Search Results (31)

Various pretreatment methods, often employed in wood biorefineries, aim to disrupt the wood architecture, thereby enhancing the efficiency of hemicellulose extraction for increasing the production of bio-ethanol, bio-gas, and bio-oil, as well as improving the pulping process. Pretreatment for the pulping process has advantages such as enhanced yield in biorefined products and reducing chemicals and energy consumption. This study examined the effect of an alkaline hydrolysis of birch sawdust on the chemical composition, aggregation ability, and surface activity of soda lignin obtained by soda pulping. The alkaline hydrolysis of birch sawdust led to a remarkable removal of hemicellulose and reduced its mechanical strength. The resorption of lignin fragments on the lignocellulosic matrix during the hydrolysis was observed. The soda pulping of the original and the treated sawdust was carried out under laboratory conditions at 165 °C for 90 min, using 4.5% sodium hydroxide. A higher yield of soda lignin and pulp was obtained from the treated sawdust. The reduced content of acidic and methoxyl groups in the chemical composition of the soda lignin from the hydrolyzed sawdust was explained by the predominance of polycondensation reactions in forming its primary structure. The changes in size and zeta potential values of the formed lignin particles, as well as in the modality of the size distribution with decreasing pH, were studied. The early-proposed suggestion about the existence of structural complementarity in the formation of the ordered lignin supermolecular structures has been testified. The higher surface activity at the air–water interface for the soda lignin extracted from the hydrolyzed sawdust, compared to the lignin from the original residue, was mainly attributed to a lower content of the acidic groups in its chemical composition, shifting the hydrophilic–hydrophobic balance of its structure toward hydrophobicity. Full article

When encountering heavy oil reservoirs during drilling, due to the change in pressure difference inside the well, heavy oil will invade the drilling fluid, and drilling fluid will spill into the reservoir along the formation fractures, affecting the drilling process. A supramolecular polymer gel-based temporary plugging agent was prepared using acrylamide (AM), butyl acrylate (BA), and styrene (ST) as reacting monomers, N, N-methylenebisacrylamide (MBA) as a crosslinking agent, ammonium persulfate (APS) as an initiator, and poly(vinyl alcohol) (PVA) as a non-covalent component. A supermolecular polymer gel with a temperature tolerance of 120 °C and acid solubility of 90% was developed. The experimental results demonstrated that a mechanically robust, thermally stable supramolecular polymer gel was successfully synthesized through the copolymerization of AM, BA, and ST, as well as the in situ formation hydrogen bonding between poly (AM-co-BA-co-ST) and PVA, leading to a three-dimensional entangled structure. The gel-forming solution possessed excellent gelling performance even in the presence of a high content of salt and heavy oil, demonstrating superior resistance to salt and heavy oil under harsh reservoir conditions. High-temperature and high-pressure plugging displacement experiments proved that the supramolecular polymer gel exhibited high pressure-bearing capacity, and the blocking strength reached 5.96 MPa in a wedge-shaped fracture with a length of 30 cm. Furthermore, the dissolution rate of the supramolecular polymer gel was as high as 96.2% at 120 °C for 48 h under a 15% HCl solution condition. Full article

This work aims to present the results of evaluating the coloristic properties of polylactic acid (PLA) fibers. PLA is common nowadays in much research, as it is a biodegradable plastic from renewable sources. However, little research is devoted to PLA fibers, and even less to applied research of colored fibers. The prepared color masterbatches, created using inorganic pigments, such as titanium dioxide and carbon black, were subsequently used to prepare dyed PLA fibers in mass. The fibers were drawn to the maximum drawn ratio. The properties of the pure and dyed fibers were investigated before and after accelerated light aging using Q-SUN equipment. The changes were recorded by Fourier Transform Infrared (FTIR) spectroscopy and colorimetric properties were recorded using a device spectrometer from TECHKON SpectroDens. We also evaluated thermal properties from the first heating via differential scanning calorimetry (DSC). The measurements were taken before and after the aging of the PLA fibers, in order to see the effect of aging on the supermolecular structure, excluding the influence of the preparation process and the influence of the kind of PLA. Using inorganic pigments showed sufficient color stability even after accelerated light aging, which is beneficial for using colored fibers in practice. Full article

