Hydrophobization and characterization of internally crosslink-reinforced cellulose fibers

Transforming hydrophilic cellulose fibers into hydrophobic, non-hygroscopic fibers could potentially lead to a variety of new products, such as flexible packaging, self-cleaning films and strength-enhancing agents in polymer composites. To achieve this, softwood cellulose pulp was chemically modified with successive chemical treatments. First the C2 and C3 hydroxyl groups of the glucose units were selectively oxidized by periodate oxidation to reactive dialdehyde units on the cellulose chain, followed by a Schiff base reaction with 1,12-diaminododecane to crosslink the microfibrils within the fiber wall. This was done, because introducing high levels of alkylation resulted in fiber disintegration, which could be prevented by crosslinking. After internal crosslinking a second Schiff base reaction was performed with butylamine. This procedure yielded highly hydrophobic and low-hygroscopic cellulosic materials. The modified cellulose fibers were investigated by a variety of techniques, including Fourier transform infrared spectroscopy, nuclear magnetic resonance, field-emission scanning electron microscopy, thermogravimetric analysis, X-ray diffraction, moisture sorption and water contact angle measurements. The water uptake of the fibers after being modified reduced from 4 to around 1 %. Various reaction conditions were studied for optimum performance.     

Adsorption of chlorhexidine onto cellulosic fibers

Comparative investigations of adsorption properties of chlorhexidine (CHX) on two cellulose fibers, bleached cotton and viscose, were studied in order to obtain dry gauzes covered with known amount of this antiseptic. Adsorption isotherm results carried out at 293 and 323 K can be described by Langmuir isotherm model, nevertheless, at high concentration correlation is better to Freundlich isotherm. Electrokinetic potential evolution with CHX concentration, shows that initial negative zeta potential of cotton and viscose diminish its absolute value as the concentration of the treatment increases; both fibers present an isoelectric point at high concentration of CHX that is 0.3 mM for viscose and 0.8 mM for cotton. Electrostatic interactions between cationic groups of CHX and carboxylic acid groups of the fibers could explain adsorption at low concentration, but when it is higher than these values, possible hydrogen bonding between the amine groups of CHX and hydroxyl groups of cellulose could explain increasing adsorption when it is hindered by electrostatic repulsion as it is predicted by Freundlich model, that describes heterogeneous surface and multilayer adsorption. Adsorption kinetics isotherms reveal that the process is quick with t _1/2 values of 5.4 min for cotton and 2.8 min for viscose. Differences in adsorption behaviour between the two fibers could be attributed to structural differences as we have observed from estimation of CI index based on FTIR spectra. Values obtained 1.6 for viscose and 2.2 for cotton could explain that the amount of CHX adsorbed on viscose is higher than it is on cotton. Finally desorption experiments performed with 0.01 M of NaCl solution at room temperature and pH 6 reveals the possibility of therapeutical application of these fibers although further investigations must be done to optimize the process.     

Diffusion of cationic polyelectrolytes into cellulosic fibers

The penetration of cationic polyelectrolytes into anionic cellulosic fibers was evaluated with fluorescent imaging techniques in order to clarify the mechanism and time scales for the diffusion process. The bulk charge of the cellulosic fibers indirectly creates a driving force for diffusion into the porous fiber wall, which is entropic in nature due to a release of counterions as the polyelectrolyte adsorbs. The individual bulk charges in the fiber cell wall also interact with the diffusing polyelectrolyte, such that the polyelectrolyte diffuses to the first available charge and consequently adsorbs and remains fixed. Thus, subsequent polyelectrolyte chains must first diffuse through the adsorbed polyelectrolyte layer before adsorbing to the next available bulk charges. This behavior differs from earlier suggested diffusion mechanisms, by which polyelectrolytes were assumed to first adsorb to the outermost surface and then reptate into the pore structure. The time scales for polyelectrolyte diffusion were highly dependent on the flexibility of the chain, which was estimated from calculations of the persistence length. The persistence length ultimately depended on the charge density and electrolyte concentration. The charge density of the polyelectrolyte had a greater influence on the time scales for diffusion. High charge density polyelectrolytes were observed to diffuse on a time scale of months, whereas the diffusion of low charge density polyelectrolytes was measured on the order of hours. An influence of the chain length, that is, steric interactions due the persistence length of the polyelectrolyte and to the tortuosity of the porous structure of the fiber wall, could only be noted for low charge density polyelectrolytes. Increasing the electrolyte concentration increased the chain flexibility by screening the electrostatic contribution to the persistence length, in turn inducing a faster diffusion process. However, a significant change in the diffusion behavior was observed at high electrolyte concentrations, at which the interaction between the polyelectrolyte charges and the fiber charges was almost completely screened.     

