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Open AccessEditorial

Bio-Based Polymers for Engineered Green Materials

by

Gianluca Tondi

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Thomas Schnabel

Polymers 2020, 12(4), 775; https://doi.org/10.3390/polym12040775 - 01 Apr 2020

Cited by 10 | Viewed by 2486

Abstract

Every [...] Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessArticle

Larch Wood Residues Valorization through Extraction and Utilization of High Value-Added Products

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Alexander Petutschnigg

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Thomas Schnabel

Polymers 2020, 12(2), 359; https://doi.org/10.3390/polym12020359 - 06 Feb 2020

Cited by 8 | Viewed by 2553

Abstract

Many of current bio-based materials are not fully or partly used for material utilization, as the composition of their raw materials and/or possible applications are unknown. This study deals with the analysis of the wood extractives from three different tissue of larch wood: [...] Read more.

Many of current bio-based materials are not fully or partly used for material utilization, as the composition of their raw materials and/or possible applications are unknown. This study deals with the analysis of the wood extractives from three different tissue of larch wood: Sapwood mainly from outer part of the log, and sound knotwood as well as dead knotwood. The extractions were performed with an accelerated solvent extractor (ASE) using hexane and acetone/water. The obtained extracts were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). Three various vibrational spectroscopy (FT-RAMAN, FT-IR and FT-NIR) methods reflect the information from the extracts to the chemical composition of the types of wood before the extraction processes. Multivariate data analysis of the spectra was used to obtain a better insight into possible classification methods. Taxifolin and kaempferol were found in larger amount in sound knotwood samples compared to larch wood with high percentage of sapwood and dead knotwood samples. While the extractions of dead knotwood samples yielded more larixol and resin acids than the other larch wood samples used. Based on the chemical composition, three lead compounds were defined for the classification of the different wood raw materials. The vibrational spectroscopy methods were applied to show their potential for a possible distinction of the three types of larch wood tissue. This new insight into the different larch wood extracts will help in the current efforts to use more environmentally friendly raw materials for innovative applications. The connection between the raw materials and extraction yields of the target values is important to transform the results from the laboratory to industry and consumer applications. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessArticle

Structure–Property Relationships of Pure Cellulose and GO/CEL Membranes Regenerated from Ionic Liquid Solutions

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Czesław Ślusarczyk

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Beata Fryczkowska

Polymers 2019, 11(7), 1178; https://doi.org/10.3390/polym11071178 - 12 Jul 2019

Cited by 10 | Viewed by 3565

Abstract

Two types of cellulose membranes were produced by a classical wet phase inversion method from a solution of the polymer in 1-ethyl-3-methylimidazolium acetate (EMIMAc) by coagulation in water and selected primary alcohols. The first type were membranes made from pure cellulose (CEL). The [...] Read more.

Two types of cellulose membranes were produced by a classical wet phase inversion method from a solution of the polymer in 1-ethyl-3-methylimidazolium acetate (EMIMAc) by coagulation in water and selected primary alcohols. The first type were membranes made from pure cellulose (CEL). The second type were membranes obtained by adding nanosized graphene oxide (GO) to the cellulose solution. The process of precipitation and selection of the coagulant affected the structure of the membranes, which in turn affected their usability and applicability. The results of the presented studies show that the physicochemical properties of the coagulant used (e.g., molecular mass and dipole moment) play important roles in this process. It was found that both the content and dimensions of the pores depended on the molecular mass of the coagulant used. It was also found that the dipole moment of coagulant molecules had a large influence on the volume content of the pores (e.g., the 1-octanol (Oc) membrane had a dipole moment of 1.71 D; Φ = 1.82%). We investigated the effect of the type of coagulant on the porous structure of CEL membranes and how this affected the transport properties of the membranes (e.g., for the distilled water (W) membrane, J_v = 5.24 ± 0.39 L/m² h; for the Oc membrane, J_v = 92.19 ± 1.51 L/m² h). The paper presents the results of adding GO nanoparticles in terms of the structure, morphology, and transport properties of GO/CEL membranes (e.g., for composite membrane F (containing 20% GO), J_v = 40.20 ± 2.33 L/m² h). In particular, it describes their extremely high ability to remove heavy metal ions. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessEditor’s ChoiceArticle

One-Pot Method of Synthesizing TEMPO-Oxidized Bacterial Cellulose Nanofibers Using Immobilized TEMPO for Skincare Applications

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Seung-Hyun Jun

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Sun-Gyoo Park

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Nae-Gyu Kang

Polymers 2019, 11(6), 1044; https://doi.org/10.3390/polym11061044 - 14 Jun 2019

Cited by 24 | Viewed by 4249

Abstract

In the skincare field, water-dispersed bacterial cellulose nanofibers synthesized via an oxidation reaction using 2,2,6,6–tetramethyl–1–piperidine–N–oxy radical (TEMPO) as a catalyst are promising bio-based polymers for engineered green materials because of their unique properties when applied to the surface of the skin, such as [...] Read more.

In the skincare field, water-dispersed bacterial cellulose nanofibers synthesized via an oxidation reaction using 2,2,6,6–tetramethyl–1–piperidine–N–oxy radical (TEMPO) as a catalyst are promising bio-based polymers for engineered green materials because of their unique properties when applied to the surface of the skin, such as a high tensile strength, high water-holding capacity, and ability to block harmful substances. However, the conventional method of synthesizing TEMPO-oxidized bacterial cellulose nanofibers (TOCNs) is difficult to scale due to limitations in the centrifuge equipment when treating large amounts of reactant. To address this, we propose a one-pot TOCN synthesis method involving TEMPO immobilized on silica beads that employs simple filtration instead of centrifugation after the oxidation reaction. A comparison of the structural and physical properties of the TOCNs obtained via the proposed and conventional methods found similar properties in each. Therefore, it is anticipated that due to its simplicity, efficiency, and ease of use, the proposed one-pot synthesis method will be employed in production scenarios to prepare production quantities of bio-based polymer nanofibers in various potential industrial applications in the fields of skincare and biomedical research. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Solvent- and Catalyst-free Synthesis, Hybridization and Characterization of Biobased Nonisocyanate Polyurethane (NIPU)

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Polymers 2019, 11(6), 1026; https://doi.org/10.3390/polym11061026 - 10 Jun 2019

Cited by 19 | Viewed by 4341

Abstract

Nonisocyanate polyurethane (NIPU) is a research hotspot in polyurethane applications because it does not use phosgene. Herein, a novel method of solvent- and catalyst-free synthesis of a hybrid nonisocyanate polyurethane (HNIPU) is proposed. First, four diamines were used to react with ethylene carbonate [...] Read more.

