Surface Of Microfibrillated Cellulose Research Articles

Preparation of microfibrillated cellulose by in situ and one step method using calcium hydroxide as swelling and grinding agent

Abstract Calcium hydroxide was used as a swelling agent and grinding aid to grind together with cellulose raw materials to prepare microfibrillated cellulose (MFC). Carbon dioxide was introduced to obtain MFC coated with calcium carbonate (CMFC). The effect of calcium hydroxide dosage on the fibrillation process of cellulose materials and the characteristics of MFCs and CMFCs were studied. Results show that when the dosage of calcium hydroxide was 5 % (based on cellulose materials), calcium hydroxide could be completely dissolved in water and had a swelling effect on cellulose materials. When the dosage reached 10 %, undissolved calcium hydroxide particles could serve as grinding media to assist in the fibrillation of cellulose materials. When the dosage exceeded 50 %, the auxiliary grinding effect of calcium hydroxide was more obvious. After accelerated carbonation, the generated calcium carbonate nanoparticles were coated on the surface of MFC, which increased its viscosity and decreased water retention value. The presence of calcium carbonate also facilitated the concentration, redispersion, and drying of MFC. The pretreatment, mechanical fibrillation, and accelerated carbonation were carried out in the same equipment without the need for heating or washing. Therefore, this study provides a in situ and one step method for the preparation of MFC.

Oven‐Drying Microfibrillated Cellulose Covered with a Low Molecular Weight Copolymer for Dispersion in a Polymer Matrix

AbstractHornification remains a great challenge to the large‐scale use of oven‐dried microfibrillated cellulose (MFC) in industrial processes due to the difficulty to redisperse the oven‐dried MFC, especially in non‐polar polymer matrices. Therefore, an MFC coverage treatment with a low molecular weight copolymer is proposed here as a method to overcome hornification. MFC‐copolymer is produced by mechanical stirring and then oven‐dried. A poly(lactic acid) (PLA)/poly(ε‐caprolactone) (PCL)/MFC‐copolymer blend is prepared by melt extrusion to assess the dispersiveness of the treated MFC into the polymer matrix. Fourier Transform Infrared (FTIR) results suggest that the copolymer terminal hydroxyls can interact with the reactive hydroxyls present on the MFC surface, decreasing MFC hydrophilicity. Scanning Electron Microscopy (SEM) confirms that the copolymer covers parts of the MFC surface, which enables the microfibrils' redispersion. The solvent‐free, eco‐friendly, and low‐cost MFC‐copolymer treatment facilitates MFC redispersion by melting extrusion process in a low polarity polymeric matrix.

Biodegradation of Composites of Polylactic Acid and Microfibrillated Lignocellulose

We present a study of the controlled biodegradation of polylactic acid (PLA) reinforced with high lignin containing microfibrillated cellulose (MFLC) isolated from chemi-thermomechanical pulp. The surface of MFLC was modified using an acetylation method to decrease its polarity. Biocomposites with different MFLC and acetylated MFLC (Ac-MFLC) contents were fabricated via a solvent casting method. The biodegradation of biocomposites was performed by burying in soil and holding at 45 °C for 30 days. After soil burial, MFLC/biocomposites exhibited higher weight loss (5.4 %) compared to neat PLA (4.2 %) and Ac-MFLC/biocomposites (4.6 %). Morphological analysis results showed surface erosion of the PLA to change with the addition MFLC and Ac-MFLC, resulting in porous formations on the surface of biocomposites. These formations led to the loosening of microfibril-PLA interface in the internal structure, resulting in a significant decrease in the storage modulus of biocomposites. The biocomposites exhibited no antimicrobial properties, confirming their biotic degradability.Graphical

Microfibrillated Cellulose Grafted with Metacrylic Acid as a Modifier in Poly(3-hydroxybutyrate)