Magnetic cellulosic materials based on TEMPO-oxidized viscose fibers

A simple method for preparation of magnetic cellulose fibers by coating (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized viscose with oleic-acid-coated or uncoated, freshly prepared magnetic nanoparticles (MNp) is presented. MNp attachment was facilitated by chemical activation of the cellulose fibers through introduction of negatively charged carboxylic groups using the well-established TEMPO-mediated oxidation protocol. The resulting composite materials preserved the intrinsic properties of the cellulose fibers, but gained notable specific features due to the presence of magnetic nanoparticles. The obtained composite materials were characterized using spectral (Fourier-transform infrared spectroscopy) and microscopic (scanning electron microscopy) methods. Thermogravimetric analyses were carried out to evaluate the thermal stability of the magnetic fibers. The magnetic properties were evaluated using vibrating-sample magnetometry.     

Grafting of acrylamide onto cellulosic fibers via dielectric-barrier discharge

Fully bleached kraft pulp (BKP) and thermomechanical pulp (TMP) fibers were grafted with acrylamide via dielectric-barrier discharge treatment at various treatment dosages. The results indicate that increased dielectric-barrier discharge treatment leads to the increased polymerization and incorporation of acrylamide onto fiber surfaces. Greater incorporation of poly(acrylamide) occurs on the BKP fibers than the TMP at the same treatment conditions. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM) indicate that dielectric-barrier discharge initiated modifications to fiber surface topo-chemistry occur across the fiber such that the sheet is randomly peppered with modified areas; however, it occurs in patches on individual fibers as opposed to occurring as an evenly distributed thin film. SEM and elemental analysis also showed that the incorporation of acrylamide onto the fiber surface increases with increased treatment dosages.     

Crosslinking and pyrolytic behavior of natural and man-made cellulosic fibers

Pyrolysis rates, energies of activation, and DSC data were obtained for cellulosic fibers crosslinked with increasing amounts of formaldehyde. Pyrolysis rates are affected by the reduction in degree of polymerization, the breaking of intermolecular hydrogen bonds, and the introduction of covalent linkages that accompany the crosslinking process. Thermal stabilization of cellulose is related mainly to the formation of interchain crosslinks. The influences of the crystallinity and orientations of the polymers upon changes in thermal stability and pyrolytic behavior due to crosslinking are demonstrated.     

Analysis of CMC attachment onto cellulosic fibers by infrared spectroscopy

Infrared spectroscopy has been used to measure the amount of carboxymethyl cellulose (CMC) attached to cellulosic fibers. CMC was attached to an unbleached kraft pulp in aqueous conditions. Isotropic handsheets were then prepared and ATR spectroscopy was used to measure the intensity of the carboxyl vibration, which correlates to the amount of attached CMC that was determined using a wet chemical approach. The ATR method is rather time consuming as several measurement points on the sample have to be averaged, although it is still much faster than the wet chemical approach. Infrared reflection absorption spectroscopy (IRRAS) using polarized light was further used to measure the amount of attached CMC. In this method the intensity of an electromagnetic wave confined to the thin layer is used to correlate the spectroscopy to the amount of CMC on the fiber surface in the paper sample. The measurement time is shorter than with the ATR method. The proposed IRRAS method could be employed as a fast and reliable way to quantify adsorption of chemicals on pulp fibers.     

One-pot eco-friendly oxidative synthesis of imine carboxymethyl dialdehyde cellulosic fibers

Cellulose - The quest to efficiently produce renewable and sustainable functional cellulosic products has prompted the development of an environmentally sensitive and cost-effective method to...     

Adsorption of octadecyltrimethylammonium chloride and adsolubilization on to cellulosic fibers

The coadsorption of different organic solutes on cellulosic fibers treated with octadecyltrimethylammonium chloride (ODTMA) has been studied. In the absence of ODTMA cellulosic fibers had little tendency to retain organic compounds. The enhanced solute incorporation was ascribed to the adsolubilization of these compounds on the aggregated domains of the adsorbed surfactant molecules at the solid/liquid interface. The specific shape of solute coadsorption isotherms indicated that the adsolubilization process may be regarded as a partition phenomenon between the aqueous bulk phase and the adsorbed surfactant aggregates. The decrease in solute uptake at the cellulose/water interface above the CMC of ODTMA was ascribed to micelle formation in the bulk solution and to the ensuing micellar solubilization of organic solutes. Preliminary experiments performed using vertical fixed bed columns showed that modified cellulosic fibers can be conveniently used as substrate for treating organic pollutants.     

