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19 pages, 1917 KiB

Open AccessArticle

Comparative Study of Green and Traditional Routes for Cellulose Extraction from a Sugarcane By-Product

by Francisca Casanova, Ricardo Freixo, Carla F. Pereira, Alessandra B. Ribeiro, Eduardo M. Costa, Manuela E. Pintado and Óscar L. Ramos

Polymers 2023, 15(5), 1251; https://doi.org/10.3390/polym15051251 - 1 Mar 2023

Cited by 9 | Viewed by 4342

Abstract

Sugarcane bagasse (SCB) is the main residue of the sugarcane industry and a promising renewable and sustainable lignocellulosic material. The cellulose component of SCB, present at 40–50%, can be used to produce value-added products for various applications. Herein, we present a comprehensive and [...] Read more.

Sugarcane bagasse (SCB) is the main residue of the sugarcane industry and a promising renewable and sustainable lignocellulosic material. The cellulose component of SCB, present at 40–50%, can be used to produce value-added products for various applications. Herein, we present a comprehensive and comparative study of green and traditional approaches for cellulose extraction from the by-product SCB. Green methods of extraction (deep eutectic solvents, organosolv, and hydrothermal processing) were compared to traditional methods (acid and alkaline hydrolyses). The impact of the treatments was evaluated by considering the extract yield, chemical profile, and structural properties. In addition, an evaluation of the sustainability aspects of the most promising cellulose extraction methods was performed. Among the proposed methods, autohydrolysis was the most promising approach in cellulose extraction, yielding 63.5% of a solid fraction with ca. 70% cellulose. The solid fraction showed a crystallinity index of 60.4% and typical cellulose functional groups. This approach was demonstrated to be environmentally friendly, as indicated by the green metrics assessed (E(nvironmental)-factor = 0.30 and Process Mass Intensity (PMI) = 20.5). Autohydrolysis was shown to be the most cost-effective and sustainable approach for the extraction of a cellulose-rich extract from SCB, which is extremely relevant for aiming the valorization of the most abundant by-product of the sugarcane industry. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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18 pages, 4006 KiB

Open AccessArticle

Drying of the Natural Fibers as A Solvent-Free Way to Improve the Cellulose-Filled Polymer Composite Performance

by Stefan Cichosz and Anna Masek

Polymers 2020, 12(2), 484; https://doi.org/10.3390/polym12020484 - 21 Feb 2020

Cited by 20 | Viewed by 4838

Abstract

When considering cellulose (UFC100) modification, most of the processes employ various solvents in the role of the reaction environment. The following article addresses a solvent-free method, thermal drying, which causes a moisture content decrease in cellulose fibers. Herein, the moisture content in UFC100 [...] Read more.

When considering cellulose (UFC100) modification, most of the processes employ various solvents in the role of the reaction environment. The following article addresses a solvent-free method, thermal drying, which causes a moisture content decrease in cellulose fibers. Herein, the moisture content in UFC100 was analyzed with spectroscopic methods, thermogravimetric analysis, and differential scanning calorimetry. During water desorption, a moisture content drop from approximately 6% to 1% was evidenced. Moreover, drying may bring about a specific variation in cellulose’s chemical structure. These changes affected the cellulose-filled polymer composite’s properties, e.g., an increase in tensile strength from 17 MPa for the not-dried UFC100 to approximately 30 MPa (dried cellulose; 24 h, 100 °C) was observed. Furthermore, the obtained tensile test results were in good correspondence with Payne effect values, which changed from 0.82 MPa (not-dried UFC100) to 1.21 MPa (dried fibers). This raise proves the reinforcing nature of dried UFC100, as the Payne effect is dependent on the filler structure’s development within a polymer matrix. This finding paves new opportunities for natural fiber applications in polymer composites by enabling a solvent-free and efficient cellulose modification approach that fulfils the sustainable development rules. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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15 pages, 3090 KiB

Open AccessArticle

Simple One Pot Preparation of Chemical Hydrogels from Cellulose Dissolved in Cold LiOH/Urea

by Jiayi Yang, Bruno Medronho, Björn Lindman and Magnus Norgren

Polymers 2020, 12(2), 373; https://doi.org/10.3390/polym12020373 - 7 Feb 2020

Cited by 28 | Viewed by 6337

Abstract

In this work, non-derivatized cellulose pulp was dissolved in a cold alkali solution (LiOH/urea) and chemically cross-linked with methylenebisacrylamide (MBA) to form a robust hydrogel with superior water absorption properties. Different cellulose concentrations (i.e., 2, 3 and 4 wt%) and MBA/glucose molar ratios [...] Read more.

In this work, non-derivatized cellulose pulp was dissolved in a cold alkali solution (LiOH/urea) and chemically cross-linked with methylenebisacrylamide (MBA) to form a robust hydrogel with superior water absorption properties. Different cellulose concentrations (i.e., 2, 3 and 4 wt%) and MBA/glucose molar ratios (i.e., 0.26, 0.53 and 1.05) were tested. The cellulose hydrogel cured at 60 °C for 30 min, with a MBA/glucose molar ratio of 1.05, exhibited the highest water swelling capacity absorbing ca. 220 g H₂O/g dry hydrogel. Moreover, the data suggest that the cross-linking occurs via a basic Michael addition mechanism. This innovative procedure based on the direct dissolution of unmodified cellulose in LiOH/urea followed by MBA cross-linking provides a simple and fast approach to prepare chemically cross-linked non-derivatized high-molecular-weight cellulose hydrogels with superior water uptake capacity. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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15 pages, 3424 KiB

Open AccessArticle

Revisiting the Dissolution of Cellulose in NaOH as “Seen” by X-rays

by Birte Martin-Bertelsen, Erika Andersson, Tobias Köhnke, Artur Hedlund, Lars Stigsson and Ulf Olsson

Polymers 2020, 12(2), 342; https://doi.org/10.3390/polym12020342 - 5 Feb 2020

Cited by 16 | Viewed by 4154

Abstract

Cotton production is reaching a global limit, leading to a growing demand for bio-based textile fibers produced by other means. Textile fibers based on regenerated cellulose from wood holds great potential, but in order to produce fibers, the components need to be dissolved [...] Read more.