Nonisocyanate polyurethane (NIPU) is a research hotspot in polyurethane applications because it does not use phosgene. Herein, a novel method of solvent- and catalyst-free synthesis of a hybrid nonisocyanate polyurethane (HNIPU) is proposed. First, four diamines were used to react with ethylene carbonate to obtain four bis(hydroxyethyloxycarbonylamino)alkane (BHA). Then, BHA reacted with dimer acid under condensation in the melt to prepare four nonisocynate polyurethane prepolymers. Further, the HNIPUs were obtained by crosslinking prepolymers and resin epoxy and cured with the program temperature rise. In addition, four amines and two resin epoxies were employed to study the effects and regularity of HNIPUs. According to the results from thermal and dynamic mechanical analyses, those HNIPUs showed a high degree of thermal stability, and the highest 5% weight loss reached about 350 °C. More importantly, the utilization of these green raw materials accords with the concept of sustainable development. Further, the synthetic method and HNIPUs don’t need isocyanates, catalysts, or solvents. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Compressive Alginate Sponge Derived from Seaweed Biomass Resources for Methylene Blue Removal from Wastewater

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Polymers 2019, 11(6), 961; https://doi.org/10.3390/polym11060961 - 02 Jun 2019

Cited by 19 | Viewed by 3312

Abstract

Low cost fabrication of water treatment polymer materials directly from biomass resources is urgently needed in recent days. Herein, a compressive alginate sponge (AS) is prepared from seaweed biomass resources through a green two-step lyophilization method. This material is much different from conventional [...] Read more.

Low cost fabrication of water treatment polymer materials directly from biomass resources is urgently needed in recent days. Herein, a compressive alginate sponge (AS) is prepared from seaweed biomass resources through a green two-step lyophilization method. This material is much different from conventional oven-, air-, vacuum-dried alginate-based adsorbents, which show limitations of shrinkage, rigidness, tight nonporous structure and restricted ions diffusion, hindering its practical applications, and was used to efficiently remove methylene blue (MB), a main colorful contaminant in dye manufacturing, from wastewater. The batch adsorption studies are carried out to determine the impact of pH, contact time and concentration of dye on the adsorption process. The maximum adsorption capacity can be obtained at 1279 mg g⁻¹, and the shape-moldable AS can be facilely utilized as a fixed-bed absorption column, providing an efficient approach for continuous removal of MB within a short time. It is also important that such a compressive AS can be regenerated by a simple squeezing method while retaining about 70% capacity for more than ten cycles, which is convenient to be reused in practical water treatment. Compressive AS demonstrates its merits of high capability, large efficiency and easy to recycle as well as low cost resources, indicating widespread potentials for application in dye contaminant control regarding environmental protection. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Reducing off-Flavour in Commercially Available Polyhydroxyalkanoate Materials by Autooxidation through Compounding with Organoclays

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Lidia García-Quiles

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Arantzazu Valdés

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Ángel Fernández Cuello

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Alfonso Jiménez

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María del Carmen Garrigós

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Pere Castell

Polymers 2019, 11(6), 945; https://doi.org/10.3390/polym11060945 - 31 May 2019

Cited by 6 | Viewed by 2637

Abstract

Polyhydroxyalkanoates (PHAs) are nowadays considered competent candidates to replace traditional plastics in several market sectors. However, commercial PHA materials exhibit unsatisfactory smells that can negatively affect the quality of the final product. The cause of this typical rancid odour is attributed to oxidized [...] Read more.

Polyhydroxyalkanoates (PHAs) are nowadays considered competent candidates to replace traditional plastics in several market sectors. However, commercial PHA materials exhibit unsatisfactory smells that can negatively affect the quality of the final product. The cause of this typical rancid odour is attributed to oxidized cell membrane glycolipids, coming from Gram-negative production strains, which remain frequently attached to PHAs granules after the extraction stage. The aim of this research is the development of customised PHA bio-nano-composites for industrial applications containing organomodified nanoclays with high adsorbance properties able to capture volatile compounds responsible for the displeasing fragrance. To this end, a methodology for the detection and identification of the key volatiles released due to oxidative degradation of PHAs has been established using a headspace solid-phase microextraction technique. We report the development of nine bio-nano-composite materials based on three types of commercial PHA matrices loaded with three species of nanoclays which represent a different polar behaviour. It has been demonstrated that although the reached outcoming effect depends on the volatile nature, natural sepiolite might result in the most versatile candidate for any the PHA matrices selected. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Pollutant Absorption as a Possible End-Of-Life Solution for Polyphenolic Polymers

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Alexander Petutschnigg

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Gianluca Tondi

Polymers 2019, 11(5), 911; https://doi.org/10.3390/polym11050911 - 20 May 2019

Cited by 17 | Viewed by 3431

Abstract

Tannin- and lignin-furanic foams are natural porous materials that have attracted high interest in the scientific and industrial communities for their high thermal and fire-resistant properties. However, no interesting solutions have been proposed for the management of their end-life as yet. In this [...] Read more.

Tannin- and lignin-furanic foams are natural porous materials that have attracted high interest in the scientific and industrial communities for their high thermal and fire-resistant properties. However, no interesting solutions have been proposed for the management of their end-life as yet. In this study, the phenolic-furanic powders derived from the foams were analyzed for their capacity to remove different pollutants like neutral, cationic, and anionic organic molecules from wastewater. It was observed that the macromolecules produced from initially bigger fractions were more suitable to remove methylene blue and sodium dodecyl sulfate (SDS) while contained absorptions were observed for riboflavin. Acidified tannin powders were also prepared to understand the role of the flavonoid in the absorption mechanism. The latter showed outstanding absorption capacity against all of the tested pollutants, highlighting the key-role of the flavonoid fraction and suggesting the limited contribution of the furanic part. All adsorbents were investigated through FT-IR and solid state ¹³C-NMR. Finally, the powders were successfully regenerated by simple ethanol washing, showing almost complete absorption recovery. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Preparation and Characterization of Microcellulose and Nanocellulose Fibers from Artemisia Vulgaris Bast

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Polymers 2019, 11(5), 907; https://doi.org/10.3390/polym11050907 - 19 May 2019

Cited by 11 | Viewed by 4376

Abstract

Artemisia vulgaris is an economic plant that is spreading widely in central China. Its unused bast generates a large amount of biomass waste annually. Utilizing the fibers in Artemisia vulgaris bast may provide a new solution to this problem. This research attempts to [...] Read more.

Artemisia vulgaris is an economic plant that is spreading widely in central China. Its unused bast generates a large amount of biomass waste annually. Utilizing the fibers in Artemisia vulgaris bast may provide a new solution to this problem. This research attempts to strengthen the understanding of Artemisia vulgaris by analyzing its fiber compositions and preparing micro- and nano-cellulose fibers, which can be used as raw materials for composites. In this work, Artemisia vulgaris bast powder (AP) and microcellulose and nanocellulose fibers (AMFs and ANFs) were produced and characterized by optical microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TG), and bacteriostatic test. The results indicated that cellulose, hemicellulose, and lignin were the main components in the Artemisia vulgaris bast. The cellulose content reached 40.9%. The Artemisia vulgaris single fibers were microcellulose fibers with an average length of 850.6 μm and a diameter of 14.4 μm. Moreover, the AMF had considerable antibacterial ability with an antibacterial ratio of 36.6%. The ANF showed a length range of 250–300 nm and a diameter of 10–20 nm, and it had a higher crystallinity (76%) and a lower thermal stability (initial degradation temperature of 183 °C) compared with raw ANF (233 °C). This study provides fundamental information on Artemisia vulgaris bast cellulose for its subsequent utilization. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Efficient Hydrophobic Modification of Old Newspaper and Its Application in Paper Fiber Reinforced Composites

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Polymers 2019, 11(5), 842; https://doi.org/10.3390/polym11050842 - 10 May 2019

Cited by 7 | Viewed by 3097

Abstract

Paper fibers have gained broad attention in natural fiber reinforced composites in recent years. The specific problem in preparing paper fiber reinforced composites is that paper fibers easily become flocculent after pulverization, which increases difficulties during melt-compounding with polymer matrix and results in [...] Read more.

