The aim of this study was to develop cellulose nanofibers with hydrophobic surface characteristics using chemical modification.
Kenaf fibers were modified using acetic anhydride and cellulose nanofibers were isolated from the acetylated kenaf using mechanical
isolation methods. Fourier transform infrared spectroscopy (FTIR) indicated acetylation of the hydroxyl groups of cellulose.
The study of the dispersion demonstrated that acetylated cellulose nanofibers formed stable, well-dispersed suspensions in
both acetone and ethanol. The contact angle measurements showed that the surface characteristics of nanofibers were changed
from hydrophilic to more hydrophobic when acetylated. The microscopy study showed that the acetylation caused a swelling of
the kenaf fiber cell wall and that the diameters of isolated nanofibers were between 5 and 50 nm. X-ray analysis showed that
the acetylation process reduced the crystallinity of the fibers, whereas mechanical isolation increased it. The method used
provides a novel processing route for producing cellulose nanofibers with hydrophobic surfaces. 相似文献
Physical adsorption is a common method to solve the contamination of methylene blue in dyeing wastewater. As a kind of adsorption material, cellulose aerogels with high porosity and surface areas have great potential application in methylene blue removal. However, the week hydrogen bonding between cellulose nanofibers making the cellulose aerogels with the poor mechanical properties and can be easily destroyed during adsorption. Hence, the preparation of cellulose aerogels with high mechanical strength is still a great challenge. Here, we report a robust super-assembly strategy to fabricate cellulose aerogels by combining cellulose nanofibers with PVA and M-K10. The resulting cellulose aerogels not only has a robust chemically cross-linked network, but also has strong H-bonds, which greatly enhance the mechanical properties. The resulting cellulose aerogels possess a low density of 19.32 mg/cm3.Furthermore, the cellulose aerogel shows 93% shape recovery under 60% strain(9.5 k Pa under 60% strain)after 100 cycles, showing excellent mechanical property. The adsorption capacity of cellulose aerogel to methylene blue solution of 20 mg/L is 2.28 mg/g and the adsorption kinetics and adsorption isotherms have also been studied. Pseudo-second-order kinetic model and Freundlich isotherm model are more acceptable for indicating the adsorption process of methylene blue on the cellulose aerogel. Thus, this compressible and durable cellulose aerogel is a very prospective material for dyeing wastewater cleanup. 相似文献
Microfibrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization.
The surface of the MFC was modified using different chemical treatments, using reactions both in aqueous- and organic solvents.
The modified MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS)
and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium
(IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount
of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate,
followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC surface as
a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC. 相似文献
A new derivative of cellulose aerogel was prepared via functionalization of cellulose with dimercaprol. Dimercaprol, as a chelating agent of Au(III), was applied for the loading of Au(III) on cellulose aerogel. The new organogold compound after characterization was used as an efficient heterogeneous catalyst in the oxidation reactions of aliphatic alcohols, benzyl alcohol, and ethylbenzene. Excellent selectivities and good conversions were obtained in the green oxidation reactions of alcohols and ethylbenzene. The high porosity of cellulose aerogel led to the good conversions with the low catalyst amounts. The significance of the presented work is the introducing of an environmentally benign process for the oxidation reactions based on a biocompatible catalyst. 相似文献
Adsorption isotherms of single and double chain cationic surfactants with different chain length (cetyltrimethyl-, didodecyl-
and dihexadecyl ammonium bromide) onto cellulose nanofibrils were determined. Nanofibrillated cellulose, also known as microfibrillated
cellulose (MFC), with varying contents of carboxyl groups (different surface charge) was prepared by TEMPO-mediated oxidation
followed by mechanical fibrillation. The fibril charge was characterized by potentiometric and conductometric titration. Surfactant
adsorption was verified by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). Wetting
and adhesion of water onto fibril films was determined by contact angle measurements. Small aggregates (admicelles) of surfactant
were shown to form on the nanofibril surfaces, well below critical micelle concentrations. The results demonstrate the possibility
of using cationic surfactants to systematically control the degree of water wettability of cellulose nanofibrils. 相似文献
In a previous study, the nematic ordered cellulose (NOC) templates successfully induced biodirected epitaxial nanodeposition
of cellulose nanofibers secreted by Gluconacetobacter xylinus along the orientation of the molecular tracks (Kondo et al. 2002). As an extended concept for the NOC, this article attempts to propose a sort of biomimic mineralization using the template.
