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1.
A wood cellulose was oxidized with catalytic amounts of 2-azaadamantane N-oxyl (AZADO) or 1-methyl-AZADO, in an NaBr/NaClO system, in water at pH 10. The oxidation efficiency, carboxylate/aldehyde contents, and degree of polymerization (DPv) of the oxidized celluloses thus obtained were evaluated in terms of the amount of AZADO or 1-methyl-AZADO catalyst added, in comparison with those prepared using the TEMPO/NaBr/NaClO system. When the AZADO/NaBr/NaClO and 1-methyl-AZADO/NaBr/NaClO oxidation systems were applied to wood cellulose using the same molar amount of TEMPO, the oxidation time needed for the preparation of oxidized celluloses with carboxylate contents of 1.2–1.3 mmol/g was reduced from ≈80 to 10–15 min. Moreover, the molar amounts of AZADO and 1-methyl-AZADO that had to be added for the preparation of oxidized celluloses with carboxylate contents of 1.2–1.3 mmol/g were reduced to 1/32 and 1/16 of the amount of TEMPO added, respectively. The DPv values for the AZADO- and 1-methyl-AZADO-oxidized celluloses after NaBH4 treatment were in the range of 600–800. This indicated that not only C6-carboxylate groups but also C2/C3 ketones were formed to some extent on the crystalline cellulose microfibril surfaces during the AZADO- and 1-methyl-AZADO-mediated oxidation. When the AZADO-oxidized wood cellulose, which had a carboxylate content of 1.2 mmol/g, was mechanically disintegrated in water, an almost transparent dispersion consisting of individually nano-dispersed oxidized cellulose nanofibrils was obtained, with a nanofibrillation yield of 89 %.  相似文献   

2.
In this work, periodate oxidized birch wood pulp and microfibrillated cellulose (MFC) were cationized using Girard’s reagent T or aminoguanidine. Cationic celluloses were used to obtain films via solvent-casting method, and the effects of the cationization route and the cellulose fiber source on the properties of the films were studied. Thermal and optical properties of the films were measured using differential scanning calorimetry and UV–Vis spectrometry, and the morphology of the films was examined using an optical microscope and a field emission scanning electron microscope. Bacterial anti-adhesive properties of the films were also studied using a modified leaf print method and against Staphylococcus aureus and Escherichia coli. Both cationizing agents exhibited similar reactivity with periodate oxidized celluloses, however, MFC had significantly higher reactivity compared to birch pulp. The films with high tensile strength (39.1–45.3 MPa) and modulus (3.5–7.3 GPa) were obtained from cationized birch pulp, aminoguanidine modification producing a film with slightly better mechanical properties. Modulus of the films was significantly increased (up to 14.0 GPa) when MFC was used as a cellulose fiber source. Compared to the unmodified MFC films, the cationic MFC films were less porous and significantly more transparent; however, they had slightly lower tensile strength values. It was found that aminoguanidine modified celluloses had no culturable bacteria on its surface and also exhibited resistance to microbial degradation, whereas there were culturable bacteria on the surface of Girard’s reagent modified films and they were partially degraded by the bacteria.  相似文献   

3.
Softwood cellulose pulp was oxidized by a two-step oxidation process with sodium periodate followed by sodium chlorite at pH 5.0. The oxidized product was first separated into two fractions by centrifugation, and the supernatant was further separated in two fractions by addition of ethanol and centrifugation. Different levels of oxidation were performed on cellulose, and the mass ratio and carboxyl content of each fraction were determined. The first precipitate, which amount decreases with increasing oxidation level, consists of short fiber fragments (microfibrils) with length of 0.6–1.8 μm and width around 120 nm, which for sufficiently high oxidation levels, could readily be made into cellulose nanofibrils by stirring. The second precipitate (after alcohol addition) has a very high crystalline index of 91 % and contains rod-like particles with length of 120–200 nm and diameter around 13 nm, reminiscent of nanocrystalline cellulose. The supernatant contains water-soluble dicarboxylated cellulose, as proven by liquid C-13 NMR.  相似文献   