The research presented in this article focuses on the use of inorganic–organic material, based on titanium dioxide and lignin, as a filler for polylactide (PLA) biocomposites. To date, no research has been conducted to understand the impact of hybrid fillers consisting of TiO₂ and lignin on the supermolecular structure and crystallization abilities of polylactide. Polymer composites containing 1, 3 or 5 wt.% of hybrid filler or TiO₂ were assessed in terms of their structure, morphology, and thermal properties. Mechanical properties, including tensile testing, bending, impact strength, and hardness, were discussed. The hybrid filler is characterized by a very good electrokinetic stability at pH greater than 3–4. The addition of all fillers led to a small decrease in the glass transition temperature but, most importantly, the addition of 1% of the hybrid filler to the PLA matrix increased the degree of crystallinity of the material by up to 20%. Microscopic studies revealed differences in the crystallization behavior and nucleation ability of fillers. The use of hybrid filler resulted in higher nucleation density and shorter induction time than in unfilled PLA or PLA with only TiO₂. The introduction of small amounts of hybrid filler also affected the mechanical properties of the composites, causing an increase in bending strength and hardness. This information may be useful from a technological process standpoint and may also help to increase the range of applicability of biobased materials. Full article

This study investigates the suitability of using caffeine-treated and untreated black cherry (Prunus serotina Ehrh.) wood as a polylactide filler. Composites containing 10%, 20%, and 30% filler were investigated in terms of increasing the nucleating ability of polylactide, as well as enhancing its resistance to microorganisms. Differential scanning calorimetry studies showed that the addition of caffeine-treated wood significantly altered the crystallization behavior of the polymer matrix, increasing its crystallization temperature and degree of crystallinity. Polarized light microscopic observations revealed that only the caffeine-treated wood induced the formation of transcrystalline structures in the polylactide. Incorporation of the modified filler into the matrix was also responsible for changes in the thermal stability and decreased hydrophilicity of the material. Most importantly, the use of black cherry wood treated with caffeine imparted antifungal properties to the polylactide-based composite, effectively reducing growth of Fusarium oxysporum, Fusarium culmorum, Alternaria alternata, and Trichoderma viride. For the first time, it was reported that treatment of wood with a caffeine compound of natural origin alters the supermolecular structure, nucleating abilities, and imparts antifungal properties of polylactide/wood composites, providing promising insights into the structure-properties relationship of such composites. Full article

The organic–inorganic hybrid compound, (o-BrAH)[H₂Co(CN)₆]_0.5·(18-crown-6)_0.5·H₂O, was synthesized and characterized by variable-temperature X-ray diffraction, single-crystal diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and dielectric measurements. Single-crystal X-ray diffraction revealed a three-dimensional cage-like structure formed through the hydrogen bonds of cobalt hexacyanide, supermolecular cations, and water molecules. Temperature variation triggered an abrupt change in the cage structure and simultaneously caused dynamic oscillation of the supramolecules within the framework of [Co(CN)₆]₃⁻, inducing a phase transition accompanied by a step-like change in the dielectric physical properties. Full article

There are various types of gel materials used in a wide range of fields, and their gelation mechanisms are extremely diverse. Furthermore, in the case of hydrogels, there exist some difficulties in understanding complicated molecular mechanisms especially with water molecules interacting through hydrogen bonding as solvents. In the present work, the molecular mechanism of the structural formation of fibrous super-molecular gel by the low molecular weight gelator, N-oleyl lactobionamide/water mixture was elucidated using the broadband dielectric spectroscopy (BDS) method. The dynamic behaviors observed for the solute and water molecules indicated hierarchical structure formation processes in various time scales. The relaxation curves obtained at various temperatures in the cooling and heating processes showed relaxation processes respectively reflecting the dynamic behaviors of water molecules in the 10 GHz frequency region, solute molecules interacting with water in MHz region, and ion-reflecting structures of the sample and electrode in kHz region. These relaxation processes, characterized by the relaxation parameters, showed remarkable changes around the sol–gel transition temperature, 37.8 °C, determined by the falling ball method and over the temperature range, around 53 °C. The latter change suggested a structure formation of rod micelles appearing as precursors before cross-linking into the three-dimensional network of the supramolecular gels. These results clearly demonstrate how effective relaxation parameter analysis is for understanding the gelation mechanism in detail. Full article

