Towards high performance wood composites through interface customization with cellulose-based adhesive.

How to efficiently produce high performance plywood is of particular interest, while its sensitivity to moisture is overcome. This paper presents a simple and scalable strategy for the preparation of high-performance plywood based on the chemical bonding theory; a wood interfacial functionalized platform (WIFP) based on (3-aminopropyl) triethoxysilane (APTES) was established. Interestingly, the APTES-enhanced dialdehyde cellulose-based adhesive (DAC-APTES) was able to effectively establish chemically active adhesive interfaces; the dry/wet shear strength of WIFP/DAC-APTES adhesive was 3.15/1.31 MPa, which was much higher than 0.7 MPa (GB/T 9846-2015). The prepared plywood showed excellent wood-polymer interface adhesion, which exceeded the force that the wood itself could withstand. In addition, the DAC-APTES adhesive exhibits moisture evaporation-induced curing behavior at room temperature and can easily support the weight of an adult weighing 65.7 Kg. This research provides a novel approach for functionalized interface design of wood products, an effective means to prepare high-performance plywood.

Amination and crosslinking of acetone-fractionated hardwood kraft lignin using different amines and aldehydes for sustainable bio-based wood adhesives.

Hardwood kraft lignin from the pulping industry is burned or discarded. Its valorization was conducted by subjecting fractionation, amination with ethylenediamine, diethylenetriamine, and monoethanolamine, and crosslinking with formaldehyde or glyoxal to obtain bio-based wood adhesives. Acetone-soluble and insoluble hardwood kraft lignin were prepared and subjected to amination and then crosslinking. Fourier transform infrared, 13C NMR, 15N NMR, and X-ray photoelectron spectroscopy results revealed successful amination with amide, imine, and ether bonds and crosslinking of all samples. Hardwood kraft lignin aminated with diethylenetriamine/ethylenediamine and crosslinked using glyoxal exhibited excellent results in comparison with samples crosslinked using formaldehyde. Acetone-insoluble hardwood kraft lignin aminated and crosslinked using diethylenetriamine and formaldehyde, respectively, exhibited excellent adhesion strength with plywood, satisfying the requirements of the Korean standards. The amination and crosslinking of industrial waste hardwood kraft lignin constitute a beneficial valorization method.

Structural Characteristics and Properties of Redissolved Silk Sericin.

Silk sericin has garnered the attention of researchers as a promising biomaterial because of its good biocompatibility and high water retention. However, despite its useful properties, the poor storage stability of sericin has restricted its extensive use in biorelated applications. This study extracted sericin from silkworm cocoon, dried and stored it as a solid, and then dissolved it in hot water conditions to improve the storage stability of sericin for its use. The dissolution behavior of the extracted sericin solids was examined in conjunction with the structural characteristics and properties of dissolved sericin. Consequently, the results of solution viscosity, gel strength, crystallinity index, and thermal decomposition temperature indicated that the molecular weight (MW) of the dissolved sericin remained constant until a dissolution time of 5 min, following which deterioration was observed. The optimum condition of dissolution of the extracted sericin solid was 5 min at 90 °C. Conclusively, the extracted sericin could be stored in a dry state and dissolved to prepare redissolved sericin aqueous solution with the same MW as extracted sericin, thereby improving the storage stability of the sericin aqueous solution.

Fabrication, Structure, and Properties of Nonwoven Silk Fabrics Prepared with Different Cocoon Layers.

In this study, five different nonwoven silk fabrics were fabricated with silk fibers from different cocoon layers, and the effect of the cocoon layer on the structural characteristics and properties of the nonwoven silk fabric was examined. The diameter of the silk fiber and thickness of the nonwoven silk fabric decreased from the outer to the inner cocoon layer. More amino acids with higher hydrophilicity (serine, aspartic acid, and glutamic acid) and lower hydrophilicity (glycine and alanine) were observed in the outer layers. From the outer to the inner layer, the overall crystallinity and contact angle of the nonwoven silk fabric increased, whereas its yellowness index, moisture retention, and mechanical properties decreased. Regardless of the cocoon layer at which the fiber was sourced, the thermal stability of fibroin and sericin and good cell viability remained unchanged. The results of this study indicate that the properties of nonwoven silk fabric can be controlled by choosing silk fibers from the appropriate cocoon layers. Moreover, the findings in this study will increase the applicability of nonwoven silk fabric in the biomedical and cosmetic fields, which require specific properties for industrialization.

