Modified Cellulose Fibers Research Articles

Effect of Surface Grafting-Modified on Structure and Property of Cellulose Fibers

Cellulose fibers were chemically modified on surface by acrylamide polymerization and glutaraldehyde crosslinking. The chemical and morphological structures of modified cellulose fibers were investigated with X-ray diffraction, FTIR spectra, and scanning electron microscopy (SEM). The crystalline conformations of the cellulose fibers were slightly changed in polymerization and crosslinking process. The wet strength of modified cellulose fibers was improved. Appreciable difference between the surfaces of native and modified cellulose fibers was observed from SEM images.

Plasma-induced polymerization for enhancing paper hydrophobicity

Hydrophobic modification of cellulose fibers was conducted via plasma-induced polymerization in an attempt to graft the hydrophobic polymer chains on paper surface, this increasing the hydrophobicity of paper. Two hydrophobic monomers, butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA), were grafted on cellulose fibers, induced by atmospheric cold plasma. Various influencing factors associated with the plasma-induced grafting were investigated. Contact-angle measurement, Fourier Transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to ascertain the occurrence of the grafting and characterized the changes of the cellulose fiber after modification. The results showed that the hydrophobicity of the modified paper sheet was improved significantly after the plasma-induced grafting. The water contact angle on the paper surface reached up to 130°. The morphological differences between modified and unmodified samples were also revealed by SEM observation. The resulting paper is promising as a green-based packaging material.

Chemical modification of cellulosic fibers for better convertibility in packaging applications

Cellulose fiber has been modified by mechanical and chemical means in order to improve paper properties, which respond to moisture and temperature. When the cellulose is first refined and then etherified using hydroxypropylation under dry conditions, the paper sheets prepared from the hydroxypropylated cellulose show improved elongation. When the level of hydroxypropylation is high enough, the paper sheets also become transparent. Additionally, the effect of cellulose activation using different mechanical methods has been compared by esterification reactions. It is shown that removal of water is the most crucial step for the esterification reactions while other methods have a lesser impact. The paper sheets prepared from the esterified cellulose fibers show an increase in contact angles and high hydrophobicity.

Modification of cellulosic fibers by UV-irradiation. Part II: After treatments effects

This work presents the comparative study on the dyeing behavior of cellulose fibers in alkaline solutions and under the influence of UV radiation. The cellulosic fabrics were pretreated followed by conventional mercerization technique or treatment with UV irradiation. For different time duration the reorganization of cellulose fibers by swelling treatments in alkaline solutions results in numerous structural modifications, causing changes of their accessibility and/or reactivity. The results revealed that the swelling of the cellulosic fibers depends on type of pre-treatment, dose of the radiation and the concentration of alkaline solution used. SEM analysis confirmed that UV irradiation of the cellulosic fibers leads to a higher swelling in comparison with any concentration of NaOH treatment. In comparison of both the treatments, the mercerized cellulosic fibers have shown better tear and tensile strength as compared to the untreated and UV irradiated one. There is adverse effect of UV radiation on the mechanical properties of UV radiation. Moreover, no loss in weight was observed after exposing the cellulose fabrics surface to UV radiation.

Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane

Transport of carbonate ions was explored through fiber supported solid membrane. A novel fiber supported solid membrane was prepared by chemical modification of cellulose fiber with citric acid, 2′2-bipyridine and magnesium carbonate. The factors affecting the permeability of carbonate ions such as immobilization of citric acid-magnesium metal ion -2′2-bipyridine complex (0 to 2.5 mmol/g range) over cellulose fiber, carbon-ate ion concentration in source phase and NaOH concentration in receiving phase were investigated. Ki-netic of carbonate, sulfate, and nitrate ions was investigated through fiber supported solid membrane. Transport of carbonate ions with/without bubbling of CO2 (0 to 10 ml/min) in source phase was explored from source to receiving phase. The novel idea is to explore the adsorptive transport of CO2 from source to receiving phase through cellulose fiber containing magnesium metal ion organic framework. © 2012 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0)

Modification of cellulosic fibers to enhance their dyeability using UV-irradiation

Present research was proposed to evaluate the effect of UV radiation on the dyeing of cellulosic fabrics with direct dyes. The cellulosic fabric was irradiated by using UV radiation assembly (180W) for different time intervals i.e., 30, 45, 60, 75 and 90min respectively. The alike set of fabrics was prepared varying the concentration of NaOH during mercerization of the fabrics. All the treated fabrics were dyed with direct dyes. The dyeing parameters such as temperature, time, pH and salt concentration were optimized. The standard methods were employed to evaluate the color strength at various levels of pH, temperature, dyeing contact time and salt concentration. Scanning electron microscope test was performed in order to evaluate the change in fibril structure and surface. The obtained results of the dyed fabrics previously treated with UV radiation and after mercerization were compared. The results revealed that the color strength of UV-irradiated fabric was high as compared to mercerized cellulosic fabrics.