Splitting tendency of cellulosic fibers. Part 3: splitting tendency of viscose and modal fibers

The splitting tendency of viscose and modal fibers in aqueous alkali solutions of LiOH, NaOH, KOH and TMAH was investigated. The viscose fibers splitted up to 5–7 fibrils, whereas modal fibers splitted up to 2–4 fibrils depending on alkali type and concentration. The fibrillar structure of lyocell enables it to split more (15–20 fibrils) than viscose and modal fibers. Splitting occurs where internal stress of fiber is high due to different alkali or void distribution inside fiber. The splitting test couldn’t be achieved for viscose and modal fibers between 1 and 5 M concentration of NaOH and TMAH solutions due to breakage of fibers during test. Above 5 M concentration, no split can be observed due to even distribution of alkali inside fiber. Paper presented at the 7th World Textile Conference, AUTEX 2007, Tampere, Finland, 26–28 June 2007. Christian-Doppler Laboratory of Textile and Fiber Chemistry of Cellulosics is a Member of European Polysaccharide Network of Excellence (EPNOE), www.epnoe.org     

Superhydrophobic,strong and transparent paper made from cellulosic fibers

Cellulose - Superhydrophobic and strong cellulosic paper was fabricated in a two-step process consisting of heavy refining and dip coating with PDMS (trimethylsiloxy-terminated poly...     

Preparation of cellulosic fibers with biological activity by immobilization of trypsin on periodate oxidized viscose fibers

In this study, a biologically active fibrous material was designed by immobilizing trypsin on viscose fibers. The viscose yarn was first oxidized with sodium periodate to produce aldehyde groups and then employed as a support for subsequent immobilization of trypsin through bovine serum albumin. The oxidation by sodium periodate caused changes in the chemical and physical properties of the modified yarn samples, which were evaluated by determining the aldehyde group content, fineness and tensile strength of yarn. The viscose fibers oxidized under the most severe conditions (0.4 % NaIO₄, 360 min) exhibited the maximum amount of introduced aldehyde groups (1.284 mmol/g), but also the highest decrease in tensile strength. The trypsin activity was assayed with N-α-benzoyl-DL-arginine p-nitroanilide hydrochloride, whereas the amount of bound trypsin was determined by Bradford method. Trypsin immobilized on oxidized viscose yarn retained 97.3 and 83.8 % of the initial activity over 60 days of storage at 4 and 25 °C, respectively, and remained firmly attached to the carrier. The potential application of obtained bioactive fibers is in the treatment of wounds.     

Adsorption of organic compounds onto polyelectrolyte immobilized-surfactant aggregates on cellulosic fibers

The adsorption of anionic surfactants with different hydrophobic chain lengths onto cellulose fibers pretreated with a cationic polyelectrolyte has been investigated. Five steps are involved in the adsorption process, which was ascribed to the formation of monolayer and bilayer surfactant aggregates. Electrostatic interaction between the residual surface charges followed by hydrophobic interaction among the alkyl chains are considered the main factors in the adsorption process. The adsorption of the anionic surfactant was found to greatly enhance the retention of organic compounds onto the polyelectrolyte-treated cellulose. The coadsorption phenomenon, which was dependent on the saturation level of the adsorbed surfactant, has been explained in terms of the accumulation of the organic solute on the hydrophobic core generated by the adsorbed layer.     

Fiber-matrix interactions in cement mortar composites reinforced with cellulosic fibers

With the aim of gaining a better understanding of the phenomena responsible of the loss of durability of cement mortar composites reinforced with vegetable fibers, this paper focuses on the analysis of the fiber-matrix interactions. More specifically we analyze the effects of the vegetable fibers on the cementitious matrix after their mixture for different periods of time and vice versa. Three kinds of cellulosic fibers with differences on its physic-chemical properties were studied: bamboo fibers, kraft pulp and cotton linters. The results show that the cellulosic fibers modify the total amount of heat released during the hydration process in the cement paste, this effect differing depending on the purity of the fibers. The high alkalinity of the cementitious matrix causes the partial dissolution of chemical components of the fibers and a harmful precipitate of the inorganic particles on its surface and/or lumen, damaging the fibers and hence decreasing its reinforcement capacity.     

Analysis of the topochemical effects of dielectric-barrier discharge on cellulosic fibers

This study investigates the fundamental topochemical effects of dielectric-barrier discharge treatment on bleached chemical pulp and unbleached mechanical pulp fiber surfaces. Fibers were treated with various levels of dielectric-barrier discharge treatment ranging from 0 to 9.27 kW/m²/min. Changes to the fiber surface topochemistry were investigated by atomic force microscopy (AFM). The AFM studies were complemented by inverse gas chromatography (IGC), contact angle evaluation, poly-electrolyte titration, viscosity testing and determination of water retention value (WRV). The static coefficient of friction and zero-span tensile index of sheets were also evaluated. Low dielectric-barrier discharge treatment levels resulted in increased surface energy and roughness. Fibers treated at high applied power levels showed surface energies and roughness levels near that of reference samples as well as evidence of degradation and decreased fiber swelling.     