Cotton production is reaching a global limit, leading to a growing demand for bio-based textile fibers produced by other means. Textile fibers based on regenerated cellulose from wood holds great potential, but in order to produce fibers, the components need to be dissolved in suitable solvents. Furthermore, the dissolution process of cellulose is not yet fully understood. In this study, we investigated the dissolution state of microcrystalline cellulose in aqueous NaOH by using primarily scattering methods. Contrary to previous findings, this study indicated that cellulose concentrations of up to 2 wt % are completely molecularly dissolved in 8 wt % NaOH. Scattering data furthermore revealed the presence of semi-flexible cylinders with stiff segments. In order to improve the dissolution capability of NaOH, the effects of different additives have been of interest. In this study, scattering data indicated that the addition of ZnO decreased the formation of aggregates, while the addition of PEG did not improve the dissolution properties significantly, although preliminary NMR data did suggest a weak attraction between PEG and cellulose. Overall, this study sheds further light on the dissolution of cellulose in NaOH and highlights the use of scattering methods to assess solvent quality. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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11 pages, 5055 KiB

Open AccessArticle

Microfibrillated Cellulose Suspension and Its Electrorheology

by Kisuk Choi, Jae Do Nam, Seung Hyuk Kwon, Hyoung Jin Choi, Md Sakinul Islam and Nhol Kao

Polymers 2019, 11(12), 2119; https://doi.org/10.3390/polym11122119 - 17 Dec 2019

Cited by 18 | Viewed by 3533

Abstract

Microfibrillated cellulose (MFC) particles were synthesized by a low-pressure alkaline delignification process, and their shape and chemical structure were investigated by SEM and Fourier transformation infrared spectroscopy, respectively. As a novel electrorheological (ER) material, the MFC particulate sample was suspended in insulating oil [...] Read more.

Microfibrillated cellulose (MFC) particles were synthesized by a low-pressure alkaline delignification process, and their shape and chemical structure were investigated by SEM and Fourier transformation infrared spectroscopy, respectively. As a novel electrorheological (ER) material, the MFC particulate sample was suspended in insulating oil to fabricate an ER fluid. Its rheological properties—steady shear stress, shear viscosity, yield stress, and dynamic moduli—under electric field strength were characterized by a rotational rheometer. The MFC-based ER fluid demonstrated typical ER characteristics, in which the shear stresses followed the Cho–Choi–Jhon model well under electric field strength. In addition, the solid-like behavior of the ER fluid was investigated with the Schwarzl equation. The elevated value of both dynamic and elastic yield stresses at applied electric field strengths was well described using a power law model (~E^1.5). The reversible and quick response of the ER fluid was also illustrated through the on–off test. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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21 pages, 8211 KiB

Open AccessArticle

Effects of Cellulose Nanocrystals and Cellulose Nanofibers on the Structure and Properties of Polyhydroxybutyrate Nanocomposites

by Bobo Zhang, Chongxing Huang, Hui Zhao, Jian Wang, Cheng Yin, Lingyun Zhang and Yuan Zhao

Polymers 2019, 11(12), 2063; https://doi.org/10.3390/polym11122063 - 11 Dec 2019

Cited by 100 | Viewed by 6750

Abstract

One of the major obstacles for polyhydroxybutyrate (PHB), a biodegradable and biocompatible polymer, in commercial applications is its poor elongation at break (~3%). In this study, the effects of nanocellulose contents and their types, including cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) on [...] Read more.

One of the major obstacles for polyhydroxybutyrate (PHB), a biodegradable and biocompatible polymer, in commercial applications is its poor elongation at break (~3%). In this study, the effects of nanocellulose contents and their types, including cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) on the crystallization, thermal, and mechanical properties of PHB composites were systematically compared. We explored the toughening mechanisms of PHB by adding CNCs and cellulose CNFs. The results showed that when the morphology of bagasse nanocellulose was rod-like and its content was 1 wt %, the toughening modification of PHB was the best. Compared with pure PHB, the elongation at break and Young’s modulus increased by 91.2% and 18.4%, respectively. Cellulose nanocrystals worked as heterogeneous nucleating agents in PHB and hence reduced its crystallinity and consequently improved the toughness of PHB. This simple approach could potentially be explored as a strategy to extend the possible applications of this biopolymer in packaging fields. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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16 pages, 2374 KiB

Open AccessArticle

Development of Bilayer Biodegradable Composites Containing Cellulose Nanocrystals with Antioxidant Properties

by Eliezer Velásquez, Adrián Rojas, Constanza Piña, María José Galotto and Carol López de Dicastillo

Polymers 2019, 11(12), 1945; https://doi.org/10.3390/polym11121945 - 26 Nov 2019

Cited by 24 | Viewed by 3360

Abstract

The interest in the development of novel biodegradable composites has increased over last years, and multilayer composites allow the design of materials with functionality and improved properties. In this work, bilayer structures based on a coated zein layer containing quercetin and cellulose nanocrystals [...] Read more.

The interest in the development of novel biodegradable composites has increased over last years, and multilayer composites allow the design of materials with functionality and improved properties. In this work, bilayer structures based on a coated zein layer containing quercetin and cellulose nanocrystals (CNC) over an extruded poly(lactic acid) (PLA) layer were developed and characterized. Bilayer composites were successfully obtained and presented a total thickness of approx. 90 µm. The coated zein layer and quercetin gave a yellowish tone to the composites. The incorporation of the zein layer containing CNC decreased the volatile release rate during thermal degradation. Regarding to mechanical properties, bilayer composites presented lower brittleness and greater ductility evidenced by a lower Young’s modulus and higher elongation values. Water permeability values of bilayer composites greatly increased with humidity and the zein coated layer containing quercetin increased this effect. Experimental data of quercetin release kinetics from bilayer structures indicated a higher release for an alcoholic food system, and the incorporation of cellulose nanocrystals did not influence the quercetin diffusion process. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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19 pages, 10676 KiB

Open AccessArticle

Cellulose Nanocrystals from Fibers of Macauba (Acrocomia Aculeata) and Gravata (Bromelia Balansae) from Brazilian Pantanal

by Ana Carolina Corrêa, Vitor Brait Carmona, José Alexandre Simão, Fabio Galvani, José Manoel Marconcini and Luiz Henrique Capparelli Mattoso

Polymers 2019, 11(11), 1785; https://doi.org/10.3390/polym11111785 - 1 Nov 2019

Cited by 16 | Viewed by 3563

Abstract

Cellulose nanocrystals (CNC) were obtained from macauba and gravata fibers. Macauba (or Bocaiuva) is a palm tree found throughout most of Brazil and Gravata is an abundant kind of bromelia with 1–2m long leaves, found in Brazilian Pantanal and Cerrado. The raw fibers [...] Read more.

