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1.
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   

2.
Nanocellulose was extracted from short bast fibers, from hemp (Cannabis sativa L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers. No bleaching was performed. The chemically pretreated fibers were then refined in a beater and treated with a cellulase enzyme, followed by mechanical defibrillation in an ultrafine friction grinder. The fibers were characterized by microscopy, infrared spectroscopy, thermogravimetric analysis and X-ray diffraction after each step of the process to understand the evolution of their morphology and composition. The obtained nanocellulose suspension was composed of short nanofibrils with widths of 5–12 nm, stacks of nanofibrils with widths of 20–200 nm, and some larger fibers. The crystallinity index was found to increase from 74% for the raw fibers to 80% for the nanocellulose. The nanocellulose retained a yellowish color, indicating the presence of some residual lignin. The properties of the nanopaper prepared with the hemp nanocellulose were similar to those of nanopapers prepared with wood pulp-derived rod-like nanofibrils.  相似文献   

3.
In this study, a hybrid nanopaper consisting of carbon nanofiber (CNF) and polyhedral oligomeric silsequioxane (POSS) or cloisite Na+ clay, has been fabricated through the papermaking process. The hybrid nanopaper was then coated on the surface of glass fiber (GF) reinforced polymer matrix composites through resin transfer molding (RTM) process. The morphologies of the hybrid nanopaper and resulting nanocomposites were characterized with scanning electron microscopy (SEM). It can be seen that the nanopaper had a porous structure with highly entangled carbon nanofibers and the polyester resin completely penetrated the nanopaper throughout the thickness. The thermal decomposition behavior of the hybrid nanopapers and nanocomposites was studied with the real‐time thermogravimetric analysis/ flourier transform infrared spectrometry (TGA/FTIR). The test results indicate that the addition of pristine nanoclay increased the thermal stability of the nanopaper, whereas the POSS particles decreased the thermal stability of the nanopaper. The fire retardant performance of composite laminates coated with the hybrid nanopaper was evaluated with cone calorimeter tests using a radiated heat flux of 50 kW/m2. The cone calorimeter test results indicate that the peak heat release rate (PHRR) decreased dramatically in composite laminates coated with the CNF‐clay nanopaper. However, the PHRRs of the CNF‐POSS nanopaper coated composite laminates increased. The formation of compact char materials was observed on the surface of the residues of the CNF‐clay nanopaper after cone calorimeter test. The flame retardant mechanisms of the hybrid nanopaper in the composite laminates are discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
Native cellulose nanofibrils (CNF) were prepared from bleached birch pulp without any chemical or enzymatic pretreatment. These CNF were modified by adsorption of a small amount of water-soluble polysaccharides and used to prepare nanopapers, which were processed into composites by lamination with an epoxy resin and subsequently cured. The results were compared to the properties of composites prepared using bacterial cellulose nanopapers, since bacterial cellulose constitutes highly pure and crystalline cellulose. It was found that both types of nanopapers significantly improved both the thermal stability and mechanical properties of the epoxy resin. As anticipated, addition of only 2 wt% of water-soluble polysaccharides efficiently hindered crack-propagation within the nanopaper and significantly improved the tensile strength and work of fracture compared to composites containing a conventional nanopaper reinforcement. The mechanical properties of the composites thus reflected the improvement of the nanopaper properties by the polysaccharides. Moreover, it was possible to predict the properties of the final composite from the mechanical performance of the nanopapers.  相似文献   

5.
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   

6.
A hybrid nanopaper consisting of carbon nanofibre (CNF) and/or clay, polyhedral oligomeric silsesquioxane (POSS), ammonium polyphosphate (APP), has been fabricated through the papermaking process. The as-prepared hybrid nanopaper was then incorporated onto the surface of glass fibre (GF) reinforced polymer matrix composites through injection moulding. The morphologies of hybrid nanopapers with and without the polymer resin were characterized with scanning electron microscopy (SEM). The polymer resin penetrated the entire nanopaper under a high-pressure compressed air system. The thermal decomposition behaviour of hybrid nanopapers infused with resin was studied with real-time thermogravimetric analysis/Fourier transform infrared spectrometry (TGA/FTIR). The test results indicate that the addition of clay in the hybrid paper increased the char residues of the nanocomposites. The fire retardant performance of composite laminates incorporating hybrid nanopaper was evaluated by cone calorimeter testing using a radiant heat flux of 50 kW/m2. The cone test results indicated that the peak heat release rate (PHRR) decreased dramatically in the case of laminate composites incorporating CNF/clay/APP hybrid paper. However, the extent of reduction of PHRR of the composite laminates incorporated with CNF/POSS/APP hybrid paper was lower. The formation of compact char materials was observed on the surface of the residues and analyzed by SEM and X-ray photoelectron spectroscopy (XPS). The flame retardant mechanisms of hybrid nanopapers in composite laminates are discussed.  相似文献   