This work proposes a new method for obtaining poly(3-hydroxybutyrate) (PHB)/microfibrillated cellulose (MC) composites with more balanced properties intended for the substitution of petroleum-based polymers in packaging and engineering applications. To achieve this, the MC surface was adjusted by a new chemical route to enhance its compatibility with the PHB matrix: (i) creating active sites on the surface of MC with γ-methacryloxypropyltrimethoxysilane (SIMA) or vinyltriethoxysilane (SIV), followed by (ii) the graft polymerization of methacrylic acid (MA). The high efficiency of the SIMA-MA treatment and the lower efficiency in the case of SIV-MA were proven by the changes observed in the Fourier transform infrared FTIR spectra of celluloses. All modified celluloses and the PHB composites containing them showed good thermal stability close to the processing temperature of PHB. SIMA-modified celluloses acted as nucleating agents in PHB, increasing its crystallinity and favoring the formation of smaller spherulites. A uniform dispersion of SIMA-modified celluloses in PHB as a result of the good compatibility between the two phases was observed by scanning electron microscopy and many agglomerations of fibers in the composite with unmodified MC. The dual role of SIMA-MA treatment, as both compatibilizer and plasticizer, was pointed out by mechanical and rheological measurements. This new method to modify MC and obtain PHB/MC composites with more balanced stiffness–toughness properties could be a solution to the high brittleness and poor processability of PHB-based materials.

Novel and wet-resilient cellulose nanofiber cryogels with tunable porosity and improved mechanical strength for methyl orange dyes removal

Interconnected macro-porous cryogels with robust and pore-tunable structures have been fabricated using chemically crosslinked microfibrillated cellulose (MFC). Periodate oxidation was initially conducted to introduce aldehyde groups into the MFC surface, followed by the freeze-induced chemical crosslinking via the formation of hemiacetal bonds between aldehyde and hydroxyl at −12 °C. The cryogels with pore-tunable structures and sharply enhanced mechanical strengths were finally achieved by re-assembly of MFCs through soaking in NaIO4 solution. Furthermore, the MFC cryogels were post-crosslinked by polyethyleneimine (PEI), bestowing the cryogels with the capability of adsorbing anionic dyes. The stress of the PEI-MFC cryogel at the 80% strain was determined to be 304.5 kPa, which is the maximum value for the nanocellulose-based cryogels reported so far. Finally, the adsorption performances of PEI-MFC cryogels for methyl orange (MO) were evaluated. Maximum adsorption capacity of 500 mg/g could be obtained by the Langmuir model, outperforming that of previous absorbent materials. Reuse experiments indicated that over 90% of adsorption capacity was retained after 6 cycles. Continuous clean-up experiments demonstrated excellent MO removal abilities of the PEI-MFC cryogel. This study shows that the novel, green strategy to fabricate the robust cryogel extends the practical applications of nanocellulose adsorbents for environmental remediation.

Mechanical properties and electrical surface charges of microfibrillated cellulose/imidazole-modified polyketone composite membranes