Cellulose nanocrystals (CNC) were obtained from macauba and gravata fibers. Macauba (or Bocaiuva) is a palm tree found throughout most of Brazil and Gravata is an abundant kind of bromelia with 1–2m long leaves, found in Brazilian Pantanal and Cerrado. The raw fibers of both fibers were mercerized with NaOH solutions and bleached; they were then submitted to acid hydrolysis using H₂SO₄ at 45 °C, varying the hydrolysis time from 15 up to 75 min. The fibers were analyzed by X-ray diffraction (XRD), FTIR Spectroscopy, scanning electron microscopy (SEM) and thermal stability by thermogravimetric analysis (TG). XRD patterns did not present changes in the crystal structure of cellulose after mercerization, but it was observed a decrease of hemicellulose and lignin contents, and consequently an increase of cellulose content with the increase of NaOH solution concentration in the mercerization. After acid hydrolysis, the cellulose nanocrystals (CNC) were also analyzed by transmission electron microscopy (TEM) which showed an acicular or rod-like aspect and nanometric dimensions of CNC from both fibers, but the higher values of aspect ratio (L/D) were found on CNC obtained from gravata after 45 min of acid hydrolysis. The mercerization and subsequent bleaching of fibers influenced the crystallinity index and thermal stability of the resulting CNC, but their properties are mainly influenced by the hydrolysis time, i. e., there is an increase in crystallinity and thermal stability up to 45 min of hydrolysis, after this time, both properties decrease, probably due to the cellulose degradation by the sulfuric acid. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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11 pages, 1996 KiB

Open AccessArticle

Characterization of Hydrothermal Deposition of Copper Oxide Nanoleaves on Never-Dried Bacterial Cellulose

by W. Ross Warren and Dennis R. LaJeunesse

Polymers 2019, 11(11), 1762; https://doi.org/10.3390/polym11111762 - 27 Oct 2019

Cited by 3 | Viewed by 3256

Abstract

Bacterial cellulose (BC) has attracted a great deal of interest due to its green synthesis and biocompatibility. The nanoscale dimension of BC nanofibers generates an enormous surface area that enhances interactions with water and soluble components within aqueous solution. Recent work has demonstrated [...] Read more.

Bacterial cellulose (BC) has attracted a great deal of interest due to its green synthesis and biocompatibility. The nanoscale dimension of BC nanofibers generates an enormous surface area that enhances interactions with water and soluble components within aqueous solution. Recent work has demonstrated that BC is a versatile platform for the formation of metal/metal oxide nanocomposites. Copper oxide (CuO) is a useful material to compare nanomaterial deposition on BC with other cellulosic materials because of copper’s colorimetric reaction as it forms copper hydroxide (Cu(OH)₂) and transitions to CuO. In this research, we found that never-dried BC readily deposits CuO into its matrix in a way that does not occur on cotton, dried BC, or regenerated cellulose fibers. We conclude that hydroxyl group availability does not adequately explain our results and that intrafibrillar pores in never-dried BC nanofibers play a critical role in CuO deposition. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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14 pages, 1501 KiB

Open AccessArticle

Evolution of Dielectric Behavior of Regenerated Cellulose Film during Isothermal Dehydration Monitored in Real Time via Dielectric Spectroscopy

by Hao Zhao, Zhen Chen and Xianfeng Du

Polymers 2019, 11(11), 1749; https://doi.org/10.3390/polym11111749 - 24 Oct 2019

Cited by 8 | Viewed by 3392

Abstract

The dielectric relaxation behavior of a regenerated cellulose (RC) film during isothermal dehydration was monitored in real time via dielectric spectroscopy, in order to investigate on one hand the influence of water on its dynamics and the variation of microstructure and phase composition [...] Read more.

The dielectric relaxation behavior of a regenerated cellulose (RC) film during isothermal dehydration was monitored in real time via dielectric spectroscopy, in order to investigate on one hand the influence of water on its dynamics and the variation of microstructure and phase composition during dehydration on the other. The progression of water loss is clearly revealed by the evolution of the dielectric relaxation behavior with drying time, which suggests two distinctly different drying stages separated by a striking transition period. The dielectric relaxation behavior at the first drying stage is found overwhelmingly dominated by ionic motion, and that at the second stage is basically a result of molecular dynamics. The mechanisms of these relaxations are proposed, through which the influence of water on the dynamics of the RC film and the variation of the microstructure and phase composition of the film at different hydration state are discussed in detail. An interesting finding is that highly ordered but noncrystalline arrangement of cellulose molecules exists, but it can be formed only when the film is in specific hydration state. This study demonstrates that dielectric spectroscopy is an effective tool in real-time monitoring kinetic process. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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9 pages, 1806 KiB

Open AccessArticle

Partially Acetylated Cellulose Dissolved in Aqueous Solution: Physical Properties and Enzymatic Hydrolysis

by Gilad Alfassi, Dmitry M. Rein, Avi Shpigelman and Yachin Cohen

Polymers 2019, 11(11), 1734; https://doi.org/10.3390/polym11111734 - 23 Oct 2019

Cited by 8 | Viewed by 3653

Abstract

Cellulose acetate is one of the most important cellulose derivatives. The use of ionic liquids in cellulose processing was recently found to act both as a solvent and also as a reagent. A recent study showed that cellulose dissolution in the ionic liquid [...] Read more.

Cellulose acetate is one of the most important cellulose derivatives. The use of ionic liquids in cellulose processing was recently found to act both as a solvent and also as a reagent. A recent study showed that cellulose dissolution in the ionic liquid 1-ethyl-3-methylimidazoliumacetate (EMIMAc) mixed with dichloromethane (DCM) resulted in controlled homogenous cellulose acetylation; yielding water-soluble cellulose acetate (WSCA). This research investigated the properties of cellulose acetate prepared in this manner, in an aqueous solution. The results revealed that WSCA fully dissolves in water, with no significant sign of molecular aggregation. Its conformation in aqueous solution exhibited a very large persistence length, estimated as over 10 nm. The WSCA exhibited surface activity, significantly reducing the surface tension of water. Because of the molecular dissolution of WSCA in water, augmented by its amphiphilicity, aqueous solutions of WSCA exhibited an overwhelmingly high rate of enzymatic hydrolysis. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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8 pages, 866 KiB

Open AccessCommunication

Side Chain Effect of Hydroxypropyl Cellulose Derivatives on Reflection Properties

by Kenichiro Hayata and Seiichi Furumi

Polymers 2019, 11(10), 1696; https://doi.org/10.3390/polym11101696 - 16 Oct 2019

Cited by 15 | Viewed by 3098

Abstract

Some cellulose derivatives are known to exhibit thermotropic and lyotropic cholesteric liquid crystal (CLC) phases with a visible reflection feature by changing the side chains and mixing with specific solvents, respectively. Although many studies have been reported so far, most of the derivatives [...] Read more.