7.
Five pulping methods using different reagents were used for the delignification of almond shells: sodium hydroxide 7.5 % v/v for 24 h at 60 °C, potassium hydroxide 7.5 % v/v for 24 h at 60 °C, formic acid/water 90/10 v/v, organosolv with ethanol/water 60/40 v/v and sodium hydroxide 15 % v/v in an autoclave for 90 min at 120 °C. The resulting cellulose pulps were evaluated using TAPPI standard methods and X-ray diffraction (XRD) to determine the lignin content and crystallinity changes. After pulping, fibers were bleached with sodium chlorite and hydrogen peroxide to obtain pure cellulose. The resulting pulps were characterized by XRD and thermogravimetry to determine the cellulose purification rates and changes in crystallinity. Then, the different pulps were acetylated, hydrolyzed and homogenized to obtain cellulose nanofibers. Nanofiber sizes were assessed by atomic force microscopy and XRD to evaluate the effect of hydrolysis on nanofibers. Finally, nanopaper sheets were produced and the properties were compared to conventional micropaper. The different treatments influenced the amount of lignin eliminated, which had a direct relationship on the subsequent bleaching treatments to obtain pure cellulose. Hence, the different chemical methods influenced the crystallinity of the fibers which also influenced the yield of cellulose nanofibers and different nanopapers.  相似文献   

8.
In the present work the evolution of physical and mechanical properties of papers and nanopapers is studied. Handsheets made of eucalyptus fibres reinforced with 0, 25, 50, 75 and 100 wt% of nanofibrillated cellulose (NFC) content were fabricated using a Rapid Köthen-like equipment. The obtained papers and nanopapers were physical- and mechanically-characterized. The results showed a significant increase in density and a reduction of porosity in the samples during their transition from paper to nanopaper; besides, nanopapers were more transparent and smoother than normal papers. These physical changes where more evident with increasing amounts of NFC. Regarding mechanical properties, nanopapers with a 100 wt% content of NFC improved their strength and rigidity in 228 and 317 %, respectively, in comparison with normal papers. The evolution of strength and rigidity from paper to nanopaper was linear in relation to the amount of NFC, which means that the ultimate tensile strength was mainly dependant on nanofibril failure.  相似文献   

9.
Elastic properties of cellulose nanopaper   总被引:1,自引:0,他引:1  
Nanopaper is a transparent film made of network-forming nanocellulose fibers. These fibers are several micrometers long with a diameter of 4–50 nm. The reported elastic modulus of nanopaper often falls short of even conservative theoretical predictions based on the modulus of crystalline cellulose, although such predictions usually perform well for other fiber composite materials. We investigate this inconsistency and suggest explanations by identifying the critical factors affecting the stiffness of nanopaper. A similar inconsistency is found when predicting the stiffness of conventional paper, and it is usually explained by the effects introduced during drying. We found that the effect of the drying cannot solely explain the relatively low elastic modulus of nanopaper. Among the factors that showed the most influence are the presence of non-crystalline regions along the length of the nanofibers, initial strains and the three-dimensional structure of individual bonds.  相似文献   

10.
Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and <1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm3, higher than that from FB NFC (0.7 g/cm3). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m2/g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides.  相似文献   

11.
Herein the reaction mechanism and the origin of stereoselectivity of asymmetric hydrogenation of oximes to hydroxylamines catalyzed by the cyclometalated iridium (III) complexes with chiral substituted single cyclopentadienyl ligands (Ir catalysts A1 and B1) under acidic condition were unveiled using DFT calculations. The catalytic cycle for this reaction consists of the dihydrogen activation step and the hydride transfer step. The calculated results indicate that the hydride transfer step is the chirality-determining step and the involvement of methanesulfonate anion (MsO) in this reaction is of importance in the asymmetric hydrogenation of oximes catalyzed by A1 and B1. The calculated energy barriers for the hydride transfer steps without an MsO anion are higher than those with an MsO anion. The differences in Gibbs free energies between TSA5−1fR/TSA5−1fS and TSB5−1fR/TSB5−1fS are 13.8/13.2 (ΔΔG = 0.6 kcal/mol) and 7.5/5.6 (ΔΔG = 1.9 kcal/mol) kcal/mol for the hydride transfer step of substrate protonated oximes with E configuration (E−2a−H+) with MsO anion to chiral hydroxylamines product R−3a/S−3a catalyzed by A1 and B1, respectively. According to the Curtin–Hammet principle, the major products are hydroxylamines S−3a for the reaction catalyzed by A1 and B1, which agrees well with the experimental results. This is due to the non-covalent interactions among the protonated substrate, MsO anion and catalytic species. The hydrogen bond could not only stabilize the catalytic species, but also change the preference of stereoselectivity of this reaction.  相似文献   