The manuscript discusses the application of dimeric imidazolium ionic liquids with an aliphatic linker of different lengths, constituting a new class of compounds called gemini, for the modification of renewable materials. This innovative functionalization with the use of ionic liquids made it possible to obtain polymer composite nanomaterials with renewable fillers, which will reduce the consumption of petroleum-based raw materials and also be directly related to the reduction of energy intensity. Renewable filler in the form of nanocellulose modified with ionic liquids, as well as polymer composites with such filler obtained by extrusion and injection molding techniques, were subjected to detailed characterization using techniques like: X-ray diffraction (XRD), Fourier transform spectroscopy (FTIR), dispersion studies (DLS), morphological analysis (SEM), differential scanning calorimetry (DSC), hot-stage polarized light microscopy and characterization of mechanical properties. The use of innovative dimeric ionic liquids proved to be an effective method to carry out efficient functionalization of cellulose. This provided a stable space structure between polysaccharide particles, limiting aggregate formation. It was shown that chemical modification with ionic liquids has a significant effect on the nucleation activity of cellulose fillers and the formation of the supermolecular structure of the polymer matrix, which consequently allowed to obtain polymer composites with excellent strength characteristics and increased flexibility, which will allow to increase their application potential. Innovative ionic liquids have contributed to obtaining green nanomaterials with excellent functional properties, which have not been described in the literature so far. Full article

The progress in the practical use of glassy carbon materials has led to a considerable interest in understanding the nature of their physical properties. The electrophysical properties are among the most demanded properties. However, obtaining such materials is associated with expensive and dirty processes. In nature, in the course of geological processes, disordered sp² carbon substances were formed, the structure of which is in many respects similar to the structure of glassy carbon and black carbon, and the electrical properties are distinguished by a high-energy storage potential and a high efficiency of shielding electromagnetic radiation. Given the huge natural reserves of such carbon (for example, in the shungite rocks of Karelia) and the relative cheapness and ease of producing materials from it, the study of potential technological applications and the disclosure of some unique electrophysical properties are of considerable interest. In this paper, we present an overview of recent studies on the structure, electrophysical properties, and technological applications of natural disordered sp² carbon with the addition of novel authors’ results. Full article

Composites suitable for rotational molding technology based on poly(ε-caprolactone) (PCL) and filled with hollow glass microspheres (HGM) or functionalized hollow glass microspheres (HGMf) were prepared via melt-compounding. The functionalization of glass microspheres was carried out by a silanization treatment in order to improve the compatibility between the inorganic particles and the polymer matrix and achieve a good dispersion of glass microspheres in the matrix and an enhanced filler–polymer adhesion. The crystallization behavior of materials was studied by DSC under isothermal and non-isothermal conditions and the nucleating effect of the glass microspheres was proven. In particular, the presence of silanized glass microspheres promoted faster crystallization rates and higher nucleation activity, which are enhanced by 75% and 50%, respectively, comparing neat PCL and the composite filled with 20 wt% HGMf. The crystalline and supermolecular structure of PCL and composites crystallized from the melt was evaluated by WAXD and SAXS, highlighting differences in terms of crystallinity index and structural parameters as a function of the adopted crystallization conditions. Full article

Polymer composites with renewable lignocellulosic fillers, despite their many advantages, are susceptible to biodegradation, which is a major limitation in terms of external applications. The work uses an innovative hybrid propolis-silane modifier in order to simultaneously increase the resistance to fungal attack, as well as to ensure good interfacial adhesion of the filler–polymer matrix. Polypropylene composites with 30% pine wood content were obtained by extrusion and pressing. The samples were exposed to the fungi: white-rot fungus Coriolus versicolor, brown-rot fungus Coniophora puteana, and soft-rot fungus Chaetomium globosum for 8 weeks. Additionally, biological tests of samples that had been previously exposed to UV radiation were carried out, which allowed the determination of the influence of both factors on the surface destruction of composite materials. The X-ray diffraction, attenuated total reflectance–Fourier transform infrared spectroscopy, and mycological studies showed a significant effect of the modification of the lignocellulose filler with propolis on increasing the resistance to fungi. Such composites were characterized by no changes in the supermolecular structure and slight changes in the intensity of the bands characteristic of polysaccharides and lignin. In the case of systems containing pine wood that had not been modified with propolis, significant changes in the crystalline structure of polymer composites were noted, indicating the progress of decay processes. Moreover, the modification of the propolis-silane hybrid system wood resulted in the inhibition of photo- and biodegradation of WPC materials, as evidenced only by a slight deterioration in selected strength parameters. The applied innovative modifying system can therefore act as both an effective and ecological UV stabilizer, as well as an antifungal agent. Full article