Some cellulose derivatives are known to exhibit thermotropic and lyotropic cholesteric liquid crystal (CLC) phases with a visible reflection feature by changing the side chains and mixing with specific solvents, respectively. Although many studies have been reported so far, most of the derivatives have the side chains of linear alkyl groups, but not the bulky phenyl groups. In this report, we synthesized a series of hydroxypropyl cellulose (HPC) derivatives that possessed both linear propionyl esters and bulky (trifluoromethyl)phenyl carbamates in the side chains. The reflection peaks of HPC derivatives shifted to longer wavelengths upon heating due to an increase in the CLC helical pitch. Such thermally induced shifting behavior of the reflection peak was crucially dependent on not only the propionyl esterification degree, but also the substituents in the side chains of HPC derivatives. When the side chains of HPC were chemically modified with both propionyl esters and bulky substituents such as 3,5-bis(trifluoromethyl)phenyl carbamates, the reflection peaks emerged at longer wavelengths at the same temperature. This probably happened because of the steric hindrance of bulky side chains, as supported by the empirical molecular modeling calculation. Although the occupied volumes of (trifluoromethyl)phenyl groups were independent of the CLC phase temperature with visible Bragg reflection, the substituent position, i.e., substituent orientation of trifluoromethyl groups affected the CLC phase temperature. Moreover, we found that the hydrogen bonds between carbamate moieties in the HPC side chains play an important role in the thermally induced shift of reflection peaks. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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17 pages, 2118 KiB

Open AccessArticle

Pretreatments of Non-Woody Cellulosic Feedstocks for Bacterial Cellulose Synthesis

by Ekaterina I. Kashcheyeva, Yulia A. Gismatulina and Vera V. Budaeva

Polymers 2019, 11(10), 1645; https://doi.org/10.3390/polym11101645 - 10 Oct 2019

Cited by 40 | Viewed by 4088

Abstract

Pretreatment of biomass is a key step in the production of valuable products, including high-tech bacterial cellulose. The efficiency of five different pretreatment methods of Miscanthus and oat hulls for enzymatic hydrolysis and subsequent synthesis of bacterial cellulose (BC) was evaluated herein: Hydrothermobaric [...] Read more.

Pretreatment of biomass is a key step in the production of valuable products, including high-tech bacterial cellulose. The efficiency of five different pretreatment methods of Miscanthus and oat hulls for enzymatic hydrolysis and subsequent synthesis of bacterial cellulose (BC) was evaluated herein: Hydrothermobaric treatment, single-stage treatments with dilute HNO₃ or dilute NaOH solution, and two-stage combined treatment with dilute HNO₃ and NaOH solutions in direct and reverse order. The performance of enzymatic hydrolysis of pretreatment products was found to increase by a factor of 4−7. All the resultant hydrolyzates were composed chiefly of glucose, as the xylose percentage in total reducing sugars (RS) was 1−9%. The test synthesis of BC demonstrated good quality of nutrient media prepared from all the enzymatic hydrolyzates, except the hydrothermobaric treatment hydrolyzate. For biosynthesis of BC, single-stage pretreatments with either dilute HNO₃ or dilute NaOH are advised due their simplicity and the high performance of enzymatic hydrolysis of pretreatment products (RS yield 79.7−83.4%). Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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20 pages, 4715 KiB

Open AccessArticle

Surface-Initiated Initiators for Continuous Activator Regeneration (SI ICAR) ATRP of MMA from 2,2,6,6–tetramethylpiperidine–1–oxy (TEMPO) Oxidized Cellulose Nanofibers for the Preparations of PMMA Nanocomposites

by Cheng-Wei Tu, Fang-Chang Tsai, Chi-Jung Chang, Cheng-Han Yang, Shiao-Wei Kuo, Jiawei Zhang, Tao Chen and Chih-Feng Huang

Polymers 2019, 11(10), 1631; https://doi.org/10.3390/polym11101631 - 9 Oct 2019

Cited by 25 | Viewed by 4683

Abstract

An effective method of oxidation from paper pulps via 2,2,6,6–tetramethylpiperidine–1–oxy (TEMPO) compound to obtain TEMPO-oxidized cellulose nanofibers (TOCNs) was demonstrated. Following by acylation, TOCN having an atom transfer radical polymerization (ATRP) initiating site of bromoisobutyryl moiety (i.e., TOCN–Br) was successfully obtained. Through a [...] Read more.

An effective method of oxidation from paper pulps via 2,2,6,6–tetramethylpiperidine–1–oxy (TEMPO) compound to obtain TEMPO-oxidized cellulose nanofibers (TOCNs) was demonstrated. Following by acylation, TOCN having an atom transfer radical polymerization (ATRP) initiating site of bromoisobutyryl moiety (i.e., TOCN–Br) was successfully obtained. Through a facile and practical technique of surface-initiated initiators for continuous activator regeneration atom transfer radical polymerization (SI ICAR ATRP) of methyl methacrylate (MMA) from TOCN–Br, controllable grafting polymer chain lengths (M_n = ca. 10k–30k g/mol) with low polydispersity (PDI < 1.2) can be achieved to afford TOCN–g–Poly(methyl methacrylate) (PMMA) nanomaterials. These modifications were monitored by Fourier-transform infrared spectroscopy (FT–IR), scanning electron microscopy (SEM), electron spectroscopy for chemical analysis (ESCA), and water contact angle analysis. Eventually, TOCN–g–PMMA/PMMA composites were prepared using the solvent blending method. Compared to the pristine PMMA (T_g = 100 °C; tensile strength (σ_T) = 17.1 MPa), the composites possessed high transparency with enhanced thermal properties and high tensile strength (T_g = 110 °C and σ_T = 37.2 MPa in 1 wt% TOCN containing case) that were investigated by ultraviolet-visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile tests. We demonstrated that minor amounts of TOCN–g–PMMA nanofillers can provide high efficacy in improving the mechanical and thermal properties of PMMA matrix. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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17 pages, 4391 KiB

Open AccessArticle

Complex Aerogels Generated from Nano-Polysaccharides and Its Derivatives for Oil–Water Separation

by Hajo Yagoub, Liping Zhu, Mahmoud H. M. A. Shibraen, Ali A. Altam, Dafaalla M. D. Babiker, Songmiao Liang, Yan Jin and Shuguang Yang

Polymers 2019, 11(10), 1593; https://doi.org/10.3390/polym11101593 - 29 Sep 2019

Cited by 34 | Viewed by 6861

Abstract

The complex aerogel generated from nano-polysaccharides, chitin nanocrystals (ChiNC) and TEMPO-oxidized cellulose nanofibers (TCNF), and its derivative cationic guar gum (CGG) is successfully prepared via a facile freeze-drying method with glutaraldehyde (GA) as cross-linkers. The complexation of ChiNC, TCNF, and CGG is shown [...] Read more.

