基于互穿网络技术构筑的氧化海藻酸钠/纤维素纳米晶/聚丙烯酰胺-明胶复合水凝胶与性能

为了提高海藻酸盐水凝胶的生物应用性,采用互穿网络技术、纤维素纳米晶(CNCs)补强和明胶表面覆积相结合的方法构建了氧化海藻酸盐/纤维素纳米晶/聚丙烯酰胺-明胶 (OSA/CNCs/PAM-GT) 复合水凝胶。通过FT-IR、TGA、 XRD、溶胀性和降解性实验以及细胞相容性测试考察了CNCs含量对OSA/CNCs/PAM-GT复合水凝胶结构和性能的影响。实验结果表明,CNCs能够与基体中的聚合物产生相互作用力。并且随着CNCs含量的增加,OSA/CNCs/PAM-GT 复合水凝胶的孔隙率下降,力学性能提高。而且它们的溶胀性和生物降解性虽然受CNCs含量增加而呈现下降的趋势,但是幅度较小,说明CNCs能够在一定程度上调控复合水凝胶的物化性能。同时,OSA/CNCs/PAM-GT 复合水凝胶展现出较好的细胞粘附、增殖和分化性能。当CNCs的含量在0.5%时,细胞增殖的效果最佳,而CNCs的含量为1.5%时,细胞分化效果最显著。因此,将CNCs掺杂到OSA/PAM互穿网络基体中能够有效地调控其生物性能,使其适用于生物医学领域。     

Interfacial modification mechanism of nanocellulose as a compatibilizer for immiscible binary poly(vinyl alcohol)/poly(ethylene oxide) blends

We undertook this study to understand reinforcement mechanism of short cellulose nanocrystals (CNCs) and long cellulose nanofibrils (CNFs) as compatibility agents for improving the interfacial miscibility of poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) blends. The effects of the two cellulose nanofibers on the morphological, mechanical, and thermal properties of the polymer blends were compared systematically. The light transparency, scanning electron microscopy, and Fourier transform infrared results show that nanocellulose between PVA and PEO eliminated the negative effects generated by the immiscible interface through increased hydrogen bonding. Thermogravimetric analysis and differential scanning calorimetry results show that crystalline region reorganization around the interface facilitated the shift of the polymer blends from multiple phases to a homogeneous phase. According to the Halpin‐Kardos and Quali models, we assumed that the potential for repairing the immiscible interface would have a larger effect than the potential of reinforcement. At the same concentration, polymer blends with CNCs showed greater light transparency, strength, modulus, and crystal structure than with those with CNFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45896.     

Fabrication of alginate/sericin/cellulose nanocrystals interpenetrating network composite hydrogels with enhanced physicochemical properties and biological activity

Sodium alginate (SA) possesses good biocompatibility and can form hydrogel materials under certain conditions, which has been widely used in tissue engineering. However, the absence of cellular recognition sites and low mechanical strength for single-component alginate (ALG) hydrogels limit their practical applications. Therefore, enhancing the shortcomings of ALG hydrogels and augmenting their characteristics hold immense importance for their medical uses. In this study, comprehensively considering the excellent properties of cellulose nanocrystals (CNCs) and sericin (SS), the alginate/sericin/cellulose nanocrystalline (ALG/SS/CNCS) composite hydrogels were constructed by interpenetrating network (IPN) technique using hydroxyapatite/D-glucono-δ-lactone (HAP/GDL) as the endogenous ionic cross-linking agent of SA, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) as the chemical covalent cross-linking agent of SS and CNCS as the reinforcing agent. The effects of SS and CNCs additions on the comprehensive properties of ALG/SS/CNCs composite hydrogels, such as their morphologies, structure, mechanical properties, swelling, degradability, and cytocompatibility were investigated. The findings indicated that the ALG/SS/CNCS IPN composite hydrogels which were created through the physical blending of SA and SS, displayed a consistent three-dimensional form and a porous configuration. The weak mechanical strength of pure ALG hydrogels can be effectively improved and the swelling stability and mechanical properties of the composite hydrogels can be enhanced through the construction of IPN network and the incorporation of CNCs, thanks to the presence of intermolecular hydrogen bonding. The biodegradability of ALG/SS/CNCS composite hydrogels increased as the SS content increased, indicating that SS facilitated their biomineralization due to its inherent susceptibility to degradation. The results of the cell compatibility test conducted in a laboratory setting showed that SS and CNCS had the ability to enhance the attachment, proliferation, and differentiation of MC3T3-E1 cells on the ALG/SS/CNCS composite hydrogels. Hence, incorporating SS and CNCS into the alginate matrix to create IPN composite hydrogels could significantly enhance the physicochemical and biological characteristics of ALG hydrogels, thus rendering them appropriate for tissue engineering purposes.     

