Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying
or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the
influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence
the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process
performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine
the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity
of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying
method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported
and discussed. 相似文献
We fabricated cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) from different cellulose materials (bleached eucalyptus pulp (BEP), spruce dissolving pulp (SDP) and cotton based qualitative filter paper (QFP) using concentrated oxalic acid hydrolysis and subsequent mechanical fibrillation (for CNFs). The process was green as acid can be easily recovered, and the prepared cellulose nanomaterials were carboxylated and thermally stable. In detail, the CNC yield from the different materials was similar. After hydrolysis, the DP of the cellulose materials decreased substantially, whereas the mechanical fibrillation of the cellulosic solid residues (CSRs) did not dramatically reduce the DP of cellulose. CNCs with different aspect ratios were produced from different starting materials by oxalic acid hydrolysis. The CNCs and CNFs obtained from BEP and QFP possessed more uniform dimensions than those from SDP. On the other hand, CNFs derived from SDP presented the best suspension stability. FTIR analyses verified esterification of cellulose by oxalic acid hydrolysis. The results from both XRD and Raman spectroscopy indicated that whereas XRD crystallinity of CNCs from BEP and QFP did not change significantly, there was some change in Raman crystallinity of these samples. Raman spectra of SDP CNCs indicated that the acid hydrolysis preferably removed cellulose I portion of the samples and therefore the CNCs became cellulose II enriched. TGA revealed that the CNCs obtained from QFP exhibited higher thermal stability compared to those from BEP and SDP, and all the CNCs possessed better thermal stability than that of CNCs from sulfuric acid hydrolysis. The excellent properties of prepared cellulose nanomaterials will be conducive to their application in different fields. 相似文献
Cellulose nanocrystals (CNCs) were first isolated from microcrystalline cellulose (MCC) by p-toluene sulfonic acid (p-TsOH) hydrolysis. Cellulose II nanocrystal (CNC II) and cellulose III nanocrystal (CNC III) were then formed by swelling the obtained cellulose I nanocrystal (CNC I) in concentrated sodium hydroxide solutions and ethylenediamine (EDA) respectively. The properties of CNC I, CNC II and CNC III were subjected to comprehensive characterization by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results indicated that CNC I, CNC II and CNC III obtained in this research had high crystallinity index and good thermal stability. The degradation temperatures of the resulted CNC I, CNC II and CNC III were 300 °C, 275 °C and 242 °C, respectively. No ester bonds were found in the resulting CNCs. CNCs prepared in this research also had large aspect ratio and high negative zeta potential.
Homogenization has been used to release microfibrils from cellulose fibres to produce microfibrillated cellulose (MFC). Oven drying, atomization or freeze-drying were used to dry MFC. Morphological differences were observed linked to the compaction of the system and the formation of microfibril agglomerates. Thermal stability of the dried MFC, checked by TGA, decreased after homogenization and drying. Char level at the end of the pyrolysis was higher than for cellulose fibres. Derivative TGA (dTGA) showed a shoulder around 250 °C for the dried MFC. Volatile degradation product detection by FTIR spectroscopy (FTIR) coupled to TGA and DSC showed that the shoulder corresponds to expected dehydration reactions of the cellulose. Increasing the contacts between microfibril(s) (bundles) and agglomerates of the freeze-dried MFC by compression promoted dehydration reactions. Homogenization and drying modified the thermal properties of the MFC. No significant influence of freeze-drying kinetics on the thermal behaviour of the MFC was observed. 相似文献
To enhance the redispersibility of dried nanocellulose, cellulose nanocrystal (CNC) cryogels were produced by freeze-drying CNC-stabilized cyclohexane-in-water Pickering emulsions. The CNC cryogels were easily redispersed in water and organic solvents; thus, the approach proposed made it possible to significantly improve CNC redispersibility in aqueous and nonaqueous media. 相似文献
Cellulose, a linear biopolymer, is present naturally in all plants. Apart from being the planet’s predominant natural polymer, it also offers a variety of features including excellent biocompatibility, lower density, substantial strength and the most beneficial mechanical characteristics, inexpensive in cost. Applying the mechanical or chemical techniques, cellulosic materials are transformed into cellulose nanofibres (CNFs) and even cellulose nanocrystals (CNCs). These CNFs and CNCs exhibit excellent capabilities in comparison with native cellulose fibre. Nowadays, nanocellulose is being used in a variety of practical applications such as product packaging, papers as well as paperboard, food sector, healthcare, hygiene products, paints, skin care products and sensors. The current review article summarizes the cellulose, processing methods for nanocellulose, techniques used for chemical modification of cellulose surface and consequently its application as reinforcement in polymeric materials. This article also provides a comprehensive discussion of the historical development in the area of nanocellulose. 相似文献