The complex aerogel generated from nano-polysaccharides, chitin nanocrystals (ChiNC) and TEMPO-oxidized cellulose nanofibers (TCNF), and its derivative cationic guar gum (CGG) is successfully prepared via a facile freeze-drying method with glutaraldehyde (GA) as cross-linkers. The complexation of ChiNC, TCNF, and CGG is shown to be helpful in creating a porous structure in the three-dimensional aerogel, which creates within the aerogel with large pore volume and excellent compressive properties. The ChiNC/TCNF/CGG aerogel is then modified with methyltrichlorosilane (MTCS) to obtain superhydrophobicity/superoleophilicity and used for oil–water separation. The successful modification is demonstrated through FTIR, XPS, and surface wettability studies. A water contact angle of 155° on the aerogel surface and 150° on the surface of the inside part of aerogel are obtained for the MTCS-modified ChiNC/TCNF/CGG aerogel, resulting in its effective absorption of corn oil and organic solvents (toluene, n-hexane, and trichloromethane) from both beneath and at the surface of water with excellent absorption capacity (i.e., 21.9 g/g for trichloromethane). More importantly, the modified aerogel can be used to continuously separate oil from water with the assistance of a vacuum setup and maintains a high absorption capacity after being used for 10 cycles. The as-prepared superhydrophobic/superoleophilic ChiNC/TCNF/CGG aerogel can be used as a promising absorbent material for the removal of oil from aqueous media. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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14 pages, 4766 KiB

Open AccessArticle

Massaranduba Sawdust: A Potential Source of Charcoal and Activated Carbon

by Jonnys P. Castro, João Rodrigo C. Nobre, Alfredo Napoli, Maria Lucia Bianchi, Jordão C. Moulin, Bor-Sen Chiou, Tina G. Williams, Delilah F. Wood, Roberto J. Avena-Bustillos, William J. Orts and Gustavo H. D. Tonoli

Polymers 2019, 11(8), 1276; https://doi.org/10.3390/polym11081276 - 31 Jul 2019

Cited by 21 | Viewed by 5476

Abstract

This paper provides proof of concept that activated carbon (AC) may be readily produced using limited conversion methods and resources from sawdust of massaranduba (Manilkara huberi) wood, thereby obtaining value-added products. Sawdust was sieved and heat-treated in an oxygen-free muffle furnace [...] Read more.

This paper provides proof of concept that activated carbon (AC) may be readily produced using limited conversion methods and resources from sawdust of massaranduba (Manilkara huberi) wood, thereby obtaining value-added products. Sawdust was sieved and heat-treated in an oxygen-free muffle furnace at 500 °C to produce charcoal. The charcoal was activated in a tubular electric furnace at 850 °C while being purged with CO₂ gas. Microstructural, thermal and physical properties of the three components: sawdust, charcoal and AC were compared by means of field emission scanning electron microscopy (FESEM), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), density and water adsorption/desorption measurements. The resulting AC had a large surface area as measured by Brunauer-Emmett-Teller (BET) comparable to other such values found in the literature. The large surface area was due to pore development at the microstructural level as shown by FESEM. XRD illustrated that sawdust had a semi-crystalline structure whereas charcoal and AC evidenced mostly amorphous structures. TGA and DSC showed that AC had high reactivity to moisture compared to sawdust and charcoal. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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11 pages, 2566 KiB

Open AccessArticle

Dynamic Self-Assembly of Polyelectrolyte Composite Nanomaterial Film

by Qiupeng Hou, Xiwen Wang and Arthur J. Ragauskas

Polymers 2019, 11(8), 1258; https://doi.org/10.3390/polym11081258 - 30 Jul 2019

Cited by 9 | Viewed by 3633

Abstract

The aim of this study is not only to investigate the feasibility of using PAH (polyallylamine hydrochloride) and PSS (poly styrene-4-sulfonic acid sodium salt) to prepare a film via a layer by layer self-assembly process entrained with silver nanoparticles, but also to show [...] Read more.

The aim of this study is not only to investigate the feasibility of using PAH (polyallylamine hydrochloride) and PSS (poly styrene-4-sulfonic acid sodium salt) to prepare a film via a layer by layer self-assembly process entrained with silver nanoparticles, but also to show that the silver nanoparticles crystalline structure can be defined and deposited on the surface of the substrate in the desired alignment structure and manner, which is of great help to research on the LBL method in the cellulose field. The effect of outermost layer variation, assembly layers, and composition of multilayers on the formation of the LBL structure on a nanofibrillated cellulose (NFC)/polyvinyl alcohol (PVA) substrate was investigated. The deposition of PAH and PSS was monitored by Fourier-transform infrared spectroscopy (FT-IR). The morphology of the LBL film layers was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). Furthermore, thermal degradation properties were investigated by thermogravimetric analysis (TGA), and physical properties of multilayer films were tested by a universal mechanical tester. The results reveal that PAH and PSS can be readily deposited on a NFC/PVA substrate by using LBL methodology to prepare self-assembled polyelectrolyte multilayer films. The surface morphology of the LBL composite changed from negative to positive charged depending on the final LBL treatment. Also, according to SEM and AFM analysis, silver nanoparticles were well dispersed in the (PAH/PSS) film, which significantly improved the thermal stability of the composite films. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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7 pages, 1727 KiB

Open AccessEditor’s ChoiceArticle

Determination of Surface Accessibility of the Cellulose Substrate According to Enzyme Sorption

by Ekaterina M. Podgorbunskikh, Aleksey L. Bychkov and Oleg I. Lomovsky

Polymers 2019, 11(7), 1201; https://doi.org/10.3390/polym11071201 - 18 Jul 2019

Cited by 23 | Viewed by 3817

Abstract

As a heterogeneous process, enzymatic hydrolysis depends on the contact area between enzymes and the cellulose substrate. The surface area of a substrate is typically evaluated through the sorption of gases (nitrogen, argon, or water vapor) or sorption of high-molecular-weight pigments or proteins. [...] Read more.

As a heterogeneous process, enzymatic hydrolysis depends on the contact area between enzymes and the cellulose substrate. The surface area of a substrate is typically evaluated through the sorption of gases (nitrogen, argon, or water vapor) or sorption of high-molecular-weight pigments or proteins. However, lignocellulosic biomass uninvolved in the reaction because of inefficient binding or even the complete inhibition of the enzymes on the surface consisting of lignin or inorganic compounds is erroneously taken into account under these conditions. The initial rate of enzymatic hydrolysis will directly depend on the number of enzymes efficiently sorbed onto cellulose. In this study, the sorption of cellulolytic enzymes was used to evaluate the surface accessibility of the cellulose substrate and its changes during mechanical pretreatment. It was demonstrated that for pure cellulose, mechanical activation did not alter the chemical composition of the surface and the initial rate of hydrolysis increased, which was inconsistent with the data on the thermal desorption of nitrogen. New active cellulose sorption sites were shown to be formed upon. the mechanical activation of plant biomass (wheat straw), and the ultimate initial rate of hydrolysis corresponding to saturation of the accessible surface area with enzyme molecules was determined. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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16 pages, 3179 KiB

Open AccessArticle

Study on Stability and Stability Mechanism of Styrene-Acrylic Emulsion Prepared Using Nanocellulose Modified with Long-Chain Fatty Acids

by Heng Zhang, Hongyan Yang, Junliang Lu, Jinyan Lang and Hongkun Gao

Polymers 2019, 11(7), 1131; https://doi.org/10.3390/polym11071131 - 3 Jul 2019

Cited by 17 | Viewed by 6925

Abstract

In this study, nanocrystalline cellulose (NCC) was grafted with lauric acid, palmitic acid, and stearic acid and used as stabilizer to prepare styrene butyl acrylate emulsion. The properties of the emulsion were determined, and the mechanism of modified NCC (MNCC) stabilized emulsion was [...] Read more.