4.
We present a novel nanostructure in the form of cellulose nanoplatelets (CNPs) with an inner array of entangled nanofibrils. The planar structure was isolated from the parenchyma cells of Agave salmiana first using basic pretreatment, then by dissolving lignin and hemicellulose using acid hydrolysis, and finally by modifying the cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). The crystallinity index was calculated following the purification process, and it was found that nanocellulose was 30% more crystalline than the raw material. Using transmission electron microscopy, it was found that the nanoplatelets comprise ~2–3 nm long cellulose entangled nanofibrils. In addition, via atomic force microscopy, the morphology of the nanoplatelets was confirmed; they were 90 nm thick for the acid hydrolyzed sample and 70 nm thick for the TEMPO-modified sample; their lateral size varied from a few to hundreds of micrometers, presenting large aspect ratios. Finally, CNPs were isolated and processed into thin paper with a thickness of 100 µm and transmittance of 86%, demonstrating great potential as a transparent film.  相似文献   

5.
The drying process in typical pulp production generates strong hydrogen bonding between cellulose microfibrils in refined cell walls and increases the difficulty in obtaining uniform cellulose nanofibers. To investigate the efficacy of alkaline treatment for cellulose nanofibrillation, this study applied a bead-milling method in NaOH solutions for the nanofibrillation of dried pulps. NaOH treatments loosened the hydrogen bonding between cellulose microfibrils in dried pulps and allowed preparation of cellulose nanofibers in 8 % NaOH with a width of approximately 12–20 nm and a cellulose I crystal form. Both the nanofiber suspensions prepared in 8 and 16 % (w/w) NaOH were formed into hydrogels by neutralization because of surface entanglement and/or interdigitation between the nanofibers. When the dried pulp was fibrillated in 16 % (w/w) NaOH, the sample after neutralization had a uniquely integrated continuous network. These results can be applied to the preparation of high-strength films and fibers with cellulose I crystal forms without prior dissolution of pulps.  相似文献   

6.
A greater ductility of cellulosic materials is important if they are to be used in increasingly advanced applications. This study explores the potential for using chemical core-shell structuring on the nanofibril level to alter the mechanical properties of cellulose fibres and sheets made thereof. The structuring was achieved by a selective oxidation of the cellulose C2–C3 bonds with sodium periodate, followed by a reduction of the aldehydes formed with sodium borohydride, i.e. locally transforming cellulose to dialcohol cellulose. The resulting fibres were morphologically characterised and the sheets made of these modified fibres were mechanically tested. These analyses showed a minor decrease in the degree of polymerisation, a significantly reduced cellulose crystal width and a greater ductility. At 27 % conversion of the available C2–C3 bonds, sheets could be strained 11 %, having a stress at break of about 90 MPa, and consequently a remarkable tensile energy absorption at rupture of about 9 kJ/kg, i.e. 3–4 times higher than a strong conventional paper. Zero-span tensile measurements indicated that the treatment increased the ductility not only of sheets but also of individual fibres. This suggests that the amorphous and molecularly more mobile dialcohol cellulose is located as a shell surrounding the crystalline core of the cellulose fibrils, and that, at deformations beyond the yield point, this facilitates plastic deformation both within and between individual fibres.  相似文献   

7.
2,3-Dialdehyde celluloses were prepared by homogeneous periodate oxidation in an aqueous solution of methylol cellulose. Since methylol cellulose stays dissolved in water for a certain time before decomposing gradually into regenerated cellulose, the oxidation reaction progressed homogeneously throughout the period. The resulting dialdehyde cellulose achieved an oxidation level of over 90 % in as little as 12 h. Reducing the dialdehyde celluloses with NaBH4 resulted in water-soluble dialcohol celluloses, which have an open-ring structure at the C2–C3 position. The dialcohol celluloses were characterized using nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The Tg of the products decreased with increasing oxidation levels. The products might be processable, and unique tensile properties were obtained by cutting the C2–C3 bonds in the glucopyranose rings. The dialcohol celluloses prepared using a cast method yielded clear and transparent films which showed unique mechanical properties by tensile tests depending on the values of oxidation level.  相似文献   