Paper fibers have gained broad attention in natural fiber reinforced composites in recent years. The specific problem in preparing paper fiber reinforced composites is that paper fibers easily become flocculent after pulverization, which increases difficulties during melt-compounding with polymer matrix and results in non-uniform dispersion of paper fibers in the matrix. In this study, old newspaper (ONP) was treated with a low dosage of gaseous methyltrichlorosilane (MTCS) to solve the flocculation. The modified ONP fibers were characterized by Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and Thermogravimetric Analysis (TG). Then the modified ONP fibers and high-density polyethylene (HDPE) were extruded and pelletized to prepare ONP/HDPE composites via injection molding. Maleic anhydride-grafted polyethylene (MAPE) was added to enhance the interfacial bonding performance with the ultimate purpose of improving the mechanical strength of the composites. The mechanical properties such as tensile, flexural, and impact strength and the water absorption properties of the composite were tested. The results showed that the formation of hydrogen bonding between ONP fibers was effectively prevented after MTCS treatment due to the reduction of exposed –OH groups at the fiber surface. Excessive dosage of MTCS led to severe fiber degradation and dramatically reduced the aspect ratio of ONP fibers. Composites prepared with ONP fibers modified with 4% (v/w) MTCS showed the best mechanical properties due to reduced polarity between the fibers and the matrix, and the relatively long aspect ratio of treated ONP fibers. The composite with or without MAPE showed satisfactory water resistance properties. MTCS was proven to be a cheap and efficient way to pretreat old newspaper for preparing paper fiber reinforced composites. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Synthesis and Properties of Tung Oil-Based Unsaturated Co-Ester Resins Bearing Steric Hindrance

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Polymers 2019, 11(5), 826; https://doi.org/10.3390/polym11050826 - 07 May 2019

Cited by 16 | Viewed by 2653

Abstract

New tung oil (TO)-based, unsaturated, co-ester (Co-UE) macromonomers bearing steric hindrance were synthesized by modifying a TO-based maleate (TOPERMA) monomer with an anhydride structure with hydroxyethyl methacrylate (HEMA) and methallyl alcohol (MAA), respectively. The obtained Co-UE monomers (TOPERMA-HEMA and TOPERMA-MAA) were then characterized [...] Read more.

New tung oil (TO)-based, unsaturated, co-ester (Co-UE) macromonomers bearing steric hindrance were synthesized by modifying a TO-based maleate (TOPERMA) monomer with an anhydride structure with hydroxyethyl methacrylate (HEMA) and methallyl alcohol (MAA), respectively. The obtained Co-UE monomers (TOPERMA-HEMA and TOPERMA-MAA) were then characterized by ¹H NMR and gel permeation chromatography (GPC). For comparison, hydroxyethyl acrylate (HEA)-modified TOPERMA (TOPERMA-HEA) was also synthesized and characterized. Subsequently, the obtained Co-UEs were thermally cured with styrene, and the ultimate properties of the resulting materials were studied. It was found that by introducing the structure of steric hindrance into the TO-based Co-UE monomer, the tensile strength and Young’s modulus of the resulting materials were improved. Furthermore, by reducing the length of the flexible chain in the Co-UE monomer, the tensile strength, Young’s modulus, and glass transition temperature (T_g) of the resultant materials were also improved. The TOPERMA-MAA resin gave the best performance in these TO-based Co-UE resins, which showed a tensile strength of 32.2 MPa, Young’s modulus of 2.38 GPa, and T_g of 130.3 °C. The developed ecofriendly materials show promise in structural plastic applications. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Recycled Heavy Bio Oil as Performance Enhancer for Rubberized Bituminous Binders

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Polymers 2019, 11(5), 800; https://doi.org/10.3390/polym11050800 - 04 May 2019

Cited by 29 | Viewed by 3162

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Asphalt rubber (AR) is a sustainable paving material with merits including waste tire consumption, low traffic noise, and enhanced mechanical performance. However, the poor workability and storage stability limited its further application. This study attempted to alleviate these two concerns of AR simultaneously [...] Read more.

Asphalt rubber (AR) is a sustainable paving material with merits including waste tire consumption, low traffic noise, and enhanced mechanical performance. However, the poor workability and storage stability limited its further application. This study attempted to alleviate these two concerns of AR simultaneously by incorporating heavy bio oil (HBO). To achieve this goal, bio-AR binders with three different mixing sequences were prepared. A series of rheological and chemical tests were conducted. Test results prove that the bio-AR binders exhibited superior rutting and fatigue resistance compared to AR binder. The viscosity values of bio-ARs were closed to AR modified with commercial warm mix additive, which indicates enhancement in workability. Due to the relatively high density of HBO, the density difference between the asphalt liquid phase and crumb rubber in the bio-AR system narrowed, which brought improved storage stability. Among bio-ARs prepared with different mixing sequences, the direct mixing one (ARB) had the most satisfied overall performance. The early incorporation of HBO had limited negative influence on binder performance, but allowed for more energy saving during the bio-AR binder production. Future study will be conducted on performance of bio-AR mixtures and quantitative estimation of its energy saving during the blending and compacting process. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Flexible Textile Strain Sensor Based on Copper-Coated Lyocell Type Cellulose Fabric

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Polymers 2019, 11(5), 784; https://doi.org/10.3390/polym11050784 - 02 May 2019

Cited by 22 | Viewed by 4805

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Integration of sensors in textile garments requires the development of flexible conductive structures. In this work, cellulose-based woven lyocell fabrics were coated with copper during an electroless step, produced at 0.0284 M copper sulfate pentahydrate, 0.079 M potassium hydrogen L-tartrate, and 0.94 M [...] Read more.

Integration of sensors in textile garments requires the development of flexible conductive structures. In this work, cellulose-based woven lyocell fabrics were coated with copper during an electroless step, produced at 0.0284 M copper sulfate pentahydrate, 0.079 M potassium hydrogen L-tartrate, and 0.94 M formaldehyde concentrations. High concentrations led to high homogeneous copper reaction rates and the heterogeneous copper deposition process was diffusion controlled. Thus, the rate of copper deposition did not increase on the cellulose surface. Conductivity of copper coatings was investigated by the resistance with a four probe technique during fabric deformation. In cyclic tensile tests, the resistance of coated fabric (19 × 1.5 cm²) decreased from 13.2–3.7 Ω at 2.2% elongation. In flex tests, the resistance increased from 5.2–6.6 Ω after 5000 bending cycles. After repeated wetting and drying cycles, the resistance increased by 2.6 × 10⁵. The resistance raised from 11–23 Ω/square with increasing relative humidity from 20–80%, which is likely due to hygroscopic expansion of fibers. This work improves the understanding of conductive copper coating on textiles and shows their applicability in flexible strain sensors. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Effect of H₂O₂ Bleaching Treatment on the Properties of Finished Transparent Wood

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Polymers 2019, 11(5), 776; https://doi.org/10.3390/polym11050776 - 01 May 2019

Cited by 58 | Viewed by 4962

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Transparent wood samples were fabricated from an environmentally-friendly hydrogen peroxide (H₂O₂) bleached basswood (Tilia) template using polymer impregnation. The wood samples were bleached separately for 30, 60, 90, 120 and 150 min to evaluate the effects on [...] Read more.