12.
13.
Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m2/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS 13C-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.  相似文献   

14.
The purpose of the present work was to prepare polypropylene (PP) matrix composited filled with chemically treated pistachio shell particles (PTx), and evaluate their effect on the composites’ thermal properties. PP-PTx composites were formulated in different PTx content (from 2 to 10 phr) in a mixing chamber, using the melt-mixing process. The PTx were chemically treated using a NaOH solution and infrared spectroscopy (FTIR). According to thermogravimetric analysis (TGA), the treatment of pistachio shell particles resulted in the remotion of lignin and hemicellulose. The thermal stability was evaluated by means of TGA, where the presence of PTx in composites showed a positive effect compared with PP pristine. Thermal properties such as crystallization temperature (Tc), crystallization enthalpy (∆Hc), melting temperature (Tm) and crystallinity were determinate by means differential scanning calorimetry (DSC); these results suggest that the PTx had a nucleation effect on the PP matrix, increasing their crystallinity. Dynamic mechanical analysis (DMA) showed that stiffness of the composites increase compared with that PP pristine, as well as the storage modulus, and the best results were found at a PTx concentration of 4 phr. At higher concentrations, the positive effect decreased; however, they were better than the reference PP.  相似文献   

15.
The solubility of dehydroabietic acid in (−)-α-pinene, p-cymene, (−)-β-caryophyllene, (−)-α-pinene + p-cymene, (−)-β-caryophyllene + p-cymene and (−)-α-pinene + (−)-β-caryophyllene were determined using the laser monitoring method at atmospheric pressure. The solubility of dehydroabietic acid was positively correlated with temperature from 295.15 to 339.46 K. (−)-α-pinene, p-cymene, and (−)-β-caryophyllene were found to be suitable for the solubilization of dehydroabietic acid. In addition, the non-random two liquid (NRTL), universal quasi-chemical (UNIQUAC), modified Apelblat, modified Wilson, modified Wilson–van’t Hoff, and λh models were applied to correlate the determined solubility data. The modified Apelblat model gave the minor deviation for dehydroabietic acid in monosolvents, while the λh equation showed the best result in the binary solvents. A comparative analysis of compatibility between solutes and solvents was carried out using Hansen solubility parameters. The thermodynamic functions of ΔsolH0, ΔsolS0, ΔsolG0 were calculated according to the van’t Hoff equation, indicating that the dissolution was an entropy-driven heat absorption process. The Conductor-like Screening Model for Real Solvents (COSMO-RS) combined with an experimental value was applied to predict the reasonable solubility data of dehydroabietic acid in the selected solvents systems. The interaction energy of the dehydroabietic acid with the solvent was analyzed by COSMO-RS.  相似文献   

16.
A global pandemic caused by the SARS-CoV-2 virus that started in 2020 and has wreaked havoc on humanity still ravages up until now. As a result, the negative impact of travel restrictions and lockdowns has underscored the importance of our preparedness for future pandemics. The main thrust of this work was based on addressing this need by traversing chemical space to design inhibitors that target the SARS-CoV-2 papain-like protease (PLpro). Pathfinder-based retrosynthesis analysis was used to generate analogs of GRL-0617 using commercially available building blocks by replacing the naphthalene moiety. A total of 10 models were built using active learning QSAR, which achieved good statistical results such as an R2 > 0.70, Q2 > 0.64, STD Dev < 0.30, and RMSE < 0.31, on average for all models. A total of 35 ideas were further prioritized for FEP+ calculations. The FEP+ results revealed that compound 45 was the most active compound in this series with a ΔG of −7.28 ± 0.96 kcal/mol. Compound 5 exhibited a ΔG of −6.78 ± 1.30 kcal/mol. The inactive compounds in this series were compound 91 and compound 23 with a ΔG of −5.74 ± 1.06 and −3.11 ± 1.45 kcal/mol. The combined strategy employed here is envisaged to be of great utility in multiparameter lead optimization efforts, to traverse chemical space, maintaining and/or improving the potency as well as the property space of synthetically aware design ideas.  相似文献   