8.
Films of cellulose nanofibrils (CNF) (referred to as nanopaper) present a great potential in many applications due to the abundance, low environmental impact, excellent oxygen barrier properties and good mechanical performance of CNF. However, the strong hygroscopic character of the natural nanofibers limits their use in environments with high relative humidity. In this paper, we introduce a simple route for the esterification and processing of CNF with the aim of reducing their hydrophilicity, and producing hydrophobic cellulose nanopaper with reduced moisture sensitivity. The preparation steps of hydrophobic nanopapers involve vacuum filtration, solvent exchange from water to acetone, and reaction with anhydride molecules bearing different hydrophobic alkyl chains by hot pressing. Porous films having a surface area between 38 and 47 g/m2 and pore sizes in the 3–200 nm range are obtained. This method preserves the crystalline structure of native cellulose, and successfully introduces hydrophobic moieties on CNF surface as confirmed by FTIR, XPS and elemental analysis. As a result, modified nanopapers have a reduced moisture uptake, both higher surface water contact angle and wet tensile properties as compared with reference non-modified nanopaper, thus illustrating the benefit of the modification for the use of cellulose nanopaper in humid environments.  相似文献   

9.
Well-dispersed cellulose II nanofibers with high purity of 92 % and uniform width of 15–40 nm were isolated from wood and compared to cellulose I nanofibers. First, ground wood powder was purified by series of chemical treatments. The resulting purified pulp was treated with 17.5 wt% sodium hydroxide (NaOH) solution to mercerize the cellulose. The mercerized pulp was further mechanically nanofibrillated to isolate the nanofibers. X-ray diffraction patterns revealed that the purified pulp had been transformed into the cellulose II crystal structure after treatment with 17.5 wt% NaOH, and the cellulose II polymorph was retained after nanofibrillation. The cellulose II nanofiber sheet exhibited a decrease in Young’s modulus (8.6 GPa) and an increase in fracture strain (13.6 %) compared to the values for a cellulose I nanofiber sheet (11.8 GPa and 7.5 %, respectively), which translated into improved toughness. The cellulose II nanofiber sheet also showed a very low thermal expansion coefficient of 15.9 ppm/K in the range of 20–150 °C. Thermogravimetric analysis indicated that the cellulose II nanofiber sheet had better thermal stability than the cellulose I nanofiber sheet, which was likely due to the stronger hydrogen bonds in cellulose II crystal structure, as well as the higher purity of the cellulose II nanofibers.  相似文献   

10.
We describe a novel class of electrically conductive transparent materials based on multiwalled carbon nanotubes (MWCNTs). Transparent nanocomposites were fabricated by incorporating an aqueous silk fibroin solution into bacterial cellulose membranes. The transparent nanocomposites had a high transmittance in the visible and infrared regions, regardless of the bacterial cellulose fiber content, due to the nanosize effect of the bacterial cellulose nanofibrils. This phenomenon allowed the preparation of a novel electrically conductive transparent paper. The high dispersity of the MWCNTs was realized by utilizing a bacterial cellulose membrane as a template to deposit them uniformly, thereby achieving electrically conductive transparent papers with outstanding optical transparency. The light transmittance and electrical conductivity varied according to the concentration of the MWCNT dispersion. Good optimal transparency and electrical properties were obtained with a light transmittance of 70.3% at 550 nm and electrical conductivity of 2.1 × 10?3 S/cm when the electrically conductive transparent paper was fabricated from a 0.02 wt % aqueous MWCNT dispersion. In addition, the electrically conductive transparent papers showed remarkable flexibility without any loss of their initial properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1235–1242, 2008  相似文献   