Influence of the nanofiber dimensions on the properties of nanocellulose/poly(vinyl alcohol) aerogels

The investigation of aerogels made from cellulose nanofibers and poly(vinyl alcohol) (PVOH) as a polymeric binder is reported. Aerogels based on different nanocellulose types were studied to investigate the influence of the nanocellulose dimensions and their rigidity on the morphology and mechanical properties of the resulting aerogels. Thus, cellulose nanocrystals (CNCs) with low (10), medium (25), and high (80) aspect ratios, isolated from cotton, banana plants, and tunicates, respectively, microfibrillated cellulose (MFC) and microcrystalline cellulose (MCC) were dispersed in aqueous PVOH solutions and aerogels were prepared by freeze‐drying. In addition to the cellulose type, the PVOH‐ and the CNC‐concentration as well as the freeze‐drying conditions were varied, and the materials were optionally cross‐linked by an annealing step or the use of a chemical cross‐linker. The data reveal that at low PVOH content, rigid, high‐aspect ratio CNCs isolated from tunicates afford aerogels that show the least amount of shrinking upon freeze‐drying and display the best mechanical properties. However, with increasing concentration of PVOH or upon introduction of a chemical cross‐linker the differences between materials made from different nanocellulose types decrease. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41740.     

纤维素辐照改性及其应用

辐照技术利用电离辐射诱发物理化学反应(例如交联、聚合、接枝、降解等)对材料进行加工或改性,与常规加工方法相比,具有节能、无环境污染等特点。将辐照技术应用于纤维素改性过程近年已成为非动力核技术应用领域研究的热点之一。本工作对目前纤维素的辐照技术及其基本反应机理进行了概述,其中包括纤维素膜材料、纤维素水凝胶、纤维素微晶/纳米材料,并对纤维素辐照改性过程的辐照环境,包括溶剂、敏化剂、温度、辐照剂量、环境氛围、结晶度等进行了总结。     

Extraction of cellulose nanocrystals and fabrication of high alumina refractory bricks using pencil chips as a waste biomass source

Extraction of “green” cellulose nanocrystals (CNCs) from waste biomass is a sustainable strategy for high valued valorization in the view of socio-economic and environmental issues. Herein, for the first time, waste pencil chips (PC) as a potential source of cellulose, were used for the extraction of CNCs. CNCs were successfully extracted from PC wastes using alkali and bleaching chemical treatments to remove hemicellulose and lignin followed by acid hydrolysis using concentrated sulfuric acid. The products after each step were characterized in terms of crystallinity, chemical structures, thermal properties, and morphologies. The XRD results showed that the crystalline index increased about 16% from PC (75%) to CNCs (91%). The FTIR analysis confirmed the removal of the hemicellulose and lignin from PC after alkali and bleaching treatments. The TGA analysis showed that the thermal stability of the CNCs is affected mainly by the dehydration reaction caused by sulfate groups. The SEM and FE-SEM images showed that after chemical treatments, defibrillation of fibers occurs and CNCs have a needle/rod like structure. Also, the specific surface aera was greatly increased from 0.495 for PC to 486.430 m²/g for CNCs. Herein, for the first time, lignin-containing cellulose extracted from PC was replaced with sawdust (SRB) in the production of alumina refractory bricks (RBs), as a pore former/binder. Interestingly, the prepared RBs (PC–NaOH/RB) had a greater amount of alumina (83%) and a lower density (0.75 g/cm³) than SRB. The classification temperature increased from 1650 for SRB to 1717 °C for PC-NaOH/RB.     

The electrospun polyhydroxybutyrate fibers reinforced with cellulose nanocrystals: Morphology and properties

Polyhydroxybutyrate (PHB) has been used in the biomedical field. However, the poor mechanical properties of PHB have limited its application. Here, electrospun fibrous nanocomposite mats reinforced with cellulose nanocrystals (CNCs) were fabricated by using PHB as polymeric matrix. The morphological, thermal, mechanical properties, as well as cytotoxicity were characterized. Increasing the concentration of CNCs caused a decrease in diameter of the electrospun fibers. Moreover, thermal analysis indicated that melting temperature of PHB/CNCs electrospun fibers were improved with the increased CNCs content. The addition of CNCs gradually enhanced the tensile strength till 8 wt % content followed by a gradual decrease at higher CNCs content (12–22 wt %) in tensile strength. The PHB/CNCs electrospun fibers were nontoxic to L‐929 and capable of supporting cell proliferation in all conditions. This study demonstrates that fibrous PHB/CNCs electrospun fibers are cytocompatible and potentially useful mechanical properties for biomedical application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43273.     