Cellulose nanocrystals (CNCs) have drawn tremendous attention because of their extraordinary physical and chemical properties as well as renewability and sustainability. In this work, after a range of pretreatments, such as freeze-drying, ball-milling, mercerization, N-methylmorpholine-N-oxide dissolution and ionic liquid dissolution, various CNCs with different crystalline properties and morphologies were obtained by hydrolysis or oxidation. XRD and AFM were used to determine the influences of pretreatments on the crystalline properties and morphologies of CNCs. New methods, i.e., specific pretreatments followed by sulfuric acid hydrolysis or 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) oxidation, were developed to obtain sphere-like CNCs. It was found that sphere-like CNCs were more likely to be obtained from cellulose materials possessing high accessibility. Pretreatments produced cellulose with various crystallinities and polymorphs, and therefore changed the yields of CNCs and influenced their morphology. CNCs prepared by TEMPO oxidation generally had smaller size than the corresponding products obtained by sulfuric acid hydrolysis. In addition, for the dissolved/regenerated cellulose, TEMPO oxidation was a better method to yield sphere-like CNCs than sulfuric acid hydrolysis. 相似文献
We have modified the standard sulphuric acid hydrolysis method for the production of cellulose nanocrystals (CNCs) to successfully isolate a novel, highly crystalline cellulose material from the spent liquor of CNCs. The novel material has a cellulose II crystal structure that is distinctly different from the cellulose I crystal structure of CNCs. The modified method uses a shorter time for the hydrolysis, followed by maintaining a high residual acid concentration for the separation of the spent liquor and CNCs, and by adding the spent liquor to water. The modified method offers an opportunity to concurrently produce CNCs in up to ~40 % yield and the novel, highly crystalline, sulphated cellulose II in ~15 % yield in separate and pure forms from sulphuric acid hydrolysis of a commercial northern bleached softwood kraft pulp. It can potentially reduce the production cost of CNCs, allow easier downstream processing of CNCs and recovery of sulphuric acid, and generate a new cellulose bio-material for product development. 相似文献
This study aims to extract and characterize cellulose nanocrystals (CNCs) from date pits (DP), an agricultural solid waste. Two methods were used and optimized for the cellulose nanocrystals (CNCs) extraction, namely the mechanical stirrer method (CNCs1) and the Soxhlet apparatus method (CNCs2) in terms of chemical used, cost, and energy consumption. The results showed that scanning electron microscopy revealed the difference in the morphology as they exhibit rough surfaces with irregular morphologies due to the strong chemical treatments during the delignification and bleaching process. Moreover, transmission electron microscopy analysis for CNCs reveals the true modification that was made through sulfuric acid hydrolysis as it presents cellulose microfibrils with a packed structure. Fourier transform infrared proved that the CNCs were successfully extracted using the two methods since most of the lignin and hemicellulose components were removed. The crystallinity index of CNCs1 and CNCs2 was 69.99%, and 67.79%, respectively, and both presented a high yield of CNCs (≥10%). Ultimately, both techniques were successful at extracting CNCs. Based on their cost-effectiveness and time consumption, it was concluded that method 1 was less expensive than method 2 based on the breakdown of the cost of each step for CNCs production. 相似文献
Bacterial cellulose (BC)/poly(ethylene glycol) (PEG) composite was prepared by immersing wet BC pellicle in PEG aqueous solution
followed by freeze-drying process. The product looks like a foam structure. The morphology of BC/PEG composite was examined
by scanning electron microscope (SEM) and compared with pristine BC. SEM images showed that PEG molecules was not only coated
on the BC fibrils surface but also penetrated into BC fiber networks. It has very well interconnected porous network structure
and large aspect surface. The composite was also characterized by Fourier transform infrared spectrum, X-ray diffraction,
thermogravimetric analysis (TGA) and tensile test. It was found that the presence of PEG affected the preferential orientation
of the (1[`1]0 1\bar{1}0 ) plane during the drying process of BC pellicle, which in turn decrease the crystallinity of dried BC. The TGA result showed
that the thermal stability was improved from 263 to 293 °C, which might be associated with strong interaction between BC and
PEG. Tensile test results indicate that the Young’s modulus and tensile strength tend to decrease. Biocompatibility of composite
was preliminarily evaluated by cell adhesion studies using 3T3 fibroblast cells. The cells incubated with BC/PEG scaffolds
for 48 h were capable of forming cell adhesion and proliferation, which showed much better biocompatibility than the pure