Transparent wood samples were fabricated from an environmentally-friendly hydrogen peroxide (H₂O₂) bleached basswood (Tilia) template using polymer impregnation. The wood samples were bleached separately for 30, 60, 90, 120 and 150 min to evaluate the effects on the changes of the chemical composition and properties of finished transparent wood. Experimental results showed decreases in cellulose, hemicellulose, and lignin content with an increasing bleaching time and while decreasing each component to a unique extent. Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) analysis indicated that the wood cell micro-structures were maintained during H₂O₂ bleaching treatment. This allowed for successful impregnation of polymer into the bleached wood template and strong transparent wood products. The transparent wood possessed a maximum optical transmittance up to 44% at 800 nm with 150 min bleaching time. Moreover, the transparent wood displayed a maximum tensile strength up to 165.1 ± 1.5 MPa with 90 min bleaching time. The elastic modulus (E_r) and hardness (H) of the transparent wood samples were lowered along with the increase of H₂O₂ bleaching treatment time. In addition, the transparent wood with 30 min bleaching time exhibited the highest E_r and H values of 20.4 GPa and 0.45 GPa, respectively. This findings may provide one way to choose optimum degrees of H₂O₂ bleaching treatment for transparent wood fabrication, to fit the physicochemical properties of finished transparent wood. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Sustainable Materials with Enhanced Mechanical Properties Based on Industrial Polyhydroxyalkanoates Reinforced with Organomodified Sepiolite and Montmorillonite

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Lidia García-Quiles

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Ángel Fernández Cuello

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Pere Castell

Polymers 2019, 11(4), 696; https://doi.org/10.3390/polym11040696 - 16 Apr 2019

Cited by 28 | Viewed by 3890

Abstract

Microplastics have become one of the greatest environmental challenges worldwide. To turn this dramatic damage around, EU regulators now want to ensure that plastic itself is fully recyclable or biodegradable. The aim of the present work is to develop a biobased and biodegradable [...] Read more.

Microplastics have become one of the greatest environmental challenges worldwide. To turn this dramatic damage around, EU regulators now want to ensure that plastic itself is fully recyclable or biodegradable. The aim of the present work is to develop a biobased and biodegradable biocomposite based on commercial polyhydroxyalkanoates (PHAs) and nanoclays, with the objective of achieving a reduction of rancid odour while avoiding any loss in thermomechanical properties, thus tackling two key disadvantages of PHAs. This research aims at completely characterising the structural, thermal and mechanical behaviour of the formulations developed, understanding the compatibility mechanisms in order to be able to assess the best commercial combinations for industrial applications in the packaging and automotive sectors. We report the development of nine nanobiocomposite materials based on three types of commercial PHA matrices: a linear poly(3-hydroxybutyrate) (P3HB); two copolymers based on poly(3-hydroxybutyrate)-co-poly(4-hydroxybutyrate) (P3HB-co-P4HB); and nanoclays, which represent a different polar behaviour. Dispersion achieved is highly relevant compared with literature results. Our findings show impressive mechanical enhancements, in particular for P3HB reinforced with sepiolite modified via aminosilanes. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Electrospin-Coating of Paper: A Natural Extracellular Matrix Inspired Design of Scaffold

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Belinda Pingguan-Murphy

Polymers 2019, 11(4), 650; https://doi.org/10.3390/polym11040650 - 09 Apr 2019

Cited by 9 | Viewed by 3457

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Paper has recently found widespread applications in biomedical fields, especially as an alternative scaffolding material for cell cultures, owing to properties such as its fibrous nature, porosity and flexibility. However, paper on its own is not an optimal material for cell cultures as [...] Read more.

Paper has recently found widespread applications in biomedical fields, especially as an alternative scaffolding material for cell cultures, owing to properties such as its fibrous nature, porosity and flexibility. However, paper on its own is not an optimal material for cell cultures as it lacks adhesion moieties specific to mammalian cells, and modifications such as hydrogel integration and chemical vapor deposition are necessary to make it a favorable scaffolding material. The present study focuses on modification of filter paper through electrospin-coating and dip-coating with polycaprolactone (PCL), a promising biomaterial in tissue engineering. Morphological analysis, evaluation of cell viability, alkaline phosphatase (ALP) activity and live/dead assays were conducted to study the potential of the modified paper-based scaffold. The results were compared to filter paper (FP) and electrospun PCL (ES-PCL) as reference samples. The results indicate that electrospin-coating paper is a simple and efficient way of modifying FP. It not only improves the morphology of the deposited electrospun layer through reduction of the fiber diameter by nearly 75%, but also greatly reduces the scaffold fabrication time compared to ES-PCL. The biochemical assays (Resazurin and ALP) indicate that electrospin-coated filter paper (ES-PCL/FP) provides significantly higher readings compared to all other groups. The live/dead results also show improved cell-distribution and cell-scaffold attachment all over the ES-PCL/FP. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Core-Shell Structured HMX@Polydopamine Energetic Microspheres: Synergistically Enhanced Mechanical, Thermal, and Safety Performances

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Polymers 2019, 11(3), 568; https://doi.org/10.3390/polym11030568 - 26 Mar 2019

Cited by 52 | Viewed by 4523

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The solid–solid phase transition, poor mechanical properties, and high sensitivity has impeded further practical applications of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) based polymer bonded explosives (PBXs). To address these issues together, a facile and effective route was employed to achieve a coating of polydopamine (PDA) on [...] Read more.

The solid–solid phase transition, poor mechanical properties, and high sensitivity has impeded further practical applications of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) based polymer bonded explosives (PBXs). To address these issues together, a facile and effective route was employed to achieve a coating of polydopamine (PDA) on the surface of explosive crystals via in situ polymerization of dopamine. Additionally, PBXs based on HMX@PDA microcapsules were prepared with a fluoropolymer as polymer binder. Improved storage modulus, static mechanical strength and toughness, and creep resistance has been achieved in as-prepared PDA modified PBXs. The β-δ phase transition temperature of as-obtained PBXs based on conventional HMX (C-HMX)@PDA was improved by 16.3 °C. The friction sensitivity of the C-HMX based PBXs showed a dramatic drop after the PDA coating. A favorable balance proposed in this paper among thermal stability, mechanical properties, and sensitivity was achieved for C-HMX based PBXs with the incorporation of PDA. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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The Effect of Glycerol, Sugar, and Maleic Anhydride on Pectin-Cellulose Thin Films Prepared from Orange Waste

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Veronika Bátori

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Magnus Lundin

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Dan Åkesson

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Patrik R. Lennartsson

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Mohammad J. Taherzadeh

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Akram Zamani

Polymers 2019, 11(3), 392; https://doi.org/10.3390/polym11030392 - 27 Feb 2019

Cited by 16 | Viewed by 4511

Abstract

This study was conducted to improve the properties of thin films prepared from orange waste by the solution casting method. The main focus was the elimination of holes in the film structure by establishing better cohesion between the major cellulosic and pectin fractions. [...] Read more.

