filtration is a suitable alternative for lignin recovery from black liquor, but studies on lignin-lean black liquor filtration are scarce. Here, we evaluated the ultrafiltration process for lignin recovery from the both fractions of black liquor acidification. The lignin-lean black liquor presented 22 wt% of total solids with 4.6 wt% of lignin. Lignin retention from the lignin-lean black liquor by the 5 kDa ultrafiltration membrane was equal to 85%, with reduction in total solid concentration from 219.8 to 68.1 g L-1. Due to the relatively high solid concentration in the lignin-lean black liquor, cake formation was the main fouling mechanism during ultrafiltrations. The precipitated lignin solution presented 4.8 wt% of total solids with equivalent lignin concentration (4.7 wt%). The used membrane was able to retain almost 100% of solids and lignin from the solution prepared from the precipitated lignin. All fouling mechanisms were responsible for flux decay in ultrafiltration of the precipitated lignin solution. Steady state fluxes for lignin-lean black liquor and precipitated lignin solution were 0.9 and 15.9 L h-1 m-2, respectively. According to TGA analyses up to 800 °C, precipitated lignin and lignin-lean black liquor presented total mass losses of 63.5% and 44.3%, respectively. Also, the permeate samples presented lower mass losses than their respective feed samples. The ultrafiltration process reduced the average weight molar mass (Mw) of the precipitated lignin solution and lignin-lean black liquor from 1817 to 486 g mol-1and from 2876 to 1095 g mol-1, respectively. Thus, the 5 kDa ultrafiltration membrane was efficient for lignin recovery from the lignin-lean black liquor, while membranes with lower cut-off should be proposed for lignin purification from the precipitated fraction.

Biodegradable hydrogel derived from cellulose acetate and EDTA as a reduction substrate of leaching NPK compound fertilizer and water retention in soil.

To study the behavior of a biodegradable hydrogel derived from cellulose acetate and ethylenediaminetetraacetic dianhydride (EDTAD), as a reduction substrate of NPK fertilizer in soil. The biodegradable hydrogel (HEDTA) was prepared from cellulose acetate (CA) with a degree substitution (DS) 2.5 by esterification crosslinking with EDTAD catalyzed by triethylamine. We systematically investigated the performance of the HEDTA in the reducing NPK (Ammonium, phosphate and potassium) fertilizer leaching. We also compare the percentage of leaching between the HEDTA and commercial fertilizers. To characterize the esterification and crosslinking between CA and EDTAD, FTIR spectroscopy and thermogravimetric analysis (DTG) were employed. The biodegradation experiments were carried out in simulated soil (23% of sand, 23% of cattle manure, 23% of soil and 31% of water) and the HEDTA was tested in the eucalyptus planting during the dry season in the São Paulo state, Brazil. The HEDTA was able to reduce the leaching of fertilizers and improve the performance of eucalyptus seedlings and reduced the mortality of the seedlings. The HEDTA showed to be an excellent substrate for slow release and water-retention in soil, reducer of the fertilizers leaching, in addition being nontoxic, biodegradable in the soil and environmentally-friendly.

Synthesis and characterization of hydrogels from cellulose acetate by esterification crosslinking with EDTA dianhydride.

Hydrogels were prepared from cellulose acetate with a degree substitution (DS) 2.5 dissolved in dimethylformamide by esterification crosslinking with Ethylenediaminetetraacetic dianhydride (EDTAD) catalyzed by triethylamine. Subsequent conversion of the unreacted carboxyl groups to sodium carboxylates by the addition of aqueous NaHCO3 was performed to enhance the water affinity of the gels. The absorbency of the products was strongly dependent on the amount of EDTAD that was esterified to cellulose acetate, and the highest absorbency was observed for the hydrogel composed of approximately 0.36 molecules of EDTAD per repeat unit of cellulose acetate. The hydrogels were synthesized with different degrees of crosslinking and were analyzed by IR spectral (FTIR), near infrared (NIR), thermogravimetry analysis (TG and DTG), and crosslink density evaluation by Flory-Rehner theory. The hydrogels have synthesized with molar ratios EDTAD/OH groups: [1/1], [1/2], and [0.1/1]. The capacity for water absorbency was studied and compared with the water absorbency of the CA.