Multilayers of cellulose derivatives and chitosan on nanofibrillated cellulose (original) (raw)
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All-cellulose multilayers: long nanofibrils assembled with short nanocrystals
Cellulose, 2013
Self-organized multilayer films were formed by sequential addition of oppositely charged cellulose I nanoparticles. The all-cellulosic multilayers were prepared via adsorption of cationicially modified cellulose nanofibrils (cat NFC) and anionic short crystalline cellulose (CNC) at pH 4.5 and pH 8.3. The properties and build-up behavior of layer-bylayer-constructed films were studied with microgravimetry (QCM-D) and the direct surface forces in these systems were explored with colloidal probe microscopy to gain information about the fundamental interplay between cat NFC and anionic CNC. The importance of the first layer on the adsorption of the consecutive layers was demonstrated by comparing pure in situ adsorption in the QCM-D with multilayer films made by spin coating the first cationic NFC layer and then subsequently adsorbing the following layers in situ in the QCM-D chamber. Differences in adsorbed amount and viscoelastic behavior were observed between those two systems. In addition, a significant pH dependence of cat NFC charge was found for both direct surface interactions and layer properties. Moreover the underlying cellulose layer in multilayer film was established to influence the surface forces especially at lower pH, where the cat NFC chains extensions were facilitated and overall charge was affected by the cationic counterpart within the layers. This enhanced understanding the effect of charge and structure on the interaction between these renewable nanoparticles is valuable when designing novel materials based on nanocellulose.
A study on the interaction of cationized chitosan with cellulose surfaces
Cellulose, 2014
This investigation describes the interaction of trimethyl chitosans (TMCs) with surfaces of cellulose thin films. The irreversible deposition/ adsorption of TMCs with different degrees of cationization was studied with regards to the salt concentration and pH. As substrates, cellulose thin films were prepared by spin coating from trimethylsilyl cellulose and subsequent regeneration to pure cellulose. The pH-dependent zeta potential of cellulose thin films and the charge of TMCs were determined by streaming potential and potentiometric charge titration methods. A quartz crystal microbalance with dissipation monitoring was further used as a nanogram sensitive balance to detect the amount of deposited TMCs and the swelling of the bound layers. The morphology of the coatings was additionally characterized by atomic force microscopy and related to the adsorption results. A lower degree of cationization leads to higher amounts of deposited TMCs at all salt concentrations. Higher amounts of salt increase the deposition of TMCs. Protonation of primary amino groups results in the immobilization of less material at lower pH values. The results from this work can further be extended to the modification of regenerated cellulosic materials to obtain surfaces, with amino-and trimethylammonium moieties. Keywords Cellulose thin films Á QCM-D Á Cationized chitosan Á AFM Á Polymer adsorption Member of the European Polysaccharide Network of Excellence (EPNOE).
Cerne, 2022
Background: In the study of biologically-based materials, nanocelluloses have been showing great prominence and positioned themselves as promising alternatives for the production of different industrialized materials. This polymer has received significant attention recently because it is produced from renewable sources and has unique properties offered by its organic nature and semi-crystalline structure. This work aimed to study the structural properties of suspensions and films by increasing MCC concentration in the form of powder with variations of 5 % (m/m) from 5 % to 30 %. Results: As expected, incorporating MCC increased the Segal index. The morphological analysis showed an increase in the diameters of the structures (NFC / MCC) in the suspensions when the presence of MCC was more significant, and films with cluster formations were observed. The films showed air permeability. Due to the MCC increase, the surface charge had results close to electrostatically stabilized nanosuspensions. An increase in the resistance to thermal degradation of the films was also observed. Conclusion: NFC has promising properties for different applications; it provides a film with a stable structure and is resistant to oxygen and tensile stresses. In addition, MCC has excellent potential due to its high crystallinity, structural characteristics, and nature. The increase of the MCC content altered the properties of the suspensions and films produced with NFC, forming a cohesive and resistant film, and influencing the performance of the different properties of the materials evaluated in this study, like air permeability, suspension stability, and thermal resistance.
Langmuir, 2009
A systematic study of the degree of molecular ordering and swelling of different nanocellulose model films has been conducted. Crystalline cellulose II surfaces were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water or by using the Langmuir-Schaefer (LS) technique. Amorphous cellulose films were also prepared by spin-coating of a precursor cellulose solution onto oxidized silicon wafers. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals and low-charged microfibrillated cellulose (LC-MFC). In addition, a dispersion of high-charged MFC was used for the buildup of polyelectrolyte multilayers with polyetheyleneimine on silica with the aid of the layerby-layer (LbL) technique. These preparation methods produced smooth thin films on the nanometer scale suitable for X-ray diffraction and swelling measurements. The surface morphology and thickness of the cellulose films were characterized in detail by atomic force microscopy (AFM) and ellipsometry measurements, respectively. To determine the surface energy of the cellulose surfaces, that is, their ability to engage in different interactions with different materials, they were characterized through contact angle measurements against water, glycerol, and methylene iodide. Small incidence angle X-ray diffraction revealed that the nanocrystal and MFC films exhibited a cellulose I crystal structure and that the films prepared from N-methylmorpholine-N-oxide (NMMO), LiCl/DMAc solutions, using the LS technique, possessed a cellulose II structure. The degree of crystalline ordering was highest in the nanocrystal films (∼87%), whereas the MFC, NMMO, and LS films exhibited a degree of crystallinity of about 60%. The N,N-dimethylacetamide (DMAc)/LiCl film possessed very low crystalline ordering (<15%). It was also established that the films had different mesostructures, that is, structures around 10 nm, depending on the preparation conditions. The LS and LiCl/DMAc films are smooth without any clear mesostructure, whereas the other films have a clear mesostructure in which the dimensions are dependent on the size of the nanocrystals, fibrillar cellulose, and electrostatic charge of the MFC. The swelling of the films was studied using a quartz crystal microbalance with dissipation. To understand the swelling properties of the films, it was necessary to consider both the difference in crystalline ordering and the difference in mesostructure of the films.