This study was conducted to improve the properties of thin films prepared from orange waste by the solution casting method. The main focus was the elimination of holes in the film structure by establishing better cohesion between the major cellulosic and pectin fractions. For this, a previously developed method was improved first by the addition of sugar to promote pectin gelling, then by the addition of maleic anhydride. Principally, maleic anhydride was introduced to the films to induce cross-linking within the film structure. The effects of concentrations of sugar and glycerol as plasticizers and maleic anhydride as a cross-linking agent on the film characteristics were studied. Maleic anhydride improved the structure, resulting in a uniform film, and morphology studies showed better adhesion between components. However, it did not act as a cross-linking agent, but rather as a compatibilizer. The middle level (0.78%) of maleic anhydride content resulted in the highest tensile strength (26.65 ± 3.20 MPa) at low (7%) glycerol and high (14%) sugar levels and the highest elongation (28.48% ± 4.34%) at high sugar and glycerol levels. To achieve a uniform film surface with no holes present, only the lowest (0.39%) level of maleic anhydride was necessary. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Mechanical Strength Enhancement of Polylactic Acid Hybrid Composites

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Polymers 2019, 11(2), 349; https://doi.org/10.3390/polym11020349 - 17 Feb 2019

Cited by 10 | Viewed by 2898

Abstract

In recent years, there has been an increasing need for materials that are environmentally friendly and have functional properties. Polylactic acid (PLA) is a biomass-based polymer, which has attracted research attention as an eco-friendly material. Various studies have been conducted on functionality imparting [...] Read more.

In recent years, there has been an increasing need for materials that are environmentally friendly and have functional properties. Polylactic acid (PLA) is a biomass-based polymer, which has attracted research attention as an eco-friendly material. Various studies have been conducted on functionality imparting and performance improvement to extend the field of application of PLA. Particularly, research on natural fiber-reinforced composites have been conducted to simultaneously improve their environmental friendliness and mechanical strength. Research interest in hybrid composites using two or more fillers to realize multiple functions are also increasing. Phase change materials (PCMs) absorb and emit energy through phase transition and can be used as a micro encapsulated structure. In this study, we fabricated hybrid composites using microcapsulated PCM (MPCM) and the natural fibrous filler, kenaf. We aimed to fabricate a composite material with improved endothermic characteristics, mechanical performance, and environmental friendliness. We analyzed the endothermic properties of MPCM and the structural characteristics of two fillers and finally produced an eco-friendly composite material. The PCM and kenaf contents were varied to observe changes in the performance of the hybrid composites. The endothermic properties were determined through differential scanning calorimetry, whereas changes in the physical properties of the hybrid composite were determined by measuring the mechanical properties. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Valorization of Alkaline Peroxide Mechanical Pulp by Metal Chloride-Assisted Hydrotropic Pretreatment for Enzymatic Saccharification and Cellulose Nanofibrillation

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Polymers 2019, 11(2), 331; https://doi.org/10.3390/polym11020331 - 14 Feb 2019

Cited by 9 | Viewed by 3264

Abstract

Developing economical and sustainable fractionation technology of lignocellulose cell walls is the key to reaping the full benefits of lignocellulosic biomass. This study evaluated the potential of metal chloride-assisted p-toluenesulfonic acid (p-TsOH) hydrolysis at low temperatures and under acid concentration [...] Read more.

Developing economical and sustainable fractionation technology of lignocellulose cell walls is the key to reaping the full benefits of lignocellulosic biomass. This study evaluated the potential of metal chloride-assisted p-toluenesulfonic acid (p-TsOH) hydrolysis at low temperatures and under acid concentration for the co-production of sugars and lignocellulosic nanofibrils (LCNF). The results indicated that three metal chlorides obviously facilitated lignin solubilization, thereby enhancing the enzymatic hydrolysis efficiency and subsequent cellulose nanofibrillation. The CuCl₂-assisted hydrotropic pretreatment was most suitable for delignification, resulting in a relatively higher enzymatic hydrolysis efficiency of 53.2%. It was observed that the higher residual lignin absorbed on the fiber surface, which exerted inhibitory effects on the enzymatic hydrolysis, while the lower lignin content substrates resulted in less entangled LCNF with thinner diameters. The metal chloride-assisted rapid and low-temperature fractionation process has a significant potential in achieving the energy-efficient and cost-effective valorization of lignocellulosic biomass. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Pyrolytic Behavior of Major Biomass Components in Waste Biomass

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Polymers 2019, 11(2), 324; https://doi.org/10.3390/polym11020324 - 13 Feb 2019

Cited by 23 | Viewed by 3537

Abstract

The pyrolytic behavior of several biomass components including cellulose, hemicellulose, lignin, and tannin, from two sources of waste biomass (i.e., pine bark and pine residues) were examined. Compared to the two aromatic-based components in the biomass, carbohydrates produced much less char but more [...] Read more.

The pyrolytic behavior of several biomass components including cellulose, hemicellulose, lignin, and tannin, from two sources of waste biomass (i.e., pine bark and pine residues) were examined. Compared to the two aromatic-based components in the biomass, carbohydrates produced much less char but more gas. Surprisingly, tannin produced a significant amount of water-soluble products; further analysis indicated that tannin could produce a large amount of catechols. The first reported NMR chemical shift databases for tannin and hemicellulose pyrolysis oils were created to facilitate the HSQC analysis. Various C–H functional groups (>30 different C–H bonds) in the pyrolysis oils could be analyzed by employing HSQC-NMR. The results indicated that most of the aromatic C–H and aliphatic C–H bonds in the pyrolysis oils produced from pine bark and pine residues resulted from the lignin and tannin components. A preliminary study for a quantitative application of HSQC-NMR on the characterization of pyrolysis oil was also done in this study. Nevertheless, the concepts established in this work open up new methods to fully characterize the whole portion of pyrolysis oils produced from various biomass components, which can provide valuable information on the thermochemical mechanisms. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Green-Synthesis of Anisotropic Peptone-Silver Nanoparticles and Its Potential Application as Anti-Bacterial Agent

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Rijuta Ganesh Saratale

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Ganesh Dattatraya Saratale

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Polymers 2019, 11(2), 271; https://doi.org/10.3390/polym11020271 - 05 Feb 2019

Cited by 23 | Viewed by 4349

Abstract

This study demonstrates a green-route-based synthesis of high-concentration suspensions of anisotropic silver nanoparticles (AgNPs) by peptone (Pep), a soluble protein hydrolysate and an abundantly used nutrient source in microbial-media. The transformation of Ag ions from solution into a high-concentration suspension of anisotropic Pep-AgNPs, [...] Read more.

This study demonstrates a green-route-based synthesis of high-concentration suspensions of anisotropic silver nanoparticles (AgNPs) by peptone (Pep), a soluble protein hydrolysate and an abundantly used nutrient source in microbial-media. The transformation of Ag ions from solution into a high-concentration suspension of anisotropic Pep-AgNPs, at an extremely low concentration of peptone (0.02%), indicates that the present green-route synthesis method follows “low volume high concentration nano-synthesis”, and, hence, enhances the economic significance of the process. Process optimization with different concentrations of AgNPs (1–5 mM), NaOH solution (5–40 mM), and peptone (0.004%–0.12%) gave the optimized Pep-AgNPs synthesis at 3 mM of AgNO₃, 20 mM of NaOH, and 0.02% of the peptone concentrations. The green-route synthesized Pep-AgNPs were structurally characterized by the TEM, XPS, FT-IR, and XRD analyses. The Pep-AgNPs against the clinically relevant bacteria Escherichia coli and Staphylococcus aureus gave significant anti-bacterial properties, with a MIC (minimum inhibitory concentration) of 100 ppm. The colony counting and morphological observation of the bacterial cell under SEM corroborated an anti-bacterial potential of the Pep-AgNPs. Therefore, Pep-AgNPs are green-route synthesized, anisotropic, and have a significant anti-bacterial potential that can be used in many relevant applications. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Effect of Operational Conditions on the Behaviour and Associated Costs of Mixed Microbial Cultures for PHA Production

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Polymers 2019, 11(2), 191; https://doi.org/10.3390/polym11020191 - 22 Jan 2019

Cited by 18 | Viewed by 4248

Abstract

Massive production and disposal of petrochemical derived plastics represent relevant environmental problems. Polyhydroxyalkanoates (PHA) are a renewable alternative that can even be produced from wastes. The production of PHA from acetate using mixed microbial cultures was studied. The effect of two key operational [...] Read more.