Influence of absorbed moisture on surface hydrophobization of ethanol pretreated and plasma treated ramie fibers

The existence of moisture in the substrate material may influence the effect of atmospheric pressure plasma treatment. Our previous study has found that the employment of ethanol pretreatment and plasma treatment can effectively induce hydrophobic surface modification of cellulose fiber to enhance the compatibility to polypropylene (PP) matrix, and this study aims to investigate the influence of fiber moisture regain on the treatment effect of this technique. Ramie fibers with three different moisture regains (MR) (2.5, 6.1 and 23.5%) are pretreated with ethanol followed by atmospheric pressure plasma treatment. Scanning electron microscope (SEM) shows that the 2.5% MR group has the most significant plasma etching effect. X-ray photoelectron spectroscopy (XPS) analysis indicates an increase of CC and a decrease of CO bond in the plasma treated groups, and the largest raise of CC bond for the 2.5% MR group. The water contact angles of the 2.5 and 6.1% MR groups increase, whereas no significant change is showed in the 23.5% MR group. The interfacial shear strengths (IFSS) measured by microbond pull-out test are raised by 44 and 25% when moisture regains are 2.5 and 6.1%, while presented no apparent improvement at high moisture regain of 23.5%. Therefore, it can be concluded that moisture regain has negative influence on the surface hydrophobization of ramie fibers in the improvement of adhesion property to PP matrix.

Surface modification of cellulose fibers with layer-by-layer self-assembly of lignosulfonate and polyelectrolyte: effects on fibers wetting properties and paper strength

To convert the hydrophilic cellulose fiber into hydrophobic, multilayers composed of cationic polyacrylamide (CPAM) and lignosulfonate (LS) were constructed on cellulose fiber surface using layer-by-layer (LBL) self-assembly technique. The presence of CPAM/LS multilayers were validated by zeta potential, X-ray photoelectron spectroscopy and atomic force microscopy (AFM). It was found that potential of fiber surface inversed after deposition of each layer, the contents of characteristic elements (i.e. S and N) of CPAM/LS multilayers increased with increasing bilayer number, furthermore, the calculated surface LS content increased linearly as a function of bilayers. AFM phase images indicated that the cellulose microfibrils on fiber surface were gradually covered by LS granules, resulting in an increase in fiber surface roughness as self-assembly proceeded. The wetting properties of modified cellulose fibers were detected by dynamic contact angle measurement. The results showed that the initial water contact angle gradually increased and the attenuation rate of the contact angle gradually decreased with the number of bilayers, suggesting that the controllable hydrophobicity of cellulose fiber can be achieved depending on the number of bilayers. It also showed that the polyelectrolyte presented in the outermost layer significantly influenced the wetting properties of cellulose fibers, and a higher hydrophobicity was observed when LS was in the outermost layer. Moreover, tensile strength test was performed on the handsheet prepared from LBL modified fibers to evaluate the effect of CPAM/LS multilayers on strength property of cellulose fiber networks. The tensile index of handsheet prepared from fibers modified with a (CPAM/LS)5 multilayer increased by 12.4% compared with that of handsheet prepared from original fibers. The print density of handsheet increased with the number of bilayers, suggesting that printability of the handsheet was improved by constructing CPAM/LS multilayers on cellulose fiber surface. This strategy will have a positive impact and potential application value in printing process control of cellulose fiber-based products.