Chemical and Thermal Characteristics of Ion-Exchanged Lignosulfonate.

Lignosulfonate features sulfonate groups, which makes it soluble in water and hence, suitable for a wide range of applications. However, its characterization is challenging because of its limited solubility in organic solvents. Thus, this study investigated the chemical and thermal characteristics of ion-exchanged sodium lignosulfonate (Na-LS) and compared it with those of industrial kraft lignin derived from softwood and hardwood. The results demonstrated that the ion exchange successfully converted Na-LS to lignosulfonic acid (H-LS), as proven by the Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and elemental analysis. H-LS has a greater apparent molecular weight than those of Na-LS and softwood and hardwood kraft lignin (SKL and HKL). According to 31P nuclear magnetic resonance (NMR) analysis, H-LS has less phenolic OH than SKL and HKL, indicating that it has more polymeric chains. Furthermore, H-LS has substantially more native side chains, such as ß-O-4 units, than SKL and HKL. Thermal analysis revealed that H-LS has a greater glass temperature (Tg) than SKL and HKL, although Na-LS has a lower Tg than SKL and HKL. In addition, H-LS degraded faster than Na-LS did because the acid condition accelerated degradation reaction.

The role of acetone-fractionated Kraft lignin molecular structure on surface adhesion to formaldehyde-based resins.

One of the key strategies for valorizing kraft lignin (KL) into value-added products such as bio-based adhesives is to perform solvent fractionation of KL to produce lignin with improved homogeneity. Understanding the structure and properties of fractionated KL will aid in the selection of the best samples for certain applications. In this study, acetone-fractionated KL from softwood and hardwood was characterized to understand its chemical structure, elemental composition, molecular weight, and thermal properties. The results revealed that acetone-insoluble KL (AIKL) fractions from softwood and hardwood have greater molecular weight, polydispersity, glass temperature, carbohydrate content, aliphatic hydroxyl groups, and a variety of native wood lignin side chains. In contrast, acetone-soluble KL (ASKL) fractions have a significantly lower molecular weight and polydispersity, a lower glass-transition temperature, a more condensed structure, more aromatic hydroxyl groups, and fewer native wood lignin side chains. In addition, the ASKL samples demonstrated stronger adhesive force and work of adhesion toward phenol-formaldehyde (PF) and urea-formaldehyde (UF) resins than the AIKL samples, regardless of the lignin source. These findings suggest that ASKL has great potential as a substitute for phenol in PF resins and as a green additive to reinforce UF resins.

Intelligent pH- and ammonia-sensitive indicator films using neutral red immobilized onto cellulose nanofibrils.

In this study, colorimetric indicator films (CIFs) were developed by integrating neutral red covalently immobilized onto TEMPO-oxidized cellulose nanofibrils (NR@TOCNFs) and poly(acrylic acid) (PAA) inside a poly(vinyl alcohol) (PVA) matrix. The successful covalent immobilization of NR onto the TOCNFs was confirmed using attenuated total reflection-Fourier transform infrared, X-ray photoelectron spectroscopy, and thermogravimetric analyses. The CIFs had a visible color change from red to yellow as the pH changed from 2.0 to 10.0. The colorimetric response of CIFs improved as the NR@TOCNF content increased, while it decreased as the PAA level increased. The critical pH ranges for the color change of CIFs were 6-7, 7-8, and 8-9 for 3 %, 5 %, and 7 % PAA, respectively, at 0.3 % NR@TOCNF. The best ammonia sensitivity was found in the indicator films containing 3 % PAA and 0.3 % NR@TOCNF. These results showed that the CIFs could be applied for freshness detection in food packaging.

Surface Modified Nanocellulose and Its Reinforcement in Natural Rubber Matrix Nanocomposites: A Review.