Massive production and disposal of petrochemical derived plastics represent relevant environmental problems. Polyhydroxyalkanoates (PHA) are a renewable alternative that can even be produced from wastes. The production of PHA from acetate using mixed microbial cultures was studied. The effect of two key operational conditions was evaluated, i.e., substrate concentration and cycle length. The effects of these factors on several responses were studied using a surface response methodology. Several reactors were operated under selected conditions for at least 10 solids retention times to ensure stable operation. Results show that conditions providing higher PHA content involve lower biomass productivities. This has a great impact on biomass production costs. Results suggest then that PHA content alone may not be a reasonable criterion for determining optimal conditions for PHB production. If production costs need to be reduced, conditions that provide a lower PHA content in the selection reactor, but a higher biomass productivity may be of interest. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessEditor’s ChoiceArticle

Poly(lactic acid)/Cellulose Films Produced from Composite Spheres Prepared by Emulsion-Solvent Evaporation Method

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Polymers 2019, 11(1), 66; https://doi.org/10.3390/polym11010066 - 04 Jan 2019

Cited by 30 | Viewed by 5873

Abstract

The compound of poly(lactic acid) (PLA) and cellulose was made by the emulsion-solvent evaporation technique in order to obtain spheres which are then compression molded to produce a biocomposite film. The effect of the dispersant (poly(vinyl alcohol)—PVA)/PLA ratio on the spheres yield was [...] Read more.

The compound of poly(lactic acid) (PLA) and cellulose was made by the emulsion-solvent evaporation technique in order to obtain spheres which are then compression molded to produce a biocomposite film. The effect of the dispersant (poly(vinyl alcohol)—PVA)/PLA ratio on the spheres yield was studied. Moreover, to evaluate the effect of cellulose particle size and surface chemistry on the process yield, unbleached eucalypt kraft pulp and microcrystalline cellulose (MCC), both unmodified and physically or chemically modified were used. PLA/cellulose spheres were characterized regarding its physical properties. It was found that the spheres yield is essentially determined by the PVA/PLA ratio and the percentage of cellulose incorporation is greatly affected by the surface chemistry of cellulose. Regarding the films, DSC runs showed a significant effect of the cellulose type incorporated into PLA matrix on the cold crystallization temperature and on the degree of crystallinity of the biocomposite films. The measurement of tensile properties of the biocomposite films revealed that the strength, elongation at break and toughness (tensile energy absorption at break) of the films incorporating unmodified and chemically modified MCC were substantially improved. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Deterioration in the Physico-Mechanical and Thermal Properties of Biopolymers Due to Reprocessing

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Polymers 2019, 11(1), 58; https://doi.org/10.3390/polym11010058 - 02 Jan 2019

Cited by 37 | Viewed by 5583

Abstract

Biopolymers are an emerging class of materials being widely pursued due to their ability to degrade in short periods of time. Understanding and evaluating the recyclability of biopolymers is paramount for their sustainable and efficient use in a cost-effective manner. Recycling has proven [...] Read more.

Biopolymers are an emerging class of materials being widely pursued due to their ability to degrade in short periods of time. Understanding and evaluating the recyclability of biopolymers is paramount for their sustainable and efficient use in a cost-effective manner. Recycling has proven to be an important solution, to control environmental and waste management issues. This paper presents the first recycling assessment of Solanyl, Bioflex, polylactic acid (PLA) and PHBV using a melt extrusion process. All biopolymers were subjected to five reprocessing cycles. The thermal and mechanical properties of the biopolymers were investigated by GPC, TGA, DSC, mechanical test, and DMA. The molecular weights of Bioflex and Solanyl showed no susceptible effect of the recycling process, however, a significant reduction was observed in the molecular weight of PLA and PHBV. The inherent thermo-mechanical degradation in PHBV and PLA resulted in 20% and 7% reduction in storage modulus, respectively while minimal reduction was observed in the storage modulus of Bioflex and Solanyl. As expected from the Florry-Fox equation, recycled PLA with a high reduction in molecular weight (78%) experienced 9% reduction in glass transition temperature. Bioflex and Solanyl showed 5% and 2% reduction in molecular weight and experienced only 2% reduction in glass transition temperature. These findings highlight the recyclability potential of Bioflex and Solanyl over PLA and PHBV. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Impact of Lignin Content on the Properties of Hemicellulose Hydrogels

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Basel Al-Rudainy

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Mats Galbe

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Monica Arcos Hernandez

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Patric Jannasch

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Ola Wallberg

Polymers 2019, 11(1), 35; https://doi.org/10.3390/polym11010035 - 27 Dec 2018

Cited by 20 | Viewed by 5256

Abstract

Hemicellulose is a promising renewable raw material for the production of hydrogels. This polysaccharide exists in large amounts in various waste streams, in which they are usually impure and heavily diluted. Several downstream processing methods can be combined to concentrate and purify the [...] Read more.

Hemicellulose is a promising renewable raw material for the production of hydrogels. This polysaccharide exists in large amounts in various waste streams, in which they are usually impure and heavily diluted. Several downstream processing methods can be combined to concentrate and purify the hemicellulose. However, such an approach can be costly; hence, the effect of impurities on the formation and properties of hydrogels must be determined. Lignin usually exists in these waste streams as a major impurity that is also difficult to separate. This compound can darken hydrogels and decrease their swellability and reactivity, as shown in many studies. Other properties and effects of lignin impurities are equally important for the end application of hydrogels and the overall process economy. In this work, we examined the feasibility of producing hydrogels from hemicelluloses that originated from sodium-based spent sulfite liquor. A combination of membrane filtration and anti-solvent precipitation was used to extract and purify various components. The influence of the purity of hemicellulose and the addition of lignosulfonates (emulated impurities in the downstream processing) to the crosslinking reaction mixture on the mechanical, thermal, and chemical properties of hydrogels was determined. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Polymeric Composites with Embedded Nanocrystalline Cellulose for the Removal of Iron(II) from Contaminated Water

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Polymers 2018, 10(12), 1377; https://doi.org/10.3390/polym10121377 - 12 Dec 2018

Cited by 13 | Viewed by 2977

Abstract

The exponential increase in heavy metal usage for industrial applications has led to the limited supply of clean water for human needs. Iron is one of the examples of heavy metals, which is responsible for an unpleasant taste of water and its discoloration, [...] Read more.