11.
The lengths of ten types of cellulose nanofibrils were evaluated by shear viscosity measurement of their dilute dispersions. Aqueous dispersions of surface-carboxylated cellulose nanofibrils with a uniform width of ~3 nm were prepared from wood cellulose by 2,2,6,6-tetramethylpiperidine-1-oxyl-mediated oxidation and successive mechanical treatment. Cellulose nanofibril samples with different average lengths were prepared by controlling the conditions of the oxidation or mechanical treatment. The viscosity-average lengths, L visc, of the nanofibrils were calculated by applying the shear viscosities of the dilute dispersions to an equation for the dilute region flow behavior of rod-like polymer molecules. The obtained L visc values ranged from 1,100 to 2,500 nm and showed a linear relationship to the length-weighted average length, L w, measured by microscopic observation; the relation was described as L visc = 1.764 × L w + 764. The influences of the electric double-layer of the nanofibrils and surface-carboxylate content on the value of L visc were also investigated.  相似文献   

12.
The length of cellulose nanofibrils (CNFs) is a significant parameter for various applications. The goal of this research was to employ a fabrication method to produce length-controlled CNFs; the chosen technique was enzy-grinding (enzyme pretreatment followed by mechanical grinding). Here, we presented the results of the optimization of the diameter and length, the characterization of the properties of CNFs and nanofilms prepared using these fibrils. The cellulose morphology, crystallinity index (CrI), chemical structure, and thermal stability were investigated as functions of the enzyme loading and hydrolysis time. The results showed that enzy-grinding could effectively reduce the diameter and length of cellulose fibrils. The average diameter was about 8.6 ± 3.6 nm, and the length could be controlled over the range from 0.76 ± 0.38 μm to ≥ 4 μm (i.e. aspect ratios from 43 to ≥ 328). After the grinding process, the CNFs maintained high thermal stability and no change in the chemical structure compared to the original pulp. The transmittance and mechanical properties of the CNF films were strongly dependent on the fibril length. The fabrication of length-controlled CNFs using the enzy-grinding process is meaningful and significant research which could be relevant to the optimization of such materials for various applications.  相似文献   

13.
Periodate oxidation breaks the C2–C3 bond in the glucose repeat units of cellulose, forming two vicinal aldehyde groups. When the cellulose is partially oxidized, three products were generated after periodate oxidation: fibrous cellulose, sterically stabilized nanocrystalline cellulose (SNCC) and dialdehyde modified cellulose. Thus, by periodate oxidation alone, we can produce nanocellulose. SNCCs were produced after 26, 42 and 84 h periodate oxidation. Their morphologies were examined by transmission electron microscopy, which show that the three SNCCs have similar diameters (5–10 nm). In contrast, the average length of SNCC decreases with aldehyde content: from approximately 590 nm after 26 h of oxidation to 100 nm for an oxidation period of 84 h. It indicates that the morphology of SNCC can be well controlled by the degree of periodate oxidation, which depends on the amount of periodate and the reaction time. Equivalent spherical diameters of SNCCs were also examined by dynamic light scattering, and the results correspond closely to the ones observed by TEM. The viscosities of SNCCs were measured by an Ubbelohde viscometer and compared with theory. Because the length of SNCC particles gradually reduces while their diameters remain almost the same, we propose that periodate reacts preferentially with the amorphous region of cellulose. After most of the amorphous regions have reacted, the reaction proceeds at the boundary of amorphous and crystalline regions, creating a reaction front that advances towards the crystalline regions, thus continually shortening them. Dynamic light scattering experiments on SNCC suspensions when adding cosolvents into them proved that SNCCs were sterically stabilized in water.  相似文献   