In the present work, microfibrillated cellulose (MFC) suspensions were produced by high-pressure homogenization and subsequently used to fabricate MFC membranes (C-1) by vacuum filtration followed by hot-pressing. A polyketone (PK50) was chemically modified by Paal-Knorr reaction to graft imidazole (IM) functional groups along its backbone structure. The resulting polymer is referred to as PK50IM80. By solution impregnation, C-1 was immersed in an aqueous solution of PK50IM80 and subsequently hot pressed, resulting in the fabrication of MFC/PK50IM80 composite membranes (C-IMP). Another method, referred to as solution mixing, consisted in adding MFC into an aqueous solution of PK50IM80 followed by vacuum filtration and hot-pressing to obtain MFC/PK50IM80 composite membranes (C-MEZC). C-IMP and C-MEZC were characterized by a wide range of analytical techniques including, X-ray photoelectron spectroscopy, Fourier-transform infrared chemical imaging, scanning electron microscopy, atomic force microscopy, dynamical mechanical analysis, tensile testing as well as streaming zeta potential, and compared to C-1 (reference material). The results suggested that C-IMP possess a more homogeneous distribution of PK50IM80 at their surface compared to C-MEZC. C-IMP was found to possess significantly enhanced Young's modulus compared to C-1 and C-MEZC. The tensile strength of C-IMP was found to improve significantly compared to C-1, whereas C-1 possessed significantly higher tensile index than C-IMP and C-MEZC. Furthermore, the presence of PK50IM80 at the surface of MFC was found to significantly shift the isoelectric point (IEP) of the membranes from pH 2.3 to a maximum value of 4.5 for C-IMP. Above the IEP, C-IMP and C-MEZC were found to possess significantly less negative electrical surface charges (plateau value of −25 mV at pH 10) when compared to C-1 (plateau value of −42 mV at pH 10). Our approach may have implication to broaden the range of filtration applications of MFC-based membranes.

Rheological and mechanical properties of polypropylene composites containing microfibrillated cellulose (MFC) with improved compatibility through surface silylation

We investigated the rheological and mechanical properties of a polypropylene (PP) composite reinforced by microfibrillated cellulose (MFC) fibers, of which the size was fractionated at ca. 24 µm by removing substances such as lignin or hemicellulose out of natural plants to exert the maximum mechanical performance of cellulose fibers. Due to the poor compatibility of MFC with a non-polar hydrophobic PP matrix, the MFC surface was modified through silylation and acetylation to increase its wetting and dispersion characteristics. The content of silylated-MFC could increase up to 30 wt% in the PP composite through large-volume process such as extrusion and injection molding. In addition, all mechanical properties of the silylated-MFC/PP composite were improved compared to untreated MFC/PP, acetylated MFC/PP composite. It was ensured by a strong shear thinning characteristic of the PP composite with silylated MFC content 30 wt% exhibiting a 69% lower viscosity (337 Pa·s at 4.7 s−1) than the neat PP at 180 °C. The same 30 wt% silylated specimens gave a well-dispersed fibrous MFC in PP, providing a tensile modulus (3.09 GPa) and a flexural modulus (3133 MPa), which were 64 and 81% higher than the neat PP, and 16 and 15% higher than the untreated-MFC composites, respectively. The flexural strength and the heat distortion temperature were also increased by 10 and 22%, compared to neat PP, respectively. In the acetylation reaction, the fibril structure of MFC was damaged due to full substitution by acetyl groups, and the reinforcing effect was insignificant as a filler in PP matrix. The developed silylated-MFC/PP composites provided excellent mechanical properties and high-loading processability that would be difficult to achieve by other eco-friendly composite systems.

Novel Composite Adsorbent Consisting of Dissolved Cellulose Fiber/Microfibrillated Cellulose for Dye Removal from Aqueous Solution

A novel composite absorbent was developed based on dissolved cellulose fibers (as matrix) reinforced with microfibrillated cellulose (MFC). Both cellulose fibers and microfibrillated cellulose were functionally modified using an organic solvent-free approach to introduce carboxyl groups onto cellulose and the surface of MFC. To further enhance the adsorption capacity, nanosized CaCO3 was added as a pore forming agent during the formation of dissolved cellulose/MFC (CMFC) composites and removed in acidic conditions afterward. The structure and morphology of as-synthesized adsorbents were identified using a scanning electron microscope, Fourier transform infrared spectroscope, thermogravimetric analyzer, and Brunauer–Emmet–Teller instrument. An orthogonal experimental design and software SPSS were utilized to reveal the impact of influencing factors (pH, temperature, and the concentration of pore forming agent) on dye removal. The results were imitated by kinetic models and adsorption isotherms, which revea...