The exponential increase in heavy metal usage for industrial applications has led to the limited supply of clean water for human needs. Iron is one of the examples of heavy metals, which is responsible for an unpleasant taste of water and its discoloration, and is also associated with elevated health risks if it persists in drinking water for a prolonged period of time. The adsorption of a soluble form of iron (Fe²⁺) from water resources is generally accomplished in the presence of natural or synthetic polymers or nanoparticles, followed by their filtration from treated water. The self-assembly of these colloidal carriers into macroarchitectures can help in achieving the facile removal of metal-chelated materials from treated water and hence can reduce the cost and improve the efficiency of the water purification process. In this study, we aim to develop a facile one-pot strategy for the synthesis of polymeric composites with embedded nanocrystalline cellulose (NCC) for the chelation of iron(II) from contaminated water. The synthesis of the polymeric composites with embedded nanoparticles was achieved by the facile coating of ionic monomers on the surface of NCC, followed by their polymerization, crosslinking, and self-assembly in the form of three-dimensional architectures at room temperature. The composites prepared were analyzed for their physiochemical properties, antifouling properties, and for their iron(II)-chelation efficacies in vitro. The results indicate that the embedded-NCC polymeric composites have antifouling properties and exhibit superior iron(II)-chelation properties at both acidic and basic conditions. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Multiscale Modification of Populus cathayana by Alkali Lignin Combined with Heat Treatment

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Haizhen Zhou

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Jingyu Li

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Erni Ma

Polymers 2018, 10(11), 1240; https://doi.org/10.3390/polym10111240 - 09 Nov 2018

Cited by 7 | Viewed by 3957

Abstract

Chemical modification of wood with green modifiers is highly desirable for sustainable development. With the aim of enhancing the water resistance and dimensional stability of fast growing wood, modifications were conducted using renewable and toxicity-free industrial lignin combined with heat treatment. Poplar ( [...] Read more.

Chemical modification of wood with green modifiers is highly desirable for sustainable development. With the aim of enhancing the water resistance and dimensional stability of fast growing wood, modifications were conducted using renewable and toxicity-free industrial lignin combined with heat treatment. Poplar (Populus cathayana) samples first underwent impregnation with alkali lignin solution and were then subjected to heat treatment at 140–180 °C for two hours. The results indicated that the modified wood showed excellent leaching resistance. The alkali lignin treatment improved surface hydrophobicity and compression strength, and decreased moisture and water uptake, thereby reducing the dimensional instability of modified wood. These changes became more pronounced as the heat-treating temperature increased. Scanning electron microscopy, confocal laser scanning microscopy, and Fourier transform infrared spectroscopy evidenced that a multiscale improvement of the alkali lignin occurred in the cell lumen and cell wall of wood fibers and vessels, with small alkali lignin molecules reacting with the wood matrix. This study paves the way for developing an effective modification approach for fast growing wood, as well as promoting the reuse of industrial lignin for high-value applications, and improves the sustainable development of the forestry industry. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Preparation and Characterization of Low-Molecular-Weight Natural Rubber Latex via Photodegradation Catalyzed by Nano TiO₂

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Polymers 2018, 10(11), 1216; https://doi.org/10.3390/polym10111216 - 01 Nov 2018

Cited by 10 | Viewed by 4931

Abstract

Natural rubber is one of the most important renewable biopolymers used in many applications due to its special properties that cannot be easily mimicked by synthetic polymers. To sustain the existence of natural rubber in industries, modifications have been made to its chemical [...] Read more.

Natural rubber is one of the most important renewable biopolymers used in many applications due to its special properties that cannot be easily mimicked by synthetic polymers. To sustain the existence of natural rubber in industries, modifications have been made to its chemical structure from time to time in order to obtain new properties and to enable it to be employed in new applications. The chemical structure of natural rubber can be modified by exposure to ultraviolet light to reduce its molecular weight. Under controlled conditions, the natural rubber chains will be broken by photodegradation to yield low-molecular-weight natural rubber. The aim of this work was to obtain what is known as liquid natural rubber via photodegradation, with titanium dioxide nanocrystals as the catalyst. Titanium dioxide, which was firstly synthesized using the sol–gel method, was confirmed to be in the form of an anatase, with a size of about 10 nm. In this work, the photodegradation was carried out in latex state and yielded low-molecular-weight natural rubber latex of less than 10,000 g/mol. The presence of hydroxyl and carbonyl groups on the liquid natural rubber (LNR) chains was observed, resulting from the breaking of the chains. Scanning electron microscopy of the NR latex particles showed that titanium dioxide nanocrystals were embedded on the latex surface, but then detached during the degradation reaction. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Natural Silkworm Cocoon Composites with High Strength and Stiffness Constructed in Confined Cocooning Space

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Polymers 2018, 10(11), 1214; https://doi.org/10.3390/polym10111214 - 31 Oct 2018

Cited by 11 | Viewed by 4092

Abstract

In this study, using round paper tubes (PTs) and rectangular cardboard boxes (CBs) as external constraints to control the size of the cocooning space, we fabricated a series of modified silkworm cocoons (PT cocoons and CB cocoons). Their microstructures, morphologies, compositions, and mechanical [...] Read more.

In this study, using round paper tubes (PTs) and rectangular cardboard boxes (CBs) as external constraints to control the size of the cocooning space, we fabricated a series of modified silkworm cocoons (PT cocoons and CB cocoons). Their microstructures, morphologies, compositions, and mechanical properties were characterized and compared with normal silkworm cocoons. These two kinds of modified silkworm cocoons exhibit dense and homogeneous layer structures. Tensile test results indicate that above a size limit of cocooning space, their tensile strengths, Young’s moduli, and strain energy densities increase with the decrease in cocooning space. Especially in comparison with the normal cocoons, the tensile strength and Young’s modulus of the PT-14 cocoon increase by 44% and 100%, respectively. Meanwhile, PT cocoons and CB cocoons, except PT-12, also possess better peeling resistance than normal cocoons. Owing to the dense structure and low porosity, the modified cocoons form robust fiber networks that result in high strength and toughness. This study provides a green and efficient method to fabricate mechanically enhanced silkworm cocoons with special shapes and dense layer structures. The method can be easily subjected to further modification processes and has potential applications in the production of high-performance green cocoon composites and biomimetic materials. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Efficient Adsorption on Benzoyl and Stearoyl Cellulose to Remove Phenanthrene and Pyrene from Aqueous Solution

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Polymers 2018, 10(9), 1042; https://doi.org/10.3390/polym10091042 - 19 Sep 2018

Cited by 16 | Viewed by 3388

Abstract

Benzoyl and stearoyl acid grafted cellulose were synthesized by a simple chemical grafting method. Using these as chemical adsorbents, polycyclic aromatic hydrocarbons (PAHs), like pyrene and phenanthrene, were effectively removed from aqueous solution. The structural and morphological properties of the synthesized adsorbents were [...] Read more.