Whitening regenerated cellulose fibers using fluorescent agent, surfactants, and salt—color indices measurements

AbstractThe whitening efficiency of regenerated cellulose fibers using sodium 4,4′‐distyrylbiphenyl sulfonate in the presence of an anionic surfactant (sodium dodecylsulfate) and a cationic surfactant (dodecyl trimethyl ammonium chloride) and salt (NaCl) was determined by fluorescence spectroscopy and color index values (brightness, whiteness, and yellowness). Epifluorescence images gave an intense blue color with an apparent uniform emission distribution. In absence of salt, the whitening efficiency was higher for aqueous solutions containing cationic surfactant below critical micellar concentration (cmc). In presence of salt, whitening efficiency was higher for anionic surfactant and more important. The concentration of surfactant required for greater brightness, whiteness, and yellowness was lower than that required in absence of salt. These data were discussed by the decrease of the cmc and by the screening of the modified cellulose fibers by counter ions coming from the salt. The role of surfactants was explained by the admicelization during the sorption process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of Plasma-Induced Polymerization on Contact Angle of Paper

Hydrophobic modification of cellulose fibres was conducted by plasma-induced polymer grafting in an attempt to increase the hydrophobicity of paper. Two hydrophobic monomers, i.e., butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA) were grafted on cellulose fibres, induced by atmospheric cold plasma. Various influencing factors associated with the plasma-induced grafting were investigated, including the contact time and reaction temperature with monomers, and the dosage of monomers. Contact-angle measurement, infrared spectrum (IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to ascertain the occurrence of the grafting. The results showed that the hydrophobic property of the modified paper sheet was improved significantly after the plasma-induced grafting. The water contact angle on the surface of the paper reached up to higher than125°.

Cation exchange chromatographic separation of amines through fiber supported solid membrane

The cation exchange chromatographic separation of pyridine, monoethanol and triethanol amines have been explored from source to receiving phase through the fiber supported solid membrane. The fibers supported solid membranes were prepared by chemically modification of cellulose fibers with introducing the carboxylic acid ion exchanging groups. The experimental variables explored were concentration of pyridine, monoethanol and triethanol amines (10 -2 to 10-6 M) in the source solution, HCl (0.01 to 0.20 M) in the receiving phase and stirring speed (50-130 rpm) of the bulk source and receiving phase. The efficiency has been evaluated of fiber supported solid membrane system for the transport of pyridine, monoethanol and triethanol amines from the source solution to receiving phase through the fiber supported solid membrane. The pre-concentration was studied of pyridine, monoethanol and triethanol amines from the dilute solutions.Key words: Pyridine, monoethanol and triethanol amines, fiber supported solid membrane; ion exchangeDOI: http://dx.doi.org/10.3329/cerb.v15i1.6788 Chemical Engineering Research Bulletin 15 (2011) 25-29

Polylactic Acid Composites Utilising Sequential Surface Treatments of Lignocellulose: Chemistry, Morphology and Properties

Polylactic acid (PLA)—maple fibre composites have been synthesised using a series of sequentially modified cellulose fibres (namely alkylation followed by either acetylation or silanation). Confirmations of the sequential modifications were made using Fourier Transform Infrared Spectroscopy and Inductively Coupled Plasma—Atomic Emission Spectroscopy and the new surface morphologies analysed using Scanning Electron Microscopy. The key advantage of the use of sequential treatments (with initial alkali treatment) was the allowance for direct grafting of suitable chemical groups onto the cellulose in the fibre due to the removal of lignin, hemicellulose and other surface impurities. However, a balance was found to exist between alkali exposure time, concentration and resulting fibre integrity. The conditions used resulted in a loss in fibre weight, fibre moisture content and tensile strength. Sequential treatments with acetylation or silane resulted in a 15–21% strength recovery from that of the alkali treated composite. Factors that influenced this recovery in strength were the improved fibre-polymer interface, namely the hydrophilic balancing of the fibres and this further affected the thermal-hydrolysis of the PLA during composite fabrication.

Structure and Activity of Paenibacillus polymyxa Xyloglucanase from Glycoside Hydrolase Family 44