BC. The prepared BC/PEG scaffolds can be used for wound dressing or tissue-engineering scaffolds. 相似文献
Summary: This study focuses on the methodology to obtain nanocellulose from vegetal fibers. An experimental planning was carried out for the treatment of curaua fibers and parameters were estimated, having the concentration of H2SO4, hydrolysis time, reaction temperature and time of applied sonication as independent variables for further statistical analysis. According to the estimated parameters, the statistically significant effects were determined for the process of obtaining nanocellulose. With the results obtained from the thermogravimetric analysis (TGA) it was observed that certain conditions led to cellulose with degradation temperatures near or even above that of the untreated cellulose fibers. The crystallinity index (IC) obtained after fiber treatment (by X-ray diffraction technique) was higher than that of the pure fiber. Treatments with high acid concentrations led to higher IC. After the statistical experimental design, mixtures of polypropylene with fibers prepared after different treatments were performed in a mini-extruder. It was possible to observe a sharp increase in the mechanical properties through the dynamic mechanical thermal analysis (DMTA). 相似文献
The aim of this paper is to report the effect of the addition of cellulose nanocrystals(CNCs) on the mechanical, thermal and barrier properties of poly(vinyl alcohol)/chitosan(PVA/Cs) bio-nanocomposites films prepared through the solvent casting process. The characterizations of PVA/Cs/CNCs films were carried out in terms of X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscopy(SEM), thermogravimetric analysis(TGA and DTG), oxygen transmission rate(OTR), and tensile tests. TEM and SEM results showed that at low loading levels, CNCs were dispersed homogenously in the PVA/Cs matrix. The tensile strength and modulus in films increased from 55.1 MPa to 98.4 MPa and from 395 MPa to 690 MPa respectively, when CNCs content went from 0 wt% to 1.0 wt%. The thermal stability and oxygen barrier properties of PVA/Cs matrix were best enhanced at 1.0 wt% of CNCs loading. The enhanced properties attained by incorporating CNCs can be beneficial in various applications. 相似文献
The effect of fiber drying on the properties of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) produced using concentrated maleic acid hydrolysis of a never dried unbleached mixed hardwood kraft pulp was evaluated. Two drying conditions, i.e., air drying and heat drying at 105 °C were employed. It was found that drying (both air and heat) enhanced acid hydrolysis to result in slightly improved LCNC yields and less entangled LCNF. This is perhaps due to the fact that drying modified the cellulose supermolecular structure to become more susceptible to acid hydrolysis and the enhanced hydrolysis severity at the fiber surface when using dried fibers. Drying substantially improved LCNC crystallinity and LCNF suspension viscoelastic behavior. The present study quantitatively elucidated the effect of pulp drying (either air or heat) on producing cellulose nanomaterials and has practical importance because commercial market pulp (heat dried) is most likely to be used commercially. 相似文献
Mechanical, thermal and oxygen barrier properties of regenerated cellulose films prepared from aqueous cellulose/alkali/urea
solutions can be markedly improved by controlling the drying conditions of the films. By pre-pressing followed by vacuum drying
under compression, the tensile strength, Young’s modulus, coefficient of thermal expansion and oxygen permeability of the
dried films reached 263 MPa, 7.3 GPa, 10.3 ppm K−1 and 0.0007 ml μm m−2 day−1 kPa−1, respectively. Thus, films produced in this way show the highest performance of regenerated cellulose films with no orientation
of cellulose chains reported to date. These improved properties are accompanied by a clear increase in cellulose II crystallinity
from 50 to 62% during pre-pressing/press-vacuum drying process. At the same time, the film density increased from 1.45 to
1.57 g cm−3, and the moisture content under equilibrium conditions decreased from 14.1 to 9.8%. Hence, the aqueous alkali/urea solvent
system has potential applications in producing new and environmentally friendly cellulose films with high performances through
control of the drying conditions. 相似文献
In cellulose nanocomposites, the surface of the nanocellulosic phase is critical with respect to nanocellulose dispersion, network formation and nanocomposite properties. Microfibrillated cellulose (MFC) has been grafted with poly(ε-caprolactone) (PCL), via ring-opening polymerization (ROP). This changes the surface characteristics of MFC and makes it possible to obtain a stable dispersion of MFC in a nonpolar solvent; it also improves MFC’s compatibility with PCL. The thermal behavior of MFC grafted with different amount of PCL has been investigated using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). From TGA measurements, the fraction of PCL in MFC-PCL samples was estimated to 16%, 19%, and 21%. The crystallization and melting behavior of free PCL and MFC-PCL were studied with DSC, and a significant difference was observed regarding melting points, crystallization temperature, degree of crystallinity, as well as the time required for crystallization. 相似文献