Two new Cu(II) crystals, {[Cu(dtp)]·H₂O}_n (1) and [Cu(Hdtp)(bdc)_0.5]_n (2) (H₂dtp = 4′-(3,5-dicarboxyphenyl)-2,2′:6′,2‴-terpyridine, H₂bdc = 1,4-benzenedicarboxylic acid) were synthesized under hydrothermal conditions. X-ray single-crystal structural analysis revealed that the 5-connective Cu(II) is in a distorted tetragonal-pyramidal coordination sphere for both compounds. Crystal 1 shows a “wave-shaped” 2D layer in the structure, while 2 bears a 1D coordination chain structure and a supermolecular 2D layer structure with a thickness of 7.9 Å via 1D chain stacking. PXRD and TGA measurements showed that 1 and 2 are air stable, with thermal stabilities near 300 °C. Full article

In this paper, native cellulose I was subjected to alkaline treatment. As a result, cellulose I was transformed to cellulose II and some nanometric particles were formed. Both polymorphic forms of cellulose were modified with poly(ethylene glycol) (PEG) and then used as fillers for polyurethane. Composites were prepared in a one-step process. Cellulosic fillers were characterized in terms of their chemical (Fourier transformation infrared spectroscopy) and supermolecular structure (X-ray diffraction), as well as their particle size. Investigation of composite polyurethane included measurements of density, characteristic processing times of foam formation, compression strength, dimensional stability, water absorption, and thermal conductivity. Much focus was put on the application aspect of the produced insulation polyurethane foams. It was shown that modification of cellulosic filler with poly(ethylene glycol) has a positive influence on formation of polyurethane composites—if modified filler was used, the values of compression strength and density increased, while water sorption and thermal conductivity decreased. Moreover, it was proven that the introduction of cellulosic fillers into the polyurethane matrix does not deteriorate the strength or thermal properties of the foams, and that composites with such fillers have good application potential. Full article

In the last few years, the scientific community around the world has devoted a lot of attention to the search for the best methods of obtaining nanocellulose. In this work, nanocellulose was obtained in enzymatic reactions with strictly defined dispersion and structural parameters in order to use it as a filler for polymers. The controlled enzymatic hydrolysis of the polysaccharide was carried out in the presence of cellulolytic enzymes from microscopic fungi—Trichoderma reesei and Aspergillus sp. It has been shown that the efficiency of bioconversion of cellulose material depends on the type of enzymes used. The use of a complex of cellulases obtained from a fungus of the genus Trichoderma turned out to be an effective method of obtaining cellulose of nanometric dimensions with a very low polydispersity. The effect of cellulose enzymatic reactions was assessed using the technique of high-performance liquid chromatography coupled with a refractometric detector, X-ray diffraction, dynamic light scattering and Fourier transform infrared spectroscopy. In the second stage, polypropylene composites with nanometric cellulose were obtained by extrusion and injection. It was found by means of X-ray diffraction, hot stage optical microscopy and differential scanning calorimetry that nanocellulose had a significant effect on the supermolecular structure, nucleation activity and the course of phase transitions of the obtained polymer nanocomposites. Moreover, the obtained nanocomposites are characterized by very good strength properties. This paper describes for the first time that the obtained cellulose nanofillers with defined parameters can be used for the production of polymer composites with a strictly defined polymorphic structure, which in turn may influence future decision making about obtaining materials with controllable properties, e.g., high flexibility, enabling the thermoforming process of packaging. Full article

In the last decade, an increasingly common method of maize stover management is to use it for energy generation, including anaerobic digestion for biogas production. Therefore, the aim of this study was to provide a chemical and structural characterization of maize stover fractions and, based on these parameters, to evaluate the potential application of these fractions, including for biogas production. In the study, maize stover fractions, including cobs, husks, leaves and stalks, were used. The biomass samples were characterized by infrared spectroscopy (FTIR), X-ray diffraction and analysis of elemental composition. Among all maize stover fractions, stalks showed the highest C:N ratio, degree of crystallinity and cellulose and lignin contents. The high crystallinity index of stalks (38%) is associated with their high cellulose content (44.87%). FTIR analysis showed that the spectrum of maize stalks is characterized by the highest intensity of bands at 1512 cm⁻¹ and 1384 cm⁻¹, which are the characteristic bands of lignin and cellulose. Obtained results indicate that the maize stover fraction has an influence on the chemical and structural parameters. Moreover, presented results indicate that stalks are characterized by the most favorable chemical parameters for biogas production. Full article