Modified cellulose nanocrystals enhancement to mechanical properties and water resistance of vegetable oil-based waterborne polyurethane

Environmentally friendly and lightweight silylated cellulose nanocrystal (SCNCs)/waterborne polyurethane (WPU) composite films that exhibit excellent mechanical properties and water resistance were prepared. The cellulose nanocrystals (CNCs) of the filamentous structure were surface-modified by γ-aminopropyltriethoxysilane (APTES) and then introduced into a castor oil-based aqueous polyurethane (WPU) matrix by in situ polymerization. The morphology and silylation degree of CNCs were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier infrared transform spectroscopy at different APTES concentrations. The results showed that the surface of the nanocellulose crystal has the best silylation morphology and thermal stability with incorporation of 6 wt % APTES. The thermal stability, mechanical properties, surface morphology, and water resistance of the nanocomposites were investigated by TGA, tensile test, SEM and optical contact angle, water absorption test, and mechanical property test after immersed in water. It was found that the effective introduction of modified CNCs resulted in a significant increase in tensile strength at high levels, and the thermal stability and hydrophobicity of the material were improved simultaneously, reaching the percolation threshold at a 0.50 wt % SCNCs as determined theoretically. This study provided an approach to the design and development of surface-modified CNCs/vegetable oil-based polymer composites by using an appropriate concentration of silane coupling agent to modify CNCs and improve the compatibility between nanocellulose and vegetable oil-based polymer matrices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48228.     

Characterization and mechanical properties of ultraviolet stimuli‐responsive functionalized cellulose nanocrystal alginate composites

The poor mechanical properties of alginate when exposed to aqueous solution have been a problem plaguing researchers within the biomedical field. In order to be able to improve the mechanical properties in a systematic manner functionalized cellulose nanocrystals (CNCs) were added to alginate and UV‐induced crosslinked following an azo‐initiated free radical polymerization. CNCs were functionalized with 4‐pentenoic acid (PA‐g‐CNCs) using a simple, environmentally friendly solvent‐free esterification. The dimensional and crystallinity properties of PA‐g‐CNCs remained unchanged following esterification. Thermogravimetric analysis, Fourier transform infrared spectroscopy, and ¹³C nuclear magnetic resonance indicated that 4‐pentenoic acid was present on the surface of CNCs through bulk analysis. These PA‐g‐CNCs were then used in the creation of composites with an azo‐initiator to induce UV‐dependent crosslinking for the improvement of the mechanical properties of alginate. It was shown that the properties of alginate can be enhanced with the addition of functionalized CNCs to nanocomposites in mechanical testing in wet and dry conditions. These results suggest that the addition of PA‐g‐CNCs and crosslinking by UV‐dependent free radical polymerization improves the performance of alginate when tested in dry conditions, but without any apparent dependence to azo‐initiated crosslinking when exposed to water in regards to mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45857.     

纤维素基水凝胶的研究进展

纤维素是世界上最丰富的天然、可再生以及可生物降解的高分子材料，在化工、材料等领域有广泛的应用。本文主要对近几年来纤维素基水凝胶的研究进展进行了归纳总结。首先，介绍了纤维素基水凝胶的研究背景。其次，列举了纤维素水基凝胶的交联方法，主要有物理交联与化学交联。其中物理交联有氢键交联、疏水性交联、离子交联等，化学交联则是酯化交联、迈克尔加成、自由基共聚合、动态共价键交联等。最后，重点介绍了纤维素基水凝胶在可降解性、生物医学性、亲水性、吸附性、导电性等领域方面的应用。此外，对于纤维素基水凝胶材料在高机械性和产业化制备等方面的发展进行了展望。     

Recent advances in nanocellulose for biomedical applications

Nanocellulose materials have undergone rapid development in recent years as promising biomedical materials because of their excellent physical and biological properties, in particular their biocompatibility, biodegradability, and low cytotoxicity. Recently, a significant amount of research has been directed toward the fabrication of advanced cellulose nanofibers with different morphologies and functional properties. These nanocellulose fibers are widely applied in medical implants, tissue engineering, drug delivery, wound‐healing, cardiovascular applications, and other medical applications. In this review, we reflect on recent advancements in the design and fabrication of advanced nanocellulose‐based biomaterials (cellulose nanocrystals, bacterial nanocellulose, and cellulose nanofibrils) that are promising for biomedical applications and discuss material requirements for each application, along with the challenges that the materials might face. Finally, we give an overview on future directions of nanocellulose‐based materials in the biomedical field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41719.     