Hydrophobization of chitosan-based films with acrolein

The structure of acrolein-modified chitosan films was studied by IR spectroscopy. Modification makes the films more hydrophobic. The physical and mechanical properties of films modified with acrolein solutions of low concentrations are improved relative to the unmodified films. The glass transition and decomposition temperatures of the samples were determined by dynamic mechanical and thermal gravimetric analysis. The possibility of using the materials for the development of matrices for tissue engineering was demonstrated.

     

Deposition of silver nanoparticles on cellulosic fibers via stabilization of carboxymethyl groups

The stabilizing role of carboxymethyl groups on the conformal deposition of Ag NPs over cellulosic fibers was elucidated while developing a method for the deposition of silver nanoparticles (NPs) on cellulose acetate (CA), cellulose and partially carboxymethylated cellulose (CMC) electrospun fibers. CMC fibers were prepared through judicious anionization of deacetylated cellulose acetate fibers. Ag NPs were chemically reduced from silver nitrate using sodium borohydride and further stabilized using citrate. Ag NPs were directly deposited onto CA, cellulose and CMC electrospun fibers at pH conditions ranging from 2.5 to 9.0. The resulting composites of Ag/fiber were characterized by field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectroscopy (EDX). The results revealed that the amount of Ag agglomerates and NPs deposited on CMC fibers was higher than that deposited on cellulose fibers at similar pH conditions, and that barely any Ag agglomerates or NPs were deposited on the CA fibers. These results implied that functional groups on the cellulose backbone played two important roles in the deposition of NPs as follows: (1) Hydrogen bonding was the main driving force for agglomeration of NPs when the medium pH was below 4.4, which corresponds to the pKa of carboxylic acid groups; (2) Carboxymethyl groups could replace citrate groups as stabilizers allowing the fabrication of a uniform and evenly distributed Ag NPs layer over CMC fibers at higher pH values. This report also highlights the importance of the substrate’s surface charge and that of the pH of the medium used, on the deposition of NPs. The composite of Ag NPs on CMC electrospun fibers appears to be a promising candidate for wound dressing applications due to its superior antibacterial properties originated by the uniform and even distribution of Ag NPs on the surface of the fibers and the wound healing aptness of the CMC fibers.     

Sorption studies on regenerated cellulosic fibers in salt–alkali mixtures

The degrees of salt sorption were determined in lyocell and viscose fibers immersed in aqueous solutions of salt–alkali mixtures with the aim of using salt sorption as an indirect measure of changes to fiber accessibility in presence of alkali. The salt–alkali mixtures used were combinations of NaOH with NaCl or NaBr, and of KOH with KCl or KBr. In general, salt sorption in fibers increased with increase in alkali concentration up to 2 mol/l, and did not change significantly thereafter. The accessibility of Br⁻ salts was greater than the Cl⁻ salts, but that of the Na⁺ salts was greater than the K⁺ salts. These trends in salt sorption indicate that salt accessibility in fibers is not influenced by the size of hydrated salt ions, but by the forces of electrostatic attraction and repulsion between the charged fiber surface and salt cations and anions.     

Physicochemical properties of new cellulosic fibers from the bark of Acacia arabica

With the growing environmental consciousness toward carbon emissions, natural fibers are the best alternative and act as a substitute for synthetic fibers due to their potential properties. New cellulosic fibers were identified from Acacia arabica bark. This study aimed at understanding the characteristics of Acacia arabica fibers (AAFs) extracted from the bark of the A. arabica, and its physicochemical properties were examined by thermal stability analyses, X-ray diffraction, chemical constitutions, and Fourier transform infrared spectroscopy analysis. Cellulose content (68.1 wt%), density (1028 kg m^?3), and crystallinity index (51.72%) properties were identified.     

Physico-chemical properties of new cellulosic fibers from the bark of Acacia planifrons

Identification of new natural fibers is growing due to their superior properties and the impetus for researchers to develop high-performance composites. This investigation was aimed at understanding the physico-chemical properties of Acacia planifrons fibers (APFs). The crystalline structure of APFs was analyzed by X-ray diffraction, and the crystallinity index (65.38%) was calculated. The chemical functional group of APFs was confirmed by Fourier transform-infrared spectroscopy, the thermal stability measured by thermogravimetric analysis, and surface characterization established by atomic force microscopy. Taken together, all the properties of APFs can play a vital role in establishing APFs as new reinforcement in polymer composites.