The enzymatic degradation of plant polysaccharides is emerging as one of the key environmental goals of the early 21st century, impacting on many processes in the textile and detergent industries as well as biomass conversion to biofuels. One of the well known problems with the use of nonstarch (nonfood)-based substrates such as the plant cell wall is that the cellulose fibers are embedded in a network of diverse polysaccharides, including xyloglucan, that renders access difficult. There is therefore increasing interest in the “accessory enzymes,” including xyloglucanases, that may aid biomass degradation through removal of “hemicellulose” polysaccharides. Here, we report the biochemical characterization of the endo-β-1,4-(xylo)glucan hydrolase from Paenibacillus polymyxa with polymeric, oligomeric, and defined chromogenic aryl-oligosaccharide substrates. The enzyme displays an unusual specificity on defined xyloglucan oligosaccharides, cleaving the XXXG-XXXG repeat into XXX and GXXXG. Kinetic analysis on defined oligosaccharides and on aryl-glycosides suggests that both the −4 and +1 subsites show discrimination against xylose-appended glucosides. The three-dimensional structures of PpXG44 have been solved both in apo-form and as a series of ligand complexes that map the −3 to −1 and +1 to +5 subsites of the extended ligand binding cleft. Complex structures are consistent with partial intolerance of xylosides in the −4′ subsites. The atypical specificity of PpXG44 may thus find use in industrial processes involving xyloglucan degradation, such as biomass conversion, or in the emerging exciting applications of defined xyloglucans in food, pharmaceuticals, and cellulose fiber modification.

Sorption of anionic polysaccharides by cellulose.

The sorption of anionic polysaccharides pectin, alginate, and xanthan with cellulose were investigated in presence of calcium. Calcium sorption to cellulose was limited by the carboxyl group content in fibers. Atomic Absorption Spectroscopy (AAS) analysis was used to measure the calcium in cellulose fibers and chemical oxygen demand (COD) analysis reveals that the divalent ions calcium can bind the polysaccharide onto cellulose fibers. The amount of calcium and polysaccharide bound in Ca2+/polysaccharide modified cellulose fibers was 5.8-12.5mM Ca2+/kg fibers and 1500-2400mg polysaccharide/kg fibers, respectively. Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (FTIR-ATR) analysis confirmed the presence of polysaccharide on calcium containing cellulose fibers. The results of alizarin dyeing experiments at the end of polysaccharide sorption further confirmed the presence of calcium in Ca2+/polysaccharide modified cellulose fibers. The basic phenomenon of interaction of soluble ionic polysaccharide and cellulosic fibers in presence of divalent cations such as calcium is a key to understand biological functions and technological applications.

Environmentally friendly superabsorbent polymers for water conservation in agricultural lands

Polymer complexes of crosslinked carboxymethyl cellulose (CMC) and starch were synthesized to form superabsorbent polymers (SAP) and their performances as a water retaining aid for irrigation were assessed. The SAP was crosslinked with aluminum sulfate octadecahydrate for optimum water retention. Starch from vegetables and chemically modified cellulose fibers were used as the basis for the polymer structure because of their biodegradability and the sustainability of their sources. The starch vegetables include potatoes, yam, cassava, and corn. Radish seeds were planted in pots that contained soil amended with the SAPs (as well as soils control with no amendment). For the first two weeks the plants were given a healthy amount of water, then watering was reduced to observe how the plants responded to drought. The plants with no amendment to the soil stopped growing after the first two weeks and showed signs of dehydration. All the plants in the amended soil continued to grow after the first two weeks and they looked much healthier. Performance evaluation of the response to the four starch types suggests that potato based SAP performed the best with 73% water retention, while corn gave 56%. The study also suggests that lower dosage of 0.12% by weight of the potato based SAP performed better than 0.24% when used for soil amendment. Key words: Carboxymethyl cellulose, starch, superabsorbent polymer, water retention, biodegradable.

Surface hydrophobicity modification of cellulose fibers by layer-by-layer self-assembly of lignosulfonates

Self-assembled multilayers of lignosulfonates (LS) were built up on both quartz slides and cellulose fibers using a Cu2+-mediated layer-by-layer (LBL) technique. The growth of LS multilayers on quartz slides was monitored by UV-Vis spectroscopy, and the absorbance at 205 nm as well as at 280 nm was found to linearly increase with the number of layers. The formation of LS multilayers on fibers surfaces was characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The XPS results showed that the surface contents of the characteristic elements, S and Cu, of LS multilayers were increased with the number of layers, which suggests the deposition of LS-Cu2+ complexes on cellulose fibers. Furthermore, there was a good linear relationship between the calculated surface LS content and the increment of LS layers. The AFM morphology results confirmed that the cellulose microfibrils on fiber surface were gradually covered by LS particles, resulting in the increase of surface roughness as self-assembly proceeded. The hydrophobicity of cellulose fiber probed by dynamic contact angle was significantly increased due to LBL self-assembly of LS on its surface. The initial contact angle was increased from 0° to 115° as the cellulose fibers were modified with a 5-layer LS multilayer. The reduction rate of the contact angle was dependent on the number of layers. When the cellulose fiber was modified by a 5-layer LS multilayer, the contact angle shifted from 115 to 98° after 0.12 s, suggesting some degree of hydrophobic character. Therefore, this technique provides a simple but effective way for promoting hydrophobicity of cellulose fibers in a controllable manner.