Improving the mechanical resistance of waterborne wood coatings by adding cellulose nanofibres

In the present study, microfibrillated cellulose (MFC) and nanocrystalline cellulose (NCC) were applied as additives for a waterborne acrylate/polyurethane-based wood coating in order to improve the mechanical resistance of coated wood surfaces. Coating mixtures containing up to 5 wt% nanocellulose were prepared by high-shear mixing and applied to wood substrates. The optical, mechanical and chemical properties of cured coatings were characterized. Surface roughness, gloss, scratch resistance, abrasion resistance and resistance against chemicals were determined according to the relevant European standards. Additionally, nanoindentation (NI) was used to assess the micromechanical properties of modified and unmodified coatings. Owing to a higher surface roughness, cellulose-filled coatings showed significantly lower levels of gloss than the unmodified coating indicating that nanocellulose acts as a matting agent. NI experiments revealed a slightly positive effect of nanocellulose addition on the hardness and modulus of the coatings. While scratch resistance improved consistently with increasing nanocellulose addition, abrasion resistance was found to improve only sporadically. Tensile tests on free-standing coating films revealed a significantly higher tensile strength and modulus for cellulose-filled coatings. Overall, the results suggest that the addition of cellulose nanofibres primarily improves the internal cohesion of the coating layer whereby MFC was more effective than NCC.     

N,P co-doped porous graphene with high electrochemical properties obtained via the laser induction of cellulose nanofibrils

Cellulose and its derivatives are natural materials with high carbon contents, but it is challenging to convert their carbon into high value-added carbonaceous materials(e.g., graphene). Here, an approach to convert the carbon in cellulose into N, P co-doped porous graphene(LIG) materials via laser induction is proposed. Cellulose nanofibrils(CNFs), a cellulose derivative with high dispersion uniformity and abundant surface hydroxyl groups, were easily formed on a bulk substrate(thickness ≥5 mm)...     

Temperature-dependent property development in hydrogels derived from hydroxypropylcellulose

Hydrogels constitute an important class of responsive materials that are employed in numerous biomedical and personal-care applications, most notably of which are controlled drug delivery, separations and superabsorbency. Since aqueous hydroxypropylcellulose (HPC) solutions exhibit lower critical solution behavior, hydrogels produced from this cellulose ether are temperature-responsive, swelling at low temperatures and contracting at high temperatures. If HPC hydrogels are synthesized at temperatures in the single-phase regime, they remain nonporous, whereas those crosslinked in the biphasic regime become microporous. In this work, we employ the modified temperature-induced phase separation (TIPS) protocol to generate nonporous and microporous HPC hydrogels crosslinked at different temperatures. The dynamic mechanical properties and swelling capacities of these hydrogels are reported as functions of crosslinking temperature.     

Recent developments in nanocellulose-based biodegradable polymers,thermoplastic polymers,and porous nanocomposites

Nanocellulose has generated a great deal of interest as a source of nanometer-sized reinforcement, because of its good mechanical properties. In the last few years, nanocellulose has also attracted much attention due to environmental concerns. This review presents an overview of recent developments in this area, including the production, characterization, properties, and range of applications of nanocellulose-based biodegradable polymers, thermoplastic polymers, and porous nanocomposites. After explaining the unique properties of nanocellulose and its various preparation techniques, an orderly introduction of various nanocellulose-reinforced biodegradable polymers such as starch, proteins, alginate, chitosan, and gelatin is provided. Subsequently, the effects of nanocellulose on the properties of thermoplastic polymers such as polyamides, polysulfone, polypropyrol, and polyacronitril are reported. The paper concludes with a presentation of new finding and cutting-edge studies on nanocellulose foam and aerogel composites. Three different types of aerogels, i.e., pristine nanocellulose-based aerogels, modified nanocellulose-based aerogels, and nanocellulose-based templates for aerogels, are discussed, as well as their preparation techniques and properties. In the case of foam composites, the research focus has been on two major preparation techniques, i.e., solvent-mixing/foaming and melt-mixing foaming, their respective challenges, and the properties of the final composites. In some cases, a comparison study between cellulose nanocrystals and cellulose nanofiber-reinforced biodegradable polymers, thermoplastics, and porous nanocomposites was carried out. Considering the vast amount of research on nanocellulose-based composites, special emphasis on such composites isprovided at the end of the review.     