In this study, nanocrystalline cellulose (NCC) was grafted with lauric acid, palmitic acid, and stearic acid and used as stabilizer to prepare styrene butyl acrylate emulsion. The properties of the emulsion were determined, and the mechanism of modified NCC (MNCC) stabilized emulsion was analyzed. Results showed that long-chain fatty acids were grafted to NCC through esterification initiated at a low temperature. When the dosage of L-MNCC, P-MNCC, and S-MNCC was 0.05%, the styrene-acrylic emulsion had 92.5%, 94.2%, and 96.3% conversion rates, respectively, and exhibited good dilution, pH, Ca²⁺, and centrifugal stability. The particle size of styrene-acrylic emulsion was approximately 460 nm, and the absolute value of the Zeta potential increased with the MNCC concentration. According to the images of optical microscopy and the transmission electron microscope, the MNCC was adsorbed onto the surface of styrene-acrylic emulsion droplets. The synergistic effect from the electrostatic repulsion of MNCC, the hydrophile lipophilicity of MNCC, and the spatial hindrance of the MNCC adsorption layer provided good stability for the styrene-acrylic emulsion. Therefore, MNCC could replace traditional surfactants in stabilizing emulsion. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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18 pages, 4561 KiB

Open AccessArticle

Natural Rubber Composites Filled with Crop Residues as an Alternative to Vulcanizates with Common Fillers

by Marcin Masłowski, Justyna Miedzianowska and Krzysztof Strzelec

Polymers 2019, 11(6), 972; https://doi.org/10.3390/polym11060972 - 3 Jun 2019

Cited by 64 | Viewed by 5529

Abstract

This present study is focused on exploring the possibility of using agricultural waste in the form of cereal straw as an active filler of biocomposites. The effect of lignocellulosic filler addition on the multifunctional properties of natural rubber composites was investigated. The results [...] Read more.

This present study is focused on exploring the possibility of using agricultural waste in the form of cereal straw as an active filler of biocomposites. The effect of lignocellulosic filler addition on the multifunctional properties of natural rubber composites was investigated. The results were compared with the properties of vulcanizates containing commonly used reinforcements in elastomer technology (carbon black, silica, chalk, talc). Rubber mixtures filled with straw showed the highest torque increase during rheometric measurements, which indirectly indicated a high degree of crosslinking and hardness of composites. It was found that the effect of straw addition on vulcanization time of elastomer blends was comparable with the results obtained for other conventional fillers. Moreover, the results confirmed that novel composites based on natural rubber filled with crop residues were attractive materials owing to their capacity for the formation of “structure” in combination with a good impact on reinforcement. Vulcanizates with the addition of straw showed the best barrier properties and resistance to thermo-oxidative aging from all tested samples. Furthermore, straw-based composites demonstrated that cereal straw waste could be used as an alternative, biodegradable and eco-friendly reinforcement of natural rubber composites. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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9 pages, 3553 KiB

Open AccessArticle

An Effective, Economical and Ultra-Fast Method for Hydrophobic Modification of NCC Using Poly(Methylhydrogen)Siloxane

by Xueqing You, Qingjian Hu, Xiaoyong Hu, Hanxian Chen, Wenbin Yang and Xinxiang Zhang

Polymers 2019, 11(6), 963; https://doi.org/10.3390/polym11060963 - 3 Jun 2019

Cited by 8 | Viewed by 3246

Abstract

Poor compatibility between nanocellulose crystals (NCCs) and major polymers has limited the application of NCC as bio-reinforcements. In this work, an effective and ultra-fast method was investigated to significantly improve the hydrophobicity of NCC by using poly(methylhydrogen)siloxane (PMHS) as modifier. PMHS possessed amounts [...] Read more.

Poor compatibility between nanocellulose crystals (NCCs) and major polymers has limited the application of NCC as bio-reinforcements. In this work, an effective and ultra-fast method was investigated to significantly improve the hydrophobicity of NCC by using poly(methylhydrogen)siloxane (PMHS) as modifier. PMHS possessed amounts of reactive –Si–H groups and hydrophobic –CH₃ groups. The former groups were reactive with the hydroxyl groups of NCC, while the latter groups afforded NCC very low surface energy. As the weight ratio of PMHS to NCC was only 0.0005%, the hydrophobicity of NCC was significantly improved by increasing the water contact angle of NCC from 0° to 134°. The effect of weight ratio of PMHS to NCC and the hydrogen content of –Si–H in PMHS on the hydrophobicity and thermal stability was investigated in detail by Fourier transform infrared spectroscopy (FTIR), (X-ray Diffraction) XRD and (thermogravimetric analysis) TGA. The results indicated that PMHS chains were covalently grafted onto NCC and PMHS modification improved the thermal stability of NCC. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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11 pages, 6051 KiB

Open AccessArticle

Twisting of Fibers Balancing the Gel–Sol Transition in Cellulose Aqueous Suspensions

by Dmitry V. Zlenko, Sergey N. Nikolsky, Alexander S. Vedenkin, Galina G. Politenkova, Aleksey A. Skoblin, Valery P. Melnikov, Maria G. Mikhaleva and Sergey V. Stovbun

Polymers 2019, 11(5), 873; https://doi.org/10.3390/polym11050873 - 13 May 2019

Cited by 8 | Viewed by 3106

Abstract

Cellulose hydrogels and films are advantageous materials that are applied in modern industry and medicine. Cellulose hydrogels have a stable scaffold and never form films upon drying, while viscous cellulose hydrosols are liquids that could be used for film production. So, stabilizing either [...] Read more.

Cellulose hydrogels and films are advantageous materials that are applied in modern industry and medicine. Cellulose hydrogels have a stable scaffold and never form films upon drying, while viscous cellulose hydrosols are liquids that could be used for film production. So, stabilizing either a gel or sol state in cellulose suspensions is a worthwhile challenge, significant for the practical applications. However, there is no theory describing the cellulose fibers’ behavior and processes underlying cellulose-gel-scaffold stabilizing. In this work, we provide a phenomenological mechanism explaining the transition between the stable-gel and shapeless-sol states in a cellulose suspension. We suppose that cellulose macromolecules and nanofibrils under strong dispersing treatment (such as sonication) partially untwist and dissociate, and then reassemble in a 3D scaffold having the individual elements twisted in the nodes. The latter leads to an exponential increase in friction forces between the fibers and to the corresponding fastening of the scaffold. We confirm our theory by the data on the circular dichroism of the cellulose suspensions, as well as by the direct scanning electron microscope (SEM) observations and theoretical assessments. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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24 pages, 13723 KiB

Open AccessEditor’s ChoiceArticle

Surface Modification of Cellulose Nanocrystals with Succinic Anhydride

by Agnieszka Leszczyńska, Paulina Radzik, Ewa Szefer, Matej Mičušík, Mária Omastová and Krzysztof Pielichowski

Polymers 2019, 11(5), 866; https://doi.org/10.3390/polym11050866 - 13 May 2019

Cited by 54 | Viewed by 8221

Abstract

The surface modification of cellulose nanocrystals (CNC) is a key intermediate step in the development of new functionalities and the tailoring of nanomaterial properties for specific applications. In the area of polymeric nanocomposites, apart from good interfacial adhesion, the high thermal stability of [...] Read more.