Mild and Modular Surface Modification of Cellulose via Hetero Diels−Alder (HDA) Cycloaddition

A combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and hetero Diels-Alder (HDA) cycloaddition was used to effect, under mild (T ≈ 20 °C), fast, and modular conditions, the grafting of poly(isobornyl acrylate) (M(n) = 9800 g mol(-1), PDI = 1.19) onto a solid cellulose substrate. The active hydroxyl groups expressed on the cellulose fibers were converted to tosylate leaving groups, which were subsequently substituted by a highly reactive cyclopentadienyl functionality (Cp). By employing the reactive Cp-functionality as a diene, thiocarbonyl thio-capped poly(isobornyl acrylate) synthesized via RAFT polymerization (mediated by benzyl pyridine-2-yldithioformiate (BPDF)) was attached to the surface under ambient conditions by an HDA cycloaddition (reaction time: 15 h). The surface-modified cellulose samples were analyzed in-depth by X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, Fourier transform infrared (FT-IR) spectroscopy as well as Fourier transform infrared microscopy employing a focal plane array detector for imaging purposes. The analytical results provide strong evidence that the reaction of suitable dienophiles with Cp-functional cellulose proceeds under mild reaction conditions (T ≈ 20 °C) in an efficient fashion. In particular, the visualization of individual modified cellulose fibers via high-resolution FT-IR microscopy corroborates the homogeneous distribution of the polymer film on the cellulose fibers.

The transport of metal ions through fiber supported solid membranes in mixed solvents

The transport of metal ions has been explored of bismuth, cadmium and lead from source solution to receiving phase through the fiber supported solid membrane system. The fibers supported solid membranes were prepared by chemically modification of cellulose fibers with the introducing the ion exchanging groups. The experimental variables explored were concentration of metal ions in the source solution, mixed solvent composition in the receiving phase and stirring speed of the bulk source solution and receiving phase. The efficiency has been evaluated for the transport of metal ions from the source to receiving phase through the fiber supported solid membrane. The pre-concentration was investigated of metal ions from the dilute solutions. The fiber supported solid membrane with two-channel systems had been investigated for the transport of metal ions from the source to receiving phase. The capillary action phenomenon helps to effectively transport the metal ions through the fiber supported solid membrane.

Degradation of Reactive Red K-2G by a Photoassisted Fenton Reaction Using a Novel Loading Phthalocyanine Sulfonic Iron Fibers as a Catalyst

Reactive dyes have been widely used in the dyeing of bright colourful silk fabrics. The discoloration and degradation of Reactive Red K-2G in waste water were discussed in this paper. A new heterogeneous photocatalyst named loading phthalocyanine sulfonic iron fibers (FePcS-F) was prepared by phthalocyanine sulfonic Iron supported by modified cellulose fibers in acidic condition. The photocatalytic degradation of Reactive Red K-2G was characterized by discoloration rate to evaluate the effect of catalyst dosage, catalyst loading (CFePcS-F) and solution pH. The results proved that increasing catalyst dosage and CFePcS-F significantly accelerated the dye degradation. FePcS-F catalyst showed higher photocatalytic activity when the solution’s pH value is equal to or less than 6.0, compared to alkaline medium.

Cellulose-Based Bio- and Nanocomposites: A Review

Cellulose macro- and nanofibers have gained increasing attention due to the high strength and stiffness, biodegradability and renewability, and their production and application in development of composites. Application of cellulose nanofibers for the development of composites is a relatively new research area. Cellulose macro- and nanofibers can be used as reinforcement in composite materials because of enhanced mechanical, thermal, and biodegradation properties of composites. Cellulose fibers are hydrophilic in nature, so it becomes necessary to increase their surface roughness for the development of composites with enhanced properties. In the present paper, we have reviewed the surface modification of cellulose fibers by various methods. Processing methods, properties, and various applications of nanocellulose and cellulosic composites are also discussed in this paper.