A method for the heterogeneous modification of nanofibrillar cellulose in aqueous media
Carbohydrate Polymers, 2014
Cellulosic substrates were modified by using sequential adsorption of functionalized carboxymethyl cellulose (CMC) and "click" chemistry in aqueous media. First, the effect of degree of substitution (DS), and level of functionalization as well as ionic strength of the medium were systematically investigated in situ by using quartz crystal microbalance with dissipation (QCM-D) in terms of the extent of adsorption of propargyl and azido functionalized CMC. It was found that the functionalization of CMC did not prevent its adsorption on cellulose. However, it was only effective in the presence of electrolytes. Moreover, the adsorption was found to be more efficient for the functionalized CMCs with low initial DS. Next, "click" chemistry, copper (I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC), was carried out for covalent attachment of different molecules on the pre-functionalized ultrathin cellulose films. The modified cellulosic surfaces were further characterized using AFM imaging and XPS. Finally, the method was successfully used in modification of nanofibrillar cellulose (NFC) in aqueous media.
Journal of Nanoparticle Research, 2011
Films made of nanofibrils were modified by adsorption of a cationic surfactant directly on the film surfaces. The nanofibrils were prepared by 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation and mechanical fibrillation, and were relatively homogeneous in size. The average nanofibril diameter and surface porosity was quantified based on computer-assisted field-emission scanning electron microscopy (FE-SEM). The cationic surfactant used in the adsorption was n-hexadecyl trimethylammonium bromide (cetyltrimethylammonium bromide, CTAB). The adsorption of CTAB was confirmed by Fourier transform infrared (FTIR) spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses. It was shown that the adsorbed layer of CTAB increased the hydrophobicity, without affecting the tensile index significantly. This capability, combined with the antiseptic properties of CTAB, may be a major advantage for several applications.
Reduction of water wettability of nanofibrillated cellulose by adsorption of cationic surfactants
Cellulose, 2011
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.
Nanofibrillated cellulose: surface modification and potential applications
Interest in nanofibrillated cellulose has been increasing exponentially because of its relatively ease of preparation in high yield, high specific surface area, high strength and stiffness, low weight and biodegradability etc. This biobased nanomaterial has been used mainly in nanocomposites due to its outstanding reinforcing potential. Solvent casting, melt mixing, in situ polymerization and electrospinning are important techniques for the fabrication of nanofibrillated cellulose-based nanocomposites. Due to hydrophilic character along with inherent tendency to form strong network held through hydrogen-bonding, nanofibrillated cellulose cannot uniformly be dispersed in most non-polar polymer matrices. Therefore, surface modification based on polymer grafting, coupling agents, acetylation and cationic modification was used in order to improve compatibility and homogeneous dispersion within polymer matrices. Nanofibrillated cellulose opens the way towards intense and promising research with expanding area of potential applications, including nanocomposite materials, paper and paperboard additive, biomedical applications and as adsorbent.
Rheologica Acta, 2017
The rheological behavior of cellulose nanocrystal (CNC) and modified CNC (mCNC) suspensions in dimethyl sulfoxide (DMSO) was investigated. The efficiency of the surface modification of CNCs by grafting an organic acid chloride to produce hydrophobic CNCs has been verified by X-ray photoelectron spectroscopy (XPS). The thermal degradation temperature of the mCNCs was found to be 165 versus 275°C for CNCs. The CNC suspensions in DMSO at 70°C underwent gelation at very low concentration (1 wt%) after 1 day. The network formation was temperature sensitive and did not occur at room temperature. For gels containing 3 wt% CNCs, the complex viscosity at 70°C increased by almost four decades after 1 day. For the mCNCs in DMSO, a weak gel was formed from the first day and temperature did not affect the gelation. Finally, the effect of adding 10 wt% of polylactide (PLA) to the solvent on the rheological properties of CNC and mCNC suspensions was investigated. The properties of suspensions containing 1.9 wt% CNCs and mCNCs increased during the first and second days, and PLA did not prevent gel formation. However, the reduced viscosity and storage modulus of the CNC and mCNC gels with PLA were lower than those of samples without PLA.
Development of Langmuir−Schaeffer Cellulose Nanocrystal Monolayers and Their Interfacial Behaviors
Langmuir, 2010
Model cellulose surfaces based on cellulose nanocrystals (CNs) were prepared by the Langmuir-Schaeffer technique. Cellulose nanocrystals were obtained by acid hydrolysis of different natural fibers, producing rodlike nanoparticles with differences in charge density, aspect ratio, and crystallinity. Dioctadecyldimethylammonium bromide (DODA-Br) cationic surfactant was used to create CN-DODA complexes that allowed transfer of the CNs from the air/liquid interface in an aqueous suspension to hydrophobic solid substrates. Langmuir-Schaeffer horizontal deposition at various surface pressures was employed to carry out such particle transfer that resulted in CN monolayers coating the substrate. The morphology and chemical composition of the CN films were characterized by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Also, their swelling behavior and stability after treatment with aqueous and alkaline solutions were studied using quartz crystal microgravimetry (QCM). Overall, it is concluded that the Langmuir-Schaeffer method can be used to produce single coating layers of CNs that were shown to be smooth, stable, and strongly attached to the solid support. The packing density of the films was controlled by selecting the right combination of surface pressure during transfer to the solid substrate and the amount of CNs available relative to the cationic charges at the interface.