17.
Efficient and selective removal of 90Sr is an important process for the safe use of nuclear energy. Herein, we investigate and assess the Sr2+ adsorption properties of a metal-organic framework UiO-66-(COOH)2 functionalized by non-bonded carboxylic groups. This MOF is an exciting class of free carboxylic functionalized MOFs that combine chemical stability with gas sorption, dye elimination, and conductivity. Specifically, we show that uniformly distributed carboxyl and water stability make it accessible for loading Sr2+ without structural changes. The FTIR spectroscopy, PXRD analysis, XPS, and SEM-EDS studies show excellent stability as well as the strong affinity between -COOH active site and Sr2+. This strong coordination interaction guarantees a high adsorption capacity of 114 mg g−1 within 5 h (pH 5 and 298 K). Combined kinetic and thermodynamic studies show that the surface complexation is strong chemisorption and cost-effective spontaneous process (ΔG = −5.49 kJ mol−1~−2.16 kJ mol−1). The fact that UiO-66-(COOH)2 not only possesses a high adsorption capacity, but also enables selectivity to Sr2+ in the presence of similar radius ions Na+ and K+, prefigures its great potential for the practical treatment of radioactive Sr2+ in polluted water.  相似文献   

18.
In this work, polyacrylonitrile/aminated polymeric nanosphere (PAN/APN) nanofibers were prepared by electrospinning of monodispersed aminated polymeric nanospheres (APNs) for removal of Cr(VI) from aqueous solution. Characterization results showed that obtained PAN/APNs possessed nitrogen functionalization. Furthermore, the adsorption application results indicated that PAN/APN nanofibers exhibited a high adsorption capacity of 556 mg/g at 298 K for Cr(VI) removal. The kinetic data showed that the adsorption process fits the pseudo-second order. A thermodynamic study revealed that the adsorption of Cr(VI) was spontaneous and endothermic. The coexisting ions Na+, Ca2+, K+, Cl, NO3 and PO43− had little influence on Cr(VI) adsorption, while SO42− in solution dramatically decreased the removal performance. In the investigation of the removal mechanism, relative results indicated that the adsorption behavior possibly involved electrostatic adsorption, redox reaction and chelation. PAN/APN nanofibers can detoxify Cr(VI) to Cr(III) and subsequently chelate Cr(III) on its surface. The unique structure and nitrogen functionalization of PAN/APN nanofibers make them novel and prospective candidates in heavy metal removal.  相似文献   

19.
The extensive use of sulfonamides seriously threatens the safety and stability of the ecological environment. Developing green inexpensive and effective adsorbents is critically needed for the elimination of sulfonamides from wastewater. The non-modified biochar exhibited limited adsorption capacity for sulfonamides. In this study, the attapulgite-doped biochar adsorbent (ATP/BC) was produced from attapulgite and rice straw by calcination. Compared with non-modified biochar, the specific surface area of ATP/BC increased by 73.53–131.26%, and the average pore width of ATP/BC decreased 1.77–3.60 nm. The removal rates of sulfadiazine and sulfamethazine by ATP/BC were 98.63% and 98.24%, respectively, at the mass ratio of ATP to rice straw = 1:10, time = 4 h, dosage = 2 g∙L−1, pH = 5, initial concentration = 1 mg∙L−1, and temperature = 20 °C. A pseudo-second-order kinetic model (R2 = 0.99) and the Freundlich isothermal model (R2 = 0.99) well described the process of sulfonamide adsorption on ATP/BC. Thermodynamic calculations showed that the adsorption behavior of sulfonamides on the ATP/BC was an endothermic (ΔH > 0), random (ΔS > 0), spontaneous reaction (ΔG < 0) that was dominated by chemisorption (−20 kJ∙mol−1 > ΔG). The potential adsorption mechanisms include electrostatic interaction, hydrogen bonding, π–π interaction, and Lewis acid–base interactions. This study provides an optional material to treat sulfonamides in wastewater and groundwater.  相似文献   

20.
A straightforward method for the synthesis of 5-substituted tetrazolo[1,5-a]pyrido[2,3-e]pyrimidines from 2,4-diazidopyrido[3,2-d]pyrimidine in SnAr reactions with N-, O-, and S- nucleophiles has been developed. The various N- and S-substituted products were obtained with yields from 47% to 98%, but the substitution with O-nucleophiles gave lower yields (20–32%). Furthermore, the fused tetrazolo[1,5-a]pyrimidine derivatives can be regarded as 2-azidopyrimidines and functionalized in copper(I)-catalyzed azide-alkyne dipolar cycloaddition (CuAAC) and Staudinger reactions due to the presence of a sufficient concentration of the reactive azide tautomer in solution. In total, seven products were fully characterized by their single crystal X-ray studies, while five of them were representatives of the tetrazolo[1,5-a]pyrido[2,3-e]pyrimidine heterocyclic system. Equilibrium constants and thermodynamic values were determined using variable temperature 1H NMR and are in agreement of favoring the tetrazole tautomeric form (ΔG298 = −3.33 to −7.52 (kJ/mol), ΔH = −19.92 to −48.02 (kJ/mol) and ΔS = −43.74 to −143.27 (J/mol·K)). The key starting material 2,4-diazidopyrido[3,2-d]pyrimidine presents a high degree of tautomerization in different solvents.  相似文献   

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