It combines morphologically controlling process with synthesis of the calcium phosphate as a major component of bones. This
process was initially mediated by the modified NOC template having a pair of roles of the ion supply sources and scaffolds
for 3D-ordering architecture of the calcium phosphate as a biomineral in the key functions for biomineralization. The successful
establishment of such an ordered deposition of the inorganic on the template was confirmed by several surface characterizations
such as atomic force microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and so on. Moreover, similarly
to human bones, the obtained major assemble states of the calcium phosphates exhibited amorphous. The above process using
the bifunctional cellulose template can be considered as a biomimic mineralization, which also opens pathways toward preparation
of potentially versatile organic–inorganic order-patterned composites under a less energy consumption. 相似文献
Water-dispersed bacterial cellulose nanofibers were prepared via an oxidation reaction using 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO) as a catalyst. It was found that TEMPO-oxidized bacterial cellulose nanofibers (TOCNs) synthesized via sodium bromide-free methods are similar to those synthesized using sodium bromide. The TOCNs retained their unique structure in water as well as in emulsion. TOCNs adhere to the skin surface while maintaining nanofibrous structures, providing inherent functions of bacterial cellulose, such as high tensile strength, high water-holding capacity, and blockage of harmful substances. When gelatin gels as model skin were coated with TOCNs, the hardness representing the elasticity was increased by 20% compared to untreated gelatin gel because TOCNs could tightly hold the gelatin structure. When porcine skin was treated with TOCNs, carboxymethyl cellulose, and hydroxyethyl cellulose, the initial water contact angles were 26.5°, 76.5°, and 64.1°, respectively. The contact angle of TOCNs dramatically decreased over time as water penetrated the fibrous structure of the TOCN film. When observed by scanning electron microscopy and confocal microscopy, TOCNs on the skin surface provided physical gaps between particles and the skin, blocking the adsorption of particulate matter to the skin surface. On the contrary, the structure of water-soluble polymers was disrupted by an external environment, such as water, so that particulate matter directly attached to the skin surface. Characterization of TOCNs on the skin surface offered insight into the function of nanofibers on the skin, which is important for their applications with respect to the skin and biomedical research. 相似文献
Molecularly imprinted polymer-coated bacterial cellulose nanofibers have been prepared by immersing solvent treated-bacterial cellulose into a dilute pre-polymerization mixture solution prior to the polymerization process. The quercetin-imprinted polymer coating bacterial cellulose (QIP-BC) nanofibers show discrete nanoparticles encapsulated along the BC nanofibers. The binding capacity of dried QIP-BC was approximately 3 mg per gram of the polymer. The obtained results indicated that QIP-BC nanofibers provided a three fold higher recognition ability for quercetin than quercetin-imprinted nanospheres. This technique can be easily used to combine two fascinating materials like BC nanofibers and molecularly imprinted polymers (MIPs) to afford promising polymer composites that are useful in various innovative applications in biomedical, pharmaceutical, and industrial sectors. 相似文献
Cellulose nanocrystal (CNC) production suffers, among other problems, from low yields. The focus of this study was to investigate the universal effect of charge density, centrifugation, and mechanical treatment as limiting causes of yield. Microcrystalline cellulose (MCC) was used as the starting material in order to eliminate the relatively arbitrary yield losses caused by the hydrolysis conditions. To disintegrate MCC into nanocrystals, high surface charge in the form of carboxylic groups was introduced by TEMPO-mediated oxidation, after which the material was mechanically treated, and separated into fine and coarse fractions. The fine fraction collected as supernatant after separation by centrifugation had a yield of 17–20% independent of the mechanical treatment method or time used. The particle sizes of these fractions did not significantly differ from each other, which raises questions on the efficiency of the mechanical treatment (sonication) and centrifugation in traditional CNC production. The results imply that radically new approaches in preparation are needed for truly meaningful increases in the CNC yield. 相似文献
Chemical pretreatment combined with high-intensity ultrasonication was performed to disintegrate cellulose nanofibers from poplar wood powders. The cellulose content in each suspension was treated as the control variable because the suspension concentration significantly influences the properties of the resultant cellulose nanofibers via ultrasonic processing. The as-obtained cellulose nanofibers were characterized by fiber diameter distribution, crystal structure, and rheological analysis. An increase of not more than 1.2 % of the cellulose content resulted in finer nanofibers. Both storage modulus and loss modulus of cellulose nanofiber suspensions rapidly increased with increasing concentration because of the gradual formation of a stronger network structure. In addition, the dynamic mechanical behavior of suspensions with fiber contents lower than 0.8 % was affected by the frequency and temperature alteration in contrast with the suspension with higher fiber contents. The sol–gel transformation and the visco-elastic transition depend on the hydroxyl bonding and the cross-linking extent of cellulose nanofibers in various concentration environments. 相似文献
Eucalyptus cellulose is usually pre-treated by oxidation with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), NaBr and NaClO at pH 10.5 and 25 °C before the mechanical process required to obtain cellulose nanofibers (CNFs). In this study, different aspects to improve the effectiveness and sustainability of the TEMPO-mediated oxidation are analyzed. The optimization was carried out at different reaction times by modifying both the concentration of the NaClO and the amount of the catalysts (TEMPO and NaBr). Results show that the carboxyl groups increased up to 1.1 mmol/g with 5 mmol NaClO/g after 50 min, and that the catalyst concentration can be reduced to 0.025 mmol TEMPO/g and 0.5 mmol NaBr/g to minimize costs while maintaining the high fibrillation degree of the CNFs. The kinetic of the reaction can be considered as zero-order with respect to NaClO, and as first order with respect to cellulose. As a result of this work, the catalyst doses are reduced up to 75% compared to the most widely used catalyst doses (0.1 mmol/g TEMPO and 1 mmol/g NaBr), obtaining highly fibrillated CNFs with a lower environmental impact. This reduction of catalyst doses will reduce the costs and facilitate the implementation of CNF production at industrial scale.