Natural rubber is of significant economic importance owing to its excellent resilience, elasticity, abrasion and impact resistance. Despite that, natural rubber has been identified with some drawbacks such as low modulus and strength and therefore opens up the opportunity for adding a reinforcing agent. Apart from the conventional fillers such as silica, carbon black and lignocellulosic fibers, nanocellulose is also one of the ideal candidates. Nanocellulose is a promising filler with many excellent properties such as renewability, biocompatibility, non-toxicity, reactive surface, low density, high specific surface area, high tensile and elastic modulus. However, it has some limitations in hydrophobicity, solubility and compatibility and therefore it is very difficult to achieve good dispersion and interfacial properties with the natural rubber matrix. Surface modification is often carried out to enhance the interfacial compatibilities between nanocellulose and natural rubber and to alleviate difficulties in dispersing them in polar solvents or polymers. This paper aims to highlight the different surface modification methods employed by several researchers in modifying nanocellulose and its reinforcement effects in the natural rubber matrix. The mechanism of the different surface medication methods has been discussed. The review also lists out the conventional filler that had been used as reinforcing agent for natural rubber. The challenges and future prospective has also been concluded in the last part of this review.

Covalent immobilization of bromocresol purple on cellulose nanocrystals for use in pH-responsive indicator films.

This study developed pH-indicator films by combining esterified cellulose nanocrystals (e-CNCs) with activated bromocresol purple (a-BCP) via covalent bonding for pH-sensitive color-changing applications. The e-CNC/a-BCP particles were incorporated into cellulose acetate polymer to prepare pH-sensitive color changing films. Binding of a-BCP to e-CNCs was proven by attenuated total reflection infrared (ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Colorimetric analysis showed that films containing 10% or 15% e-CNC/a-BCP particles had critical color changes either at pH 4-5, or pH 7-8. The films with 10% e-CNC/a-BCP particles also revealed excellent leaching resistance under acidic conditions. Color changes were reversible between pH 2 and 10. These pH-indicator films had visible color changes in response to pH variations, color reversibility, leaching resistance, and sufficient rigidity even though mechanical properties decreased as the e-CNC/a-BCP content increased from 0% to 15%.

Optimum oxidation for direct and efficient extraction of carboxylated cellulose nanocrystals from recycled MDF fibers by ammonium persulfate.

For the first time, this study demonstrates a direct extraction of carboxylated cellulose nanocrystals (c-CNCs) from recycled medium density fiberboard (r-MDF) fibers by ammonium persulfate (APS) without any chemical pre-treatment. The aim of this research was to find an optimum condition for isolating c-CNCs from r-MDF fibers by studying the effect of reaction parameters on the characteristics of c-CNCs. The rod-like c-CNCs had an average length and width of 170 to 365 nm and 13 to 17 nm, leading to an aspect ratio of 13∼21. The optimum conditions for a maximum yield and crystallinity were obtained at a reaction temperature of 70 °C, reaction time of 16 h and APS concentration of 1.5 mol L-1. Thermal analysis also revealed lower thermal stability of the c-CNCs compared to r-MDF fibers. The APS oxidation is a viable option for converting r-MDF fibers into value-added c-CNCs.

A Review on Citric Acid as Green Modifying Agent and Binder for Wood.

Citric acid (CA) can be found naturally in fruits and vegetables, particularly citrus fruit. CA is widely used in many fields but its usage as a green modifying agent and binder for wood is barely addressed. Esterification is one of the most common chemical reactions applied in wood modification. CA contains three carboxyl groups, making it possible to attain at least two esterification reactions that are required for crosslinking when reacting with the hydroxyl groups of the cell wall polymers. In addition, the reaction could form ester linkages to bring adhesivity and good bonding characteristics, and therefore CA could be used as wood binder too. This paper presents a review concerning the usage of CA as a wood modifying agent and binder. For wood modification, the reaction mechanism between wood and CA and the pros and cons of using CA are discussed. CA and its combination with various reactants and their respective optimum parameters are also compiled in this paper. As for the major wood bonding component, the bonding mechanism and types of wood composites bonded with CA are presented. The best working conditions for the CA in the fabrication of wood-based panels are discussed. In addition, the environmental impacts and future outlook of CA-treated wood and bonded composite are also considered.