14.
Chemically modified cellulose micro- and nanofibrils were successfully used as paper strength additives. Three different kinds of cellulose nanofibrils (CNFs) were studied: carboxymethylated CNFs, periodate-oxidised carboxymethylated CNFs and dopamine-grafted carboxymethylated CNFs, all prepared from bleached chemical fibres of dissolving grade, and one microfibrillated cellulose from unbleached kraft fibres. In addition to mechanical characterization of the final paper sheets the fibril retention, sheet density and sheet morphology were also studied as a function of addition of the four different cellulose fibrils. In general, the cellulose fibrils, when used as additives, significantly increased the tensile strength, Young’s modulus and strain-at-break of the paper sheets. The effects of the different fibrils on these properties were compared and evaluated and used to analyse the underlying mechanisms behind the strengthening effect. The strength-enhancing effect was most pronounced for the periodate-oxidised CNFs when they were added together with polyvinyl amine (PVAm) or poly(dimethyldiallylammonium chloride) (pDADMAC). The addition of periodate-oxidised CNFs, with pDADMAC as retention aid, resulted in a 37% increase in tensile strength at a 2 wt% addition and an 89% increase at a 15 wt% addition (from 67 to 92 and 125 kNm/kg, respectively) compared to a reference with only pDADMAC. Wet-strong sheets with a wet tensile index of 30 kNm/kg were also obtained when periodate-oxidised CNFs and PVAm were combined. This significant increase in wet strength is suggested to be the result of a formation of cross-links between the aldehyde groups, introduced by the periodate oxidation, and hydroxyl groups on the lignocellulosic fibres and the primary amines of PVAm. Even though less significant, there was also an increase in wet tensile strength when pDADMAC was used together with periodate-oxidised fibrils which shows that the aldehyde groups are able to increase the wet strength without the presence of the primary amines of the PVAm. As an alternative method to strengthen the fibre network, carboxymethylated CNFs grafted with dopamine, by an ethyl dimethylaminopropyl carbodiimide coupling, were used as a strength additive. When used as an additive, these CNFs showed a strong propensity to form films on and around the fibres and significantly increased the mechanical properties of the sheets. Their addition resulted in an increase in the Young´s modulus by 41%, from 5.1 to 7.2 GPa, and an increase in the tensile strength index of 98% (from 53 to 105 kNm/kg) with 5 wt% retained dopamine-grafted CNFs.  相似文献   

15.
Hemp bast (α-cellulose 79.4%, Klason lignin 4.9%) was directly oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation in water at pH 10 and room temperature for 2 h. The level of added NaClO in oxidation varied from 5 to 30 mmol/g (based on dry weight of hemp bast). Weight recovery ratios of the TEMPO-oxidized hemp bast celluloses were in the range of 81–91%, and their carboxylate contents increased up to 1.2 mmol/g with the increased NaClO addition level. The lignin contents decreased to 0.5–0.9% after oxidation, and the viscosity-average degrees of polymerization decreased from 1100 to 560 because of depolymerization during oxidation. Thus, direct TEMPO-mediated oxidation of hemp bast introduced a significant number of carboxylate groups and simultaneously achieved sufficient delignification. Small amounts of xylose, mannose, and rhamnose originating from hemicelluloses remained in the TEMPO-oxidized hemp bast samples prepared by oxidation with 5–20 mmol/g NaClO. However, oxidation with 30 mmol/g NaClO completely removed these hemicellulose-originating sugars, and produced almost pure TEMPO-oxidized cellulose. When TEMPO-oxidized hemp bast samples were mechanically disintegrated in water, their nanofibrillation yields were 58–65%. After removal of unfibrillated fractions by centrifugation, transparent dispersions showed birefringence when observed between cross-polarizers, while atomic force microscopy images showed near-individually dispersed nanofibril elements with widths of ~2 nm.  相似文献   

