Lignin as a High-Value Bioaditive in 3D-DLP Printable Acrylic Resins and Polyaniline Conductive Composite.

With increasing environmental awareness, lignin will play a key role in the transition from the traditional materials industry towards sustainability and Industry 4.0, boosting the development of functional eco-friendly composites for future electronic devices. In this work, a detailed study of the effect of unmodified lignin on 3D printed light-curable acrylic composites was performed up to 4 wt.%. Lignin ratios below 3 wt.% could be easily and reproducibly printed on a digital light processing (DLP) printer, maintaining the flexibility and thermal stability of the pristine resin. These low lignin contents lead to 3D printed composites with smoother surfaces, improved hardness (Shore A increase ~5%), and higher wettability (contact angles decrease ~19.5%). Finally, 1 wt.% lignin was added into 3D printed acrylic resins containing 5 wt.% p-toluensulfonic doped polyaniline (pTSA-PANI). The lignin/pTSA-PANI/acrylic composite showed a clear improvement in the dispersion of the conductive filler, reducing the average surface roughness (Ra) by 61% and increasing the electrical conductivity by an order of magnitude (up to 10-6 S cm-1) compared to lignin free PANI composites. Thus, incorporating organosolv lignin from wood industry wastes as raw material into 3D printed photocurable resins represents a simple, low-cost potential application for the design of novel high-valued, bio-based products.

Spectroscopic and Microscopic Study of Peroxyformic Pulping of Agave Waste.

The peroxyformic process is based on the action of a carboxylic acid (mainly formic acid) and the corresponding peroxyacid. The influences of processing time (60-180 min), formic acid concentration (80-95%), temperature (60-80°C), and hydrogen peroxide concentration (2-4%) on peroxyformic pulping of agave leaves were studied by surface response methodology using a face-centered factorial design. Empirical models were obtained for the prediction of yield, κ number (KN) and pulp viscosity as functions of the aforementioned variables. Mathematical optimization enabled us to select a set of operational variables that produced the best fractionation of the material with the following results: pulp yield (26.9%), KN (3.6), and pulp viscosity (777 mL/g). Furthermore, this work allowed the description and evaluation of changes to the agave fibers during the fractionation process using different microscopic and spectroscopic techniques, and provided a comprehensive and qualitative view of the phenomena occurring in the delignification of agave fibers. The use of confocal and scanning electron microscopy provided a detailed understanding of the microstructural changes to the lignin and cellulose in the fibers throughout the process, whereas Raman spectroscopy and X-ray diffraction analysis indicated that cellulose in the pulp after treatment was mainly of type I.

Evaluation of agave fiber delignification by means of microscopy techniques and image analysis.

Recently, the use of different types of natural fibers to produce paper and textiles from agave plants has been proposed. Agave atrovirens can be a good source of cellulose and lignin; nevertheless, the microstructural changes that happen during delignification have scarcely been studied. The aim of this work was to study the microstructural changes that occur during the delignification of agave fibers by means of microscopy techniques and image analysis. The fibers of A. atrovirens were obtained from leaves using convective drying, milling, and sieving. Fibers were processed using the Acetosolv pulping method at different concentrations of acetic acid; increasing acid concentration promoted higher levels of delignification, structural damage, and the breakdown of fiber clumps. Delignification followed by spectrometric analysis and microstructural studies were carried out by light, confocal laser scanning and scanning electron microscopy and showed that the delignification process follows three stages: initial, bulk, and residual. Microscopy techniques and image analysis were efficient tools for microstructural characterization during delignification of agave fibers, allowing quantitative evaluation of the process and the development of linear prediction models. The data obtained integrated numerical and microstructural information that could be valuable for the study of pulping of lignocellulosic materials.

Milox fractionation of empty fruit bunches from Elaeis guineensis.

Milox pulping of EFB was used to obtain pulps. In the first Milox stage, the influences of operating variables on pulp properties were studied and polynomial and neural fuzzy models that reproduced the experimental results with errors less than 10% were developed. Operating variables were found (93 wt.% of formic acid, 3 wt.% of hydrogen peroxide, and 165 min) that yielded acceptable pulp properties (40.5% yield, 50.3% brightness and 608 mL/g viscosity) at reasonable chemical and energy costs. The second stage was studied by subjecting the liquors of the previously optimized first stage to different treatment times. This time should be 30 min or less, to avoid a negative effect on viscosity. The residual liquor from the first Milox stage contained virtually no precipitable lignin and only low amounts of sugar (wt.%): glucose 0.71, xylose 4.22, galactose 1.19, mannose 0.22, all on original raw material dry.

Miscanthus x giganteus bark organosolv fractionation: fate of lipophilic components and formation of valuable phenolic byproducts.

The behavior of Miscanthus x giganteus bark lipophilic extractives during three acid organosolv pulping processes (Acetosolv, formic acid fractionation, and Milox) was investigated. It was demonstrated that nearly 90% of the lipophilic extractives were removed from pulps by either dissolution in the organosolv liquors (fatty acids and alcohols) or extensive degradation (sterols). The organosolv liquors were found to be rich in vanillin, syringaldehyde, and ferulic, vanillic, and p-coumaric acids. The Acetosolv fractionation process was found to be the most efficient in the removal of lipophilic components from pulps, and it was also the process that generated higher amounts of valuable monomeric phenolic compounds that could be exploited within the biorefinery context.

Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation.

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these suitable for different applications. These results suggest that refinement of M. x giganteus via organosolv processes could potentially turn this grass into a valuable source of both fiber and lignin.

Bleaching Miscanthus x giganteus Acetosolv pulps with hydrogen peroxide/acetic acid. Part 1: Behaviour in aqueous alkaline media.

Miscanthus x giganteus bark samples subjected to fractionation by the Acetosolv process under optimal conditions were bleached using hydrogen peroxide and acetic acid in aqueous media under alkaline conditions. The influence of the main operational variables in the bleaching of Acetosolv pulps of M. x giganteus (i.e. hydrogen peroxide concentration, 3-7%; temperature, 55-75 degrees C; pH 9-11), obtained after treatments, have been assessed on pulp yield, kappa number, viscosity and brightness of bleached pulps. For this purpose, a rotatable and orthogonal second-order factorial design of experiments was used, in order to identify the optimum operating conditions. The obtained empirical mathematical models demonstrate that, in general, the bleaching was efficient, achieving pulps with kappa numbers below 10. The chemical composition and physicochemical properties of the bleached pulps fulfilled the requirements for forthcoming bleaching stages. Moreover, an alkaline extraction stage to eliminate saponifiable groups of Acetosolv pulps was studied, as well as the necessity of use chelating agents in the stage with hydrogen peroxide.