A technique of immobilizing an enzyme/antibody was developed using cellulose hydrogel prepared from an aqueous alkali-urea
solvent. Partial oxidation by sodium periodate activated the cellulose gel for introducing aldehyde groups. Proteins were
covalently introduced to cellulose gel by a Schiff base formation between the aldehyde and the amino groups of proteins, and
stabilized by a reduction of imines. Coloring reactions confirmed the high activity of the immobilized enzymes. The activity
of the immobilized enzymes increased with aldehyde content, but the effect leveled off at a low degree of oxidation, at approximately
8.1 of oxidized glucose/100 glucose unit. The amount of immobilized peroxidase calculated from the activity was 8.0 ng/g for
an aldehyde content of 0.18 mmol/g: 14.6 ng/g for both 0.46 mmol/g and 1.04 mmol/g. The same method could be applied to the
peroxidase antibody. Thus, various active proteins could be immobilized on cellulose gels by mild and facile processing. Owing
to high mechanical and chemical stability of cellulose, this technique and resulting materials are potentially useful in biochemical
processing and sensing technologies. 相似文献
Cellulose nanofibers (CNFs) were isolated from four kinds of plant cellulose fibers by a chemical-ultrasonic treatment. The
chemical composition, morphology, crystalline behavior, and thermal properties of the nanofibers and their intermediate products
were characterized and compared. The CNFs extracted from wood, bamboo, and wheat straw fibers had uniform diameters of 10–40 nm, whereas the flax fibers were not uniformly nanofibrillated because of their initially high cellulose content. The chemical
composition of each kind of nanofibers was mainly cellulose because hemicelluloses and lignin were significantly removed during
chemical process. The crystallinity of the nanofibers increased as the chemical treatments were applied. The degradation temperature
of each kind of nanofiber reached beyond 330 °C. Based on the properties of the CNFs, we expect that they will be suitable
for use in green nanocomposites, filtration media and optically transparent films. 相似文献
Green all-cellulose nanocomposites were fabricated by adding reinforcing cellulose nanofiber (CNF) to a matrix of dissolved cellulose. CNFs were isolated from one dried native hardwood bleached Kraft pulp and office waste recycled deinked copy/printing paper (DIP) by using the TEMPO oxidation method. The cellulose was dissolved by using DIP and DMAc/LiCl solvent without heat treatment and solvent exchange to form a matrix of the all-cellulose nanocomposites. The DIP was not only selected for CNF isolation, but also for the cellulose matrix. The isolated CNFs and the all-cellulose nanocomposites were characterized by atomic force microscopy, thermogravimetry–differential thermal analysis, X-ray diffraction and mechanical tensile testing. The green all-cellulose nanocomposites made without heat treatment offered better thermal stability, crystallinity and mechanical properties than the heat treated ones. CNFs isolated from two resources show similar reinforcement capacity in all-cellulose nanocomposites. All-cellulose nanocomposite fabrication by dissolving cellulose without heat treatment and solvent exchange is a simple way that saves energy and chemicals. 相似文献
The possibility of fabricating carbon nanofibers from cellulose nanofibers was investigated. Cellulose nanofiber of ~50 nm
in diameter was produced using ball milling in an eco-friendly manner. The effect of the drying techniques of cellulose nanofibers
on the morphology of carbon residue was studied. After pyrolysis of freeze-dried cellulose nanofibers below 600 °C, amorphous
carbon fibers of ~20 nm in diameter were obtained. The pyrolysis of oven-dried precursors resulted in the loss of original
fibrous structures. The different results arising from the two drying techniques are attributed to the difference in the spatial
distance between cellulose nanofiber precursors. 相似文献
Due to their abundance, high strength and stiffness, low weight and biodegradability, nano-scale cellulose fiber materials
(e.g., microfibrillated cellulose and bacterial cellulose) serve as promising candidates for bio-nanocomposite production.