Benzoyl and stearoyl acid grafted cellulose were synthesized by a simple chemical grafting method. Using these as chemical adsorbents, polycyclic aromatic hydrocarbons (PAHs), like pyrene and phenanthrene, were effectively removed from aqueous solution. The structural and morphological properties of the synthesized adsorbents were determined through X-ray diffraction analysis (XRD), thermal gravimetric analysis (TGA), Fourier transform infrared (FT-IR), FE-SEM, and NMR analyses. Through this method, it was confirmed that benzoyl and stearoyl acid were successfully grafted onto the surface of cellulose. The 5 mg of stearoyl grafted cellulose (St–Cell) remove 96.94% pyrene and 97.61% phenanthrene as compared to unmodified cellulose, which adsorbed 1.46% pyrene and 2.99% phenanthrene from 0.08 ppm pyrene and 0.8 ppm phenanthrene aqueous solution, suggesting that those results show a very efficient adsorption performance as compared to the unmodified cellulose. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Influence of the Lignin Content on the Properties of Poly(Lactic Acid)/lignin-Containing Cellulose Nanofibrils Composite Films

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Polymers 2018, 10(9), 1013; https://doi.org/10.3390/polym10091013 - 11 Sep 2018

Cited by 52 | Viewed by 5031

Abstract

Poly(lactic acid) (PLA)/lignin-containing cellulose nanofibrils (L-CNFs) composite films with different lignin contents were produced bythe solution casting method. The effect of the lignin content on the mechanical, thermal, and crystallinity properties, and PLA/LCNFs interfacial adhesion wereinvestigated by tensile tests, thermogravimetric analysis, differential scanning [...] Read more.

Poly(lactic acid) (PLA)/lignin-containing cellulose nanofibrils (L-CNFs) composite films with different lignin contents were produced bythe solution casting method. The effect of the lignin content on the mechanical, thermal, and crystallinity properties, and PLA/LCNFs interfacial adhesion wereinvestigated by tensile tests, thermogravimetric analysis, differential scanning calorimetry (DSC), dynamic mechanical analysis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The tensile strength and modulus of the PLA/9-LCNFs (9 wt % lignin LCNFs) composites are 37% and 61% higher than those of pure PLA, respectively. The glass transition temperature (T_g) decreases from 61.2 for pure PLA to 52.6 °C for the PLA/14-LCNFs (14 wt % lignin LCNFs) composite, and the composites have higher thermal stability below 380 °C than pure PLA. The DSC results indicate that the LCNFs, containing different lignin contents, act as a nucleating agent to increase the degree of crystallinity of PLA. The effect of the LCNFs lignin content on the PLA/LCNFs compatibility/adhesion was confirmed by the FTIR, SEM, and T_g results. Increasing the LCNFs lignin content increases the storage modulus of the PLA/LCNFs composites to a maximum for the PLA/9-LCNFs composite. This study shows that the lignin content has a considerable effect on the strength and flexibility of PLA/LCNFs composites. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Reinforcement of Thermoplastic Corn Starch with Crosslinked Starch/Chitosan Microparticles

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Polymers 2018, 10(9), 985; https://doi.org/10.3390/polym10090985 - 04 Sep 2018

Cited by 24 | Viewed by 4732

Abstract

Microparticles of corn starch and chitosan crosslinked with glutaraldehyde, produced by the solvent exchange technique, are studied as reinforcement fillers for thermoplastic corn starch plasticized with glycerol. The presence of 10% w/w chitosan in the microparticles is shown to be essential [...] Read more.

Microparticles of corn starch and chitosan crosslinked with glutaraldehyde, produced by the solvent exchange technique, are studied as reinforcement fillers for thermoplastic corn starch plasticized with glycerol. The presence of 10% w/w chitosan in the microparticles is shown to be essential to guaranteeing effective crosslinking, as demonstrated by water solubility assays. Crosslinked chitosan forms an interpenetrating polymer network with starch chains, producing microparticles with a very low solubility. The thermal stability of the microparticles is in agreement with their polysaccharide composition. An XRD analysis showed that they have crystalline fraction of 32% with V_a-type structure, and have no tendency to undergo retrogradation. The tensile strength, Young’s modulus, and toughness of thermoplastic starch increased by the incorporation of the crosslinked starch/chitosan microparticles by melt-mixing. Toughness increased 360% in relation to unfilled thermoplastic starch. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessEditor’s ChoiceReview

A Review on the Partial and Complete Dissolution and Fractionation of Wood and Lignocelluloses Using Imidazolium Ionic Liquids

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Hatem Abushammala

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Jia Mao

Polymers 2020, 12(1), 195; https://doi.org/10.3390/polym12010195 - 11 Jan 2020

Cited by 67 | Viewed by 5225

Abstract

Ionic liquids have shown great potential in the last two decades as solvents, catalysts, reaction media, additives, lubricants, and in many applications such as electrochemical systems, hydrometallurgy, chromatography, CO₂ capture, etc. As solvents, the unlimited combinations of cations and anions have given [...] Read more.

Ionic liquids have shown great potential in the last two decades as solvents, catalysts, reaction media, additives, lubricants, and in many applications such as electrochemical systems, hydrometallurgy, chromatography, CO₂ capture, etc. As solvents, the unlimited combinations of cations and anions have given ionic liquids a remarkably wide range of solvation power covering a variety of organic and inorganic materials. Ionic liquids are also considered “green” solvents due to their negligible vapor pressure, which means no emission of volatile organic compounds. Due to these interesting properties, ionic liquids have been explored as promising solvents for the dissolution and fractionation of wood and cellulose for biofuel production, pulping, extraction of nanocellulose, and for processing all-wood and all-cellulose composites. This review describes, at first, the potential of ionic liquids and the impact of the cation/anion combination on their physiochemical properties and on their solvation power and selectivity to wood polymers. It also elaborates on how the dissolution conditions influence these parameters. It then discusses the different approaches, which are followed for the homogeneous and heterogeneous dissolution and fractionation of wood and cellulose using ionic liquids and categorize them based on the target application. It finally highlights the challenges of using ionic liquids for wood and cellulose dissolution and processing, including side reactions, viscosity, recyclability, and price. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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Open AccessEditor’s ChoiceReview

Nanocelluloses: Natural-Based Materials for Fiber-Reinforced Cement Composites. A Critical Review

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Polymers 2019, 11(3), 518; https://doi.org/10.3390/polym11030518 - 19 Mar 2019

Cited by 78 | Viewed by 8139

Abstract

Nanocelluloses (NCs) are bio-based nano-structurated products that open up new solutions for natural material sciences. Although a high number of papers have described their production, properties, and potential applications in multiple industrial sectors, no review to date has focused on their possible use [...] Read more.

Nanocelluloses (NCs) are bio-based nano-structurated products that open up new solutions for natural material sciences. Although a high number of papers have described their production, properties, and potential applications in multiple industrial sectors, no review to date has focused on their possible use in cementitious composites, which is the aim of this review. It describes how they could be applied in the manufacturing process as a raw material or an additive. NCs improve mechanical properties (internal bonding strength, modulus of elasticity (MOE), and modulus of rupture (MOR)), alter the rheology of the cement paste, and affect the physical properties of cements/cementitious composites. Additionally, the interactions between NCs and the other components of the fiber cement matrix are analyzed. The final result depends on many factors, such as the NC type, the dosage addition mode, the dispersion, the matrix type, and the curing process. However, all of these factors have not been studied in full so far. This review has also identified a number of unexplored areas of great potential for future research in relation to NC applications for fiber-reinforced cement composites, which will include their use as a surface treatment agent, an anionic flocculant, or an additive for wastewater treatment. Although NCs remain expensive, the market perspective is very promising. Full article

(This article belongs to the Special Issue Bio-Based Polymers for Engineered Green Materials)

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