Morphology and properties tuning of PLA/cellulose nanocrystals bio-nanocomposites by means of reactive functionalization and blending with PVAc

A novel method for the preparation of PLA bio-nanocomposites containing cellulose nanocrystals (CNCs) is reported. In order to enhance interfacial adhesion and dispersion of nanocrystals into PLA matrix, functionalization of PLA and CNCs by radical grafting of glycidyl methacrylate (GMA) and pre-dispersion of CNCs in poly (vinyl acetate) (PVAc) emulsion were applied. Morphologies, thermal and mechanical properties of nanocomposites for CNCs content of 1–6 wt.% were examined. Addition of functionalized components (PLA-GMA, CNC-GMA) and/or PVAc dispersed CNCs both improved the phase distribution of nanofiller and tensile properties, compared to the binary PLA/CNC nanocomposites. Thermal analyses demonstrated that glass transition, melting temperature and crystallinity of PLA were affected by the PVAc amount. Nanocomposites with PVAc dispersed CNCs exhibited higher thermal resistance than other composites. The filler effectiveness (CFE) was evaluated for all samples on the basis of storage modulus values: CNC-GMA and PVAc dispersed CNCs (3 wt. %) resulted the most effective fillers.     

纤维素纳米纤丝/聚乙烯醇复合材料热性能与力学性能研究

通过溶液浇铸法制备了纤维素纳米纤丝(CNFs)/聚乙烯醇(PVA)复合材料,利用TG、DSC、DMA等方法考察了CNFs对PVA热性能与力学性能的影响。结果表明:CNFs的加入提高了PVA的结晶度与熔点,但随着CNFs含量的增加,由于CNFs与PVA之间存在较强的氢键作用,限制了PVA分子链的运动,使得PVA的熔点与结晶度略有下降;CNFs的加入使得PVA的玻璃化转变温度、拉伸强度与弹性模量提高,添加2%CNFs的PVA复合材料的拉伸强度与弹性模量均达到最大值,分别较纯PVA提升了28.9%与14.1%。     

Tensile and morphological properties of nanocrystalline cellulose and nanofibrillated cellulose reinforced PLA bionanocomposites: A review

In recent years, bionanocomposites have received growing attention in science and industry due to their renewability, biodegradability and superior mechanical properties. Nanocellulose is another promising material that use as a reinforcement filler for bionanocomposite materials due to its lightweight, high surface area, high mechanical strength, high aspect ratio and low density. Different nanocellulose loading, sources, surface modification/functionalization and properties of nanocellulose are important in the production of bionanocomposites. In general, nanocellulose reinforced PLA bionanocomposite offers enhancement in tensile strength and elastic modulus. However, only minimal nanocellulose loadings are required for optimal results due to the incompatibility between the hydrophilic nanocellulose and hydrophobic PLA. This paper reviews the sources of nanocellulose and the properties of nanocellulose with a focus on the tensile and morphological properties of PLA bionanocomposites. Applications of nanocellulose in various industries are discussed in this article. This review article provides some important information. First, this study reviewed the application of nanostructured cellulose in biodegradable polymers. There are two types of nanostructured cellulose: nanocrystalline cellulose (NCC) and nanofibrillated cellulose (NFC). Second, the status on articles published on nanocellulose and PLA/nanocellulose over the past 10 years is reported. Third, the authors of this paper implemented a holistic and critical review to provide a comprehensive understanding of the different properties between NCC and NFC, the application of nanocellulose in bionanocomposites, as well as the properties of PLA and PLA bionanocomposites. Moreover, the influence of NCC and NFC on the tensile and morphological properties of bionanocomposites is covered in this article.     

High-strength,ultrastretchable hydrophobic association hydrogel reinforced by tailored modified carboxymethyl cellulose

A new pathway to construct high-strength, ultrastretchable hydrogels based on tailored modified carboxymethyl cellulose (TMCMC)and hydrophobic association(HPA) system was investigated. TMCMC was prepared from degradation of carboxymethyl cellulose (CMC)/N,N′-methylene bisacrylamide (MBA) chemical cross-linked hydrogels. The residual double bonds of TMCMC, confirmed by ¹H-NMR and FTIR analysis, reacted with acrylamide in HPA to form TMCMC/HPA hydrogels, and the homogeneous and fine spatial network structure of TMCMC/HPA hydrogel could be observed by scanning electron microscopy. Rheological analysis revealed that the coexistence of physical and chemical crosslinking in TMCMC/HPA hydrogels. Further studies showed that TMCMC/HPA hydrogel with MBA content of 0.5 wt% has outstanding mechanical properties, and its fracture stress, elongation and tensile strength reach 1.17 MPa, 3717.05% and 15.68 MJ·m⁻³, respectively. Moreover, the hydrogel displayed good swelling resistance and stable strain electrical signal response.