Esterification was used to improve the thermal stability of nanocellulose to extend its application as reinforcing filler to polymer matrices with high melting point. The effect of the structure of ester groups on thermal stability was studied in detail. Various types of nanocellulose esters (straight-chain, C2–C14; cyclic adamantoyl, ADM; aromatic benzoyl, BNZ; and branched pivaloyl, PIV) with degree of substitution values in the range of 0.40–0.47 were prepared from bacterial cellulose nanofibers and nanocrystals. The reaction conditions used to prepare the esters maintained the viscosity-average degree of polymerization (DPv) and crystallinity of the starting materials. Thermogravimetric analysis showed that the temperature at maximum weight loss rate (Tmax) increased after esterification. The structure of the ester groups and the DPv, however, showed no varying effect on Tmax. The 5 % weight loss temperature (WLT) which was used to assess the thermal stability at the onset of thermal degradation varied with the type of ester. Lower 5 % WLT was observed in straight-chain esters than those of the bulky esters of ADM, BNZ and PIV; which also showed high resistance to weight loss when subjected to isothermal heating. To understand the event at the onset of thermal degradation, low temperature pyrolysis was conducted. The evolved gases were separated and identified by gas chromatography–mass spectrometry technique. Results showed that at the onset of thermal degradation, levoglucosan (LG) is produced from the untreated BC nanocrystals. After esterification, LG formation was inhibited. The removal of the ester groups or deprotection is the main event at the onset of thermal degradation of nanocellulose esters. From the structure of the pyrolysis products, the mechanism of thermal deprotection of nanocellulose esters is proposed for the first time. 相似文献
A piqued interest in nanocellulose has recently arisen due to the growing need to use sustainable and renewable materials in place of those that are derived from petrochemical resources. Although current commercial uses of nanocellulose remain limited, research over the past two decades demonstrates numerous applications including reinforcing agents in polymer and cement composites, coatings, foams, gels, tissue scaffolds, and rheological modifiers, amongst others. Because of the hydrophilic nature of nanocellulose many of the potential uses will likely be in water-based formulations or employ water-based processing methods. Thus understanding the interactions between nanocellulose and water-soluble polymers is critical. Although polyelectrolyte adsorption to cellulose is well understood, adsorption of non-ionic polymers is less clear, with hydrogen bonding often cited as a governing factor. Recent work suggests that in fact hydrogen bonding does not play a significant role in nanocellulose systems, and that non-ionic polymer adsorption is largely entropically driven. Herein we review current literature that investigates non-ionic polymer adsorption to cellulose nanocrystals (CNCs) and draw upon previous papermaking research to better understand the mechanisms involved. Additionally we analyze recent work that compares the adsorption of polyethylene glycol (PEG) to CNCs and fumed silica that provides further insight into this phenomenon. Our findings, along with current literature, suggest that hydrogen bonding does not significantly impact polymer adsorption in aqueous media despite reports to the contrary. 相似文献
The horse chestnut seed shell (HC) and chestnut seed shell (CT) were evaluated as renewable, sustainable, and cheap raw materials transformed into valuable products, “cellulose nanocrystals (CNCs).” Alkali and bleaching treatments were performed to obtain horse chestnut cellulose (HCS) and chestnut cellulose (CTS) and subsequently isolated to the horse chestnut cellulose nanocrystal (HC-CNC) and chestnut cellulose nanocrystal (CT-CNC) by sulphuric acid hydrolysis. Raw materials and their products were comparatively investigated at each stage of the isolation process. The cellulose, hemicellulose, and lignin content of HC and CT were determined via chemical composition analysis. The structural analysis was performed using Fourier transform infrared spectroscopy and X-ray diffraction technics for CNCs. Morphological analysis and size range determination of the samples were carried out via atomic force microscopy (AFM) and particle size analysis. Zeta potential and particle size distribution were determined by analyzing the surface and particle size. The thermal behaviors were investigated at different phases of treatments using thermal gravimetric analysis (TGA/DTG). HC-CNC demonstrates a higher crystallinity index value of 85.49% and a lower yield of 20.46%, whereas CT-CNC shows a lower crystallinity of 65.06% and a higher yield of 36.59%. A differentiation in structural, thermal, and morphological properties of extracted celluloses and isolated CNCs was observed depending on the source of the raw materials. However, a morphological alteration in CNC structures has emerged relative to precursor cellulose after the acid hydrolysis process as an essential finding via AFM studies. The solid wastes horse chestnut and chestnut seed shells offer great potential as suitable, sustainable, and environmentally friendly starting raw materials to produce CNC and in applications, including wastewater treatments, biosensing, wound dressing, and reinforcement for polymer composites due to their excellent thermal and structural properties.