The surface modification of cellulose nanocrystals (CNC) is a key intermediate step in the development of new functionalities and the tailoring of nanomaterial properties for specific applications. In the area of polymeric nanocomposites, apart from good interfacial adhesion, the high thermal stability of cellulose nanomaterial is vitally required for the stable processing and improvement of material properties. In this respect, the heterogeneous esterification of CNC with succinic anhydride was investigated in this work in order to obtain CNC with optimised surface and thermal properties. The influence of reaction parameters, such as time, temperature, and molar ratio of reagents, on the structure, morphology and thermal properties, were systematically studied over a wide range of values by DLS, FTIR, XPS, WAXD, SEM and TGA methods. It was found that the degree of surface substitution of CNC increased with the molar ratio of succinic anhydride to cellulose hydroxyl groups (SA:OH), as well as the reaction time, whilst the temperature of reaction showed a moderate effect on the degree of esterification in the range of 70–110 °C. The studies on the thermal stability of modified nanoparticles indicated that there is a critical extent of surface esterification below which only a slight decrease of the initial temperature of degradation was observed in pyrolytic and oxidative atmospheres. A significant reduction of CNC thermal stability was observed only for the longest reaction time (240 min) and the highest molar ratio of SA:OH. This illustrates the possibility of manufacturing thermally stable, succinylated, CNC by controlling the reaction conditions and the degree of esterification. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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14 pages, 4992 KiB

Open AccessArticle

Development of Diallylimidazolium Methoxyacetate/DMSO (DMF/DMA) Solvents for Improving Cellulose Dissolution and Fabricating Porous Material

by Airong Xu, Lin Chen, Yongxin Wang, Rukuan Liu and Wentian Niu

Polymers 2019, 11(5), 845; https://doi.org/10.3390/polym11050845 - 10 May 2019

Cited by 15 | Viewed by 5738

Abstract

Cellulose is the most abundant natural biopolymer, with unique properties such as biodegradability, biocompability, nontoxicity, and so on. However, its extensive application has actually been hindered, because of its insolubility in water and most solvents. Herein, highly efficient cellulose solvents were developed by [...] Read more.

Cellulose is the most abundant natural biopolymer, with unique properties such as biodegradability, biocompability, nontoxicity, and so on. However, its extensive application has actually been hindered, because of its insolubility in water and most solvents. Herein, highly efficient cellulose solvents were developed by coupling diallylimidazolium methoxyacetate ([A₂im][CH₃OCH₂COO]) with polar aprotic solvents dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). Attractively, these solvents showed extraordinarily powerful dissolution performance for cellulose (e.g., 26.1 g·100g⁻¹) in [A₂im][CH₃OCH₂COO]/DMSO(R_DMSO = 1.01 solvent even at 25 °C), which is much more advantageous over previously reported solvents. To our knowledge, such powerful cellulose solvents have not been reported before. The cellulose dissolution mechanism is proposed to be of three combined factors: (1) The hydrogen bond interactions of the H2, H4 and H6 in [A₂im]⁺ and the carboxyl O atom in [CH₃OCH₂COO]⁻, along with the hydroxyl H atom and O atom in cellulose, are main driving force for cellulose dissolution; (2) the dissociation of [A₂im][CH₃OCH₂COO] by DMF increases the anion and cation concentrations and thus promotes cellulose dissolution; (3) at the same time, DMF also stabilizes the dissolved cellulose chains. Meanwhile, the porous cellulose material with a varying morphologic structure could be facially fabricated by modulating the cellulose solution concentration. Additionally, the dissolution of cellulose in the solvents is only a physical process, and the regenerated cellulose from the solvents retains sufficient thermostability and a chemical structure similar to the original cellulose. Thus, this work will provide great possibility for developing cellulose-based products at ambient temperatures or under no extra heating/freezing conditions. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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16 pages, 3096 KiB

Open AccessArticle

Dissolution and Hydrolysis of Bleached Kraft Pulp Using Ionic Liquids

by Guillermo Reyes, María Graciela Aguayo, Arturo Fernández Pérez, Timo Pääkkönen, William Gacitúa and Orlando J. Rojas

Polymers 2019, 11(4), 673; https://doi.org/10.3390/polym11040673 - 12 Apr 2019

Cited by 26 | Viewed by 5428

Abstract

Forestry industries in Chile are facing an important challenge—diversifying their products using green technologies. In this study, the potential use of Ionic Liquids (ILs) to dissolve and hydrolyze eucalyptus wood (mix of Eucalyptus nitens and Eucalyptus globulus) kraft pulp was studied. The [...] Read more.

Forestry industries in Chile are facing an important challenge—diversifying their products using green technologies. In this study, the potential use of Ionic Liquids (ILs) to dissolve and hydrolyze eucalyptus wood (mix of Eucalyptus nitens and Eucalyptus globulus) kraft pulp was studied. The Bleached Hardwood Kraft Pulp (BHKP) from a Chilean pulp mill was used together with five different ILs: 1-butyl-3-methylimidazolium chloride [bmim][Cl], 1-butyl-3-methylimidazolium acetate [bmim][Ac], 1-butyl-3-methylimidazolium hydrogen sulfate [bmim][HSO₄], 1-ethyl-3-methylimidazolium chloride [emim][Cl], 1-ethyl-3-methylimidazolium acetate [emim][Ac]. Experimentally, one vacuum reactor was designed to study the dissolution/hydrolysis process for each ILs; particularly, the cellulose dissolution process using [bmim][Cl] was studied proposing one molecular dynamic model. Experimental characterization using Atomic Force Microscopy, conductometric titration, among other techniques suggest that all ILs are capable of cellulose dissolution at different levels; in some cases, the dissolution evolved to partial hydrolysis appearing cellulose nanocrystals (CNC) in the form of spherical aggregates with a diameter of 40–120 nm. Molecular dynamics simulations showed that the [bmim][Cl] anions tend to interact actively with cellulose sites and water molecules in the dissolution process. The results showed the potential of some ILs to dissolve/hydrolyze the cellulose from Chilean Eucalyptus, maintaining reactive forms. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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15 pages, 4651 KiB

Open AccessArticle

Thermoplastic Elastomer Biocomposites Filled with Cereal Straw Fibers Obtained with Different Processing Methods—Preparation and Properties

by Justyna Miedzianowska, Marcin Masłowski and Krzysztof Strzelec

Polymers 2019, 11(4), 641; https://doi.org/10.3390/polym11040641 - 9 Apr 2019

Cited by 21 | Viewed by 4437

Abstract

This work is focused on thermoplastic elastomers composites (TPEs) reinforced with straw. Crop waste with different particle size was used as a filler of ethylene-octene rubber (EOR). Application of cheap and renewable natural fiber like straw into a TPE medium is not fully [...] Read more.