Effect of storage and drying temperature on the gelation behavior and structural characteristics of sericin.

Owing to unique properties, including the wound healing effect, sericin gel and films have attracted significant attention in the biomedical and cosmetic fields. The structural characteristics and properties of sericin gels and films are especially important owing to their effect on the performance of sericin in biomedical and cosmetic applications. In the present study, the effect of temperature on the gelation behavior, gel disruption, and sol-gel transition of sericin was examined using rheometry. In addition, the effect of the drying temperature on the structural characteristics of the sericin film was determined via Fourier transform infrared (FTIR) spectroscopy. The strength of the sericin gel increased and the gelation process was prolonged with decreasing storage temperatures. FTIR and differential scanning calorimetry (DSC) results also revealed that the crystallinity and the thermal decomposition temperature of the sericin film increased with decreasing drying temperature. The sericin gels were disrupted at a storage time of 40min when they were stored at temperatures higher than 50°C, and the corresponding gel strength decreased with increasing temperature. Furthermore, the thermo-reversible nature of gel-sol transition of sericin was confirmed by rheological and FTIR measurements.

A novel approach for FE-SEM imaging of wood-matrix polymer interface in a biocomposite.

Understanding the interface between polymer and biomass in composite products is important for developing high performance products, as the quality of adhesion at the interface determines composite properties. For example, with greater stiffness compared to polymer matrix, such as that of high density polyethylene, the wood component enhances stiffness of wood-polymer composites, provided there is good adhesion between composite components. However, in composites made from wood flour (wood particles) and synthetic resins it is often difficult to clearly resolve particle-matrix interfaces in the conventionally employed microscopy method that involves SEM examination of fractured faces of composites. We developed a novel approach, where composites made from high density polyethylene and wood flour were examined and imaged with a FE-SEM (field emission scanning electron microscope) in transverse sections cut through the composites. Improved definition of the interface was achieved using this approach, which enabled a more thorough comparison to be made of the features of the interface between wood particles and the matrix in composites with and without a coupling agent, as it was possible to clearly resolve the interfaces for particles of all sizes, from large particles consisting of many cells down to tiny cell wall fragments, particularly in composites that did not incorporate the coupling agent used to enhance particle adhesion with the matrix polymer. The method developed would be suitable particularly for high definition SEM imaging of a wide range of composites made combining wood and agricultural residues with synthetic polymers.

MRT letter: high resolution SEM imaging of nano-architecture of cured urea-formaldehyde resin using plasma coating of osmium.

Nanoarchitecture of cured urea-formaldehyde (UF) resins was examined with a field-emission scanning electron microscope (FE-SEM) after coating samples with osmium, which is considered to produce particles of considerably smaller size compared to other metal coatings used in SEM studies. This method enabled comparison of the nanoarchitecture of UF resins of low (1.0) and high (1.6) formaldehyde/urea (F/U) mole ratios to be made, based on imaging of extremely small size particles as part of UF resin architecture, not described before. Imaging revealed presence of relatively large globular particles (148.084-703.983 nm size range) as well as smaller substructures (28.004-39.604 nm size range) as part of the architecture of 1.0-mole UF resin. Globular particles were also present in 1.6 mole UF resin, but of considerably smaller size (14.760-50.269 nm). The work presented demonstrates usefulness of osmium coating in unraveling the intricacies of the nanostructural organization of cured UF resins, prompting wider application of this immensely useful but grossly underutilized metal coating type in high resolution SEM examination of biological and materials samples.

Villous adenoma of the urinary bladder.

Villous adenomas arising in the urinary tract are an uncommon occurrence. They have been identified in the urachus, urethra, prostate, and throughout the bladder. Villous adenomas arising in the bladder are rare tumors that have been described as isolated cases and a few case series. We report a new case of a large villous adenoma arising in the bladder that was treated by transurethral resection.