Such new high-value materials are the subject of continuing research and are commercially interesting in terms of new products
from the pulp and paper industry and the agricultural sector. Cellulose nanofibers can be extracted from various plant sources
and, although the mechanical separation of plant fibers into smaller elementary constituents has typically required high energy
input, chemical and/or enzymatic fiber pre-treatments have been developed to overcome this problem. A challenge associated
with using nanocellulose in composites is the lack of compatibility with hydrophobic polymers and various chemical modification
methods have been explored in order to address this hurdle. This review summarizes progress in nanocellulose preparation with
a particular focus on microfibrillated cellulose and also discusses recent developments in bio-nanocomposite fabrication based
on nanocellulose. 相似文献
Biobased nanofibers are increasingly considered in purification technologies due to their high mechanical properties, high specific surface area, versatile surface chemistry and natural abundance. In this work, cellulose and chitin nanofibers functionalized with carboxylate entities have been prepared from pulp residue (i.e., a waste product from the pulp and paper production) and crab shells, respectively, by chemically modifying the initial raw materials with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation reaction followed by mechanical disintegration. A thorough investigation has first been carried out in order to evaluate the copper(II) adsorption capacity of the oxidized nanofibers. UV spectrophotometry, X-ray photoelectron spectroscopy and wavelength dispersive X-rays analysis have been employed as characterization tools for this purpose. Pristine nanofibers presented a relatively low content of negative charges on their surface thus adsorbing a low amount of copper(II). The copper adsorption capacity of the nanofibers was enhanced due to the oxidation treatment since the carboxylate groups introduced on the nanofibers surface constituted negative sites for electrostatic attraction of copper ions (Cu2+). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55 mg g?1 for highly oxidized cellulose and chitin nanofibers, respectively. Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic water. Finally, the adsorption capacity of oxidized cellulose nanofibers for other metal ions, such as nickel(II), chromium(III) and zinc(II), was also demonstrated. We conclude that TEMPO oxidized biobased nanofibers from waste resources represent an inexpensive and efficient alternative to classical sorbents for heavy metal ions removal from contaminated water. 相似文献
This work demonstrates a simple fabrication of cellulose nanofibers by direct electrospinning of dissolved cellulose solutions. The hard- and softwood pulps and the outer mantles of tunicate were dissolved in a mixture of trifluoroacetic acid and dichloroethane by stirring and ultrasonication to give highly viscoelastic, clear solutions. These solutions were electrospun to form continuous nanofibers made of unsubstituted cellulose, which were confirmed by scanning electron microscopy (SEM) and IR spectroscopy. Statistical analysis of the SEM images of the nanofibers suggested that there are positive correlations between diameters of the nanofibers and concentration of the cellulose solution. The mean diameters of the nanofibers obtained from softwood pulp (DP of cellulose ≈ 1200) solutions were larger than those from hardwood pulp (DP of cellulose ≈ 500) at the same concentrations. This indicates that the DP of cellulose is one of the important parameters to control the diameters of the electrospun cellulose nanofibers. 相似文献
Nanofibrillated cellulose (NFC) from three agricultural crop (rice straw, corn and rapeseed stalk) residues was isolated with high-yield production using either high pressure homogenisation or a high speed blender. The fibres were extracted from the neat biomass via an NaClO2/acetic acid and alkali pulping process. TEMPO-mediated oxidation pretreatment at pH 7 and 10 was accomplished to facilitate the release of the cellulose microfibrils. The fibrillation yield, transparency degree and morphological characteristics of the ensuing NFC were analysed using the centrifugation method, transmittance measurement and SEM observation. The energy consumption during the disintegration process was also accessed. It was shown that the mode of lignin removal and the fibre pretreatment notably affected the nanofibrillation efficiency and energy demand. A successful production of NFC with yield exceeding 90 %, using a simple Waring blender, was achieved when the NaClO2/acetic acid delignification followed by a TEMPO-NaBr–NaClO oxidation at pH 10 was adopted. 相似文献