16.
In the past, the direct production of lignin-containing nanofibers from wood materials has been very limited, and nanoscale fibers (nanocelluloses) have been mainly isolated from chemically delignified, bleached cellulose pulp. In this study, we have introduced a newly adapted, heat-intensified disc nanogrinding process for the enhanced nanofibrillation of wood nanofibers (WNF) with a high lignin content (27.4 wt%). The WNF produced this way have many unique and intriguing properties in their naturally occurring form, for example, being able to be dispersed in ethanol and having ethanol solution viscosities higher than water solution viscosities. When WNF nanopapers were formed with ethanol, the properties of the nanofibers were recoverable without a notable decrease in the viscosity or mechanical strength after redispersing them in water. The preservation of lignin in the WNF was noticed as an increase in the water contact angles (89°), the rapid removal of water in the fabrication of the nanopapers, and the enhanced strength of the nanopapers when subjected to high pressure and heat. The nanopapers fabricated from the WNF were mechanically stable, having an elastic modulus of 6.2 GPa, a maximum stress of 103.4 MPa, and a maximum strain of 3.5%. Throughout the study, characteristics of the WNF were compared to those of the delignified and bleached reference cellulose nanofibers. We envision that the exciting characteristics of the WNF and their lower cost of production compared to that of bleached cellulose nanofibers may offer new opportunities for nanocellulose and biocomposite research.  相似文献   

17.
Rod-like cellulose nanowhiskers and spherical cellulose nanoparticles were prepared from wood-pulp-derived cellulose powder by mechanical refining processes such as high-pressure homogenization (HPH) and ball-milling (BM). The nanowhiskers obtained by the HPH method were found to be 200–500 nm long and 11–16 nm wide. The diameters of the nanoparticles were in the range 40–200 nm, depending on the BM time, and were reduced to 25–50 nm after extra HPH. By adjusting the BM time, cellulose nanoparticles having different polymorphs with similar morphologies were prepared. The X-ray diffraction patterns revealed the recrystallization of cellulose I (1 h of BM time) or cellulose II (4–8 h of BM time) in ball-milled nanoparticles after water washing and solvent exchange treatments. The nanowhisker widths derived from the specific surface areas (SSA) by adsorption methods such as Congo red dye, nitrogen, and water vapor, sorptions were in agreement with those obtained from transmission electron microscopy and atomic force microscopy images. Similar SSA values were obtained for micro- and nano-scale cellulose materials using water vapor adsorption methods, and the SSAs of nanoparticles obtained by different adsorption methods are also discussed.  相似文献   

18.
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   

19.
The effect of temperature during cellulose compression has been studied using mechanical testing, particle size analysis, density and pressure–volume–temperature (PVT) measurements, crystallinity index, scanning electron microscope photographs and water sorption isotherms. Commercial cellulose powder samples with different crystallinity levels were compacted at high pressure (177 MPa) for 10 min at two different temperatures: 25 and 160 °C. Three point bending test results for compressed samples are discussed. When pressure was applied directly to powders at room temperature, the cellulose sample with the highest level of crystallinity showed an increase in its crystallinity index of about 5 %, while this was about 22 % for the sample with the lowest level. These increases were even higher at 160 °C attaining 8 and 33 % respectively. Using density measurements, a densification phase related to this crystallinization was observed, and the PVT diagrams from different cellulose samples showed that this was associated with high temperatures. Water sorption isotherms were made on cellulose samples before and after compression. They showed a diminution of cellulose sorption capacity after compression at 160 °C, revealing the effect of temperature on high-pressure cellulose compression, reducing specific surface area. Events of this nature suggest a sintering mechanism, when temperature is associated with high pressure during cellulose compression.  相似文献   

20.
The characterization of new natural fiber is increasing due to its excellent properties. This drives investigators to create high performance composites. The present investigation was designed to study the physicochemical properties of fibers obtained from the leaf of the Artistida hystrix. The Artistida hystrix fibers (AHFs) had crystallinity index (44.85%), cellulose (59.54 wt%), hemicellulose (11.35 wt%), lignin (8.42 wt%), and density (540 kg m?3). The tensile strength of AHFs was 440 ± 13.4 MPa with an average strain rate of 1.57 ± 0.04%. The calculated microfibril angle of AHFs was 12.64 ± 0.45°, which influenced the mechanical properties.  相似文献   

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