This work is focused on thermoplastic elastomers composites (TPEs) reinforced with straw. Crop waste with different particle size was used as a filler of ethylene-octene rubber (EOR). Application of cheap and renewable natural fiber like straw into a TPE medium is not fully recognized and explored. The effect of fiber orientation induced by two processing techniques on the different mechanical properties of composites was investigated. Microscopic images were used to present the tested straw fractions and observe the arrangement and dispersion of fibers in the polymer matrix. It was found that the usage of an injection molding process allowed for the forming of a more homogenous dispersion of short fiber particles in the elastomer matrix. An oriented straw filler and polymer chains resulted in the improved mechanical strength of the whole system as evidenced by the obtained values of tensile strength almost two times higher for injected composites. In addition, all composites showed very good resistance to thermo-oxidative aging, where the aging factor oscillated within the limits of one, regardless of the processing method and the amount of bioadditive used. On the other hand, vulcanized composites were characterized by greater tear resistance, for which Fmit values increased by up to 600% compared to the reference sample. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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21 pages, 10923 KiB

Open AccessArticle

Multifunctional Nanocomposite Cellulose Fibers Doped in Situ with Silver Nanoparticles

by Olga Rac-Rumijowska, Irena Maliszewska, Marta Fiedot-Toboła, Iwona Karbownik and Helena Teterycz

Polymers 2019, 11(3), 562; https://doi.org/10.3390/polym11030562 - 25 Mar 2019

Cited by 24 | Viewed by 4553

Abstract

This paper presents a method for the preparation of nanocomposite cellulose fibers doped with silver nanoparticles (AgNPs), as well as the effect of silver nanoparticles on the structure and properties of fibers. The fibers were obtained by an environmentally friendly method using N-Methylmorpholine [...] Read more.

This paper presents a method for the preparation of nanocomposite cellulose fibers doped with silver nanoparticles (AgNPs), as well as the effect of silver nanoparticles on the structure and properties of fibers. The fibers were obtained by an environmentally friendly method using N-Methylmorpholine N-oxide (NMMO) as a solvent, in a non-polluting closed system. Doping with silver nanoparticles was carried out as a direct (in situ) reduction of Ag⁺ ions in the presence of a stabilizing agent during the preparation of the spinning solution. SEM images of the surface and cross section of the fibers showed that the distribution of nanoparticles in the fibers’ volume was uniform. The fibers exhibited very good antibacterial properties in relation to Staphylococcus aureus, Escherichia coli, Acinetobacter baumannii, and Candida albicans. Flammability analysis showed that the fibers were subjected to a one-stage combustion process and that the silver nanoparticles reduced the heat release rate (HRR) of the fibers by 36%. TG studies showed that the modification of cellulose fibers with silver nanoparticles promoted the formation of mill scale in the combustion of fibers, which was directly related to the reduction of flammability. Tests of the electrical properties showed that the linear resistance of cellulose fibers containing 3 wt % silver was 10⁸ Ω/cm. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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28 pages, 6414 KiB

Open AccessEditor’s ChoiceReview

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

by Omar A. El Seoud, Marc Kostag, Kerstin Jedvert and Naved I. Malek

Polymers 2019, 11(12), 1917; https://doi.org/10.3390/polym11121917 - 21 Nov 2019

Cited by 45 | Viewed by 7134

Abstract

This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly [...] Read more.

This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into “mini-crystals”, and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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20 pages, 4968 KiB

Open AccessReview

Brief Overview on Bio-Based Adhesives and Sealants

by Solange Magalhães, Luís Alves, Bruno Medronho, Ana C. Fonseca, Anabela Romano, Jorge F.J. Coelho and Magnus Norgren

Polymers 2019, 11(10), 1685; https://doi.org/10.3390/polym11101685 - 15 Oct 2019

Cited by 52 | Viewed by 11265

Abstract

Adhesives and sealants (AS) are materials with excellent properties, versatility, and simple curing mechanisms, being widely used in different areas ranging from the construction to the medical sectors. Due to the fast-growing demand for petroleum-based products and the consequent negative environmental impact, there [...] Read more.

Adhesives and sealants (AS) are materials with excellent properties, versatility, and simple curing mechanisms, being widely used in different areas ranging from the construction to the medical sectors. Due to the fast-growing demand for petroleum-based products and the consequent negative environmental impact, there is an increasing need to develop novel and more sustainable sources to obtain raw materials (monomers). This reality is particularly relevant for AS industries, which are generally dependent on non-sustainable fossil raw materials. In this respect, biopolymers, such as cellulose, starch, lignin, or proteins, emerge as important alternatives. Nevertheless, substantial improvements and developments are still required in order to simplify the synthetic routes, as well as to improve the biopolymer stability and performance of these new bio-based AS formulations. This environmentally friendly strategy will hopefully lead to the future partial or even total replacement of non-renewable petroleum-based feedstock. In this brief overview, the general features of typical AS are reviewed and critically discussed regarding their drawbacks and advantages. Moreover, the challenges faced by novel and more ecological alternatives, in particular lignocellulose-based solutions, are highlighted. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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18 pages, 1284 KiB

Open AccessReview

Emulsion Formation and Stabilization by Biomolecules: The Leading Role of Cellulose

by Carolina Costa, Bruno Medronho, Alexandra Filipe, Isabel Mira, Björn Lindman, Håkan Edlund and Magnus Norgren

Polymers 2019, 11(10), 1570; https://doi.org/10.3390/polym11101570 - 26 Sep 2019

Cited by 131 | Viewed by 13735

Abstract

Emulsion stabilization by native cellulose has been mainly hampered because of its insolubility in water. Chemical modification is normally needed to obtain water-soluble cellulose derivatives. These modified celluloses have been widely used for a range of applications by the food, cosmetic, pharmaceutic, paint [...] Read more.

Emulsion stabilization by native cellulose has been mainly hampered because of its insolubility in water. Chemical modification is normally needed to obtain water-soluble cellulose derivatives. These modified celluloses have been widely used for a range of applications by the food, cosmetic, pharmaceutic, paint and construction industries. In most cases, the modified celluloses are used as rheology modifiers (thickeners) or as emulsifying agents. In the last decade, the structural features of cellulose have been revisited, with particular focus on its structural anisotropy (amphiphilicity) and the molecular interactions leading to its resistance to dissolution. The amphiphilic behavior of native cellulose is evidenced by its capacity to adsorb at the interface between oil and aqueous solvent solutions, thus being capable of stabilizing emulsions. In this overview, the fundamentals of emulsion formation and stabilization by biomolecules are briefly revisited before different aspects around the emerging role of cellulose as emulsion stabilizer are addressed in detail. Particular focus is given to systems stabilized by native cellulose, either molecularly-dissolved or not (Pickering-like effect). Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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