The effect of surface modification of microfibrillated cellulose (MFC) by acid chlorides on the structural and thermomechanical properties of biopolyamide 4.10 nanocomposites

Microfibrillated cellulose (MFC) has recently been identified as an innovative product of wood and agriculture industry with potential applications as reinforcement and carrier for functional properties of polymer composite materials, such as improved barrier and optical properties. The widespread commercial application of MFC in polymer technology still requires the development of new methods of MFC surface modifications in order to provide stong interfacial adhesion and good dispersibility of additive in polymer matrix. In this work microfibrillated cellulose was modified by acid chlorides arranged in a homologous series that showed high efficiency in changing the surface properties of the material. The modified MFC displayed hydrophobic character combined with preserved fibrillar morphology and high crystallinity. Chemical modification of MFC was assessed by Fourier transformed infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) analyses. Despite the fact that the reactivity of acid chloride slightly decreased with increasing chain length the total effect on MFC wetting with water was most pronounced for the modifier with the longest alkyl chain. Completely bio-based engineering nanocomposites of biopolyamide 4.10 (PA4.10) and surface modified MFC were prepared by melt blending. Structural, morphological and thermomechanical analysis by scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic mechanical analysis (DMA) methods evidenced clear dependence of composite performance on the length of alkyl chain attached to the MFC surface. The modification of MFC by hexanoyl chloride produced nanofiller with good dispersibility in PA4.10 matrix and was favorable in terms of dynamic mechanical properties of composites. While PA4.10 composites containing MFC functionalized by longer alkyl chains (more than 10 carbon atoms) showed a decrease of storage modulus due to insufficient interfacial interactions or plasticization effect.

Arsenic removal by magnetite-loaded amino modified nano/microcellulose adsorbents: Effect of functionalization and media size

Comparative adsorption study related to benefits of parent media size, i.e. microfibrillated cellulose (MC) versus nanocellulose (NC) support, for the preparation of magnetite (MG) based high performance adsorbent for arsenic removal was conducted. Precipitation of MG on amino terminal branched organic structure, L, either linked by maleic acid residue on NC surface (NC-MA/L) or linked by oxalyl bridge on MC surface (MC-O/L) produced NC-MA/L-MG and MC-O/L-MG adsorbents, respectively. Precipitation of nanosized MG on amino functionalized NC-MA/L and MC-O/L, performed according to optimized procedure, contributed to improved textural properties and adsorptive/kinetic performances of novel adsorbents. Adsorption capacity of arsenate, As(V), was in favor of NC-MA/L-MG (85.3 versus 18.5mgg−1) while MC-O/L-MG exhibited faster kinetics (0.541 versus 0.189gmg−1min−1). Lower capacity of arsenite, As(III), removal, 68.3mgg−1 for NC-MA/L-MG and 17.8mgg−1 for MC-O/L-MG, were obtained. Calculated activation energies, 13.28 and 10.87kJmol−1 for NC-MA/L-MG and MC-O/L-MG with respect to As(V), respectively, suggest, in accordance with results of Weber-Morris fitting, that internal mass transfer controls adsorption process. Model free adsorption kinetics confirmed beneficial uses of MC-O/L-MG due to low activation energy dependence on the extent of adsorption.

Effect of polyelectrolyte morphology and adsorption on the mechanism of nanocellulose flocculation

The effect of polyelectrolyte morphology, charge density, molecular weight and concentration on the adsorption and flocculation of Microfibrillated Cellulose (MFC) were investigated. Linear Cationic Polyacrylamide (CPAM) and Branched Polyethylenimine (PEI) of varying charge density and molecular weight were added at different dosages to MFC suspensions. The flocculation mechanisms were quantified by measuring gel point by sedimentation, and floc size, strength and reflocculation ability through Focussed Beam Reflectance Measurements. Polymer adsorption was quantified through zeta potential and adsorption measurements using polyelectrolyte titration. The flocculation mechanism of MFC is shown to be dependent on polyelectrolyte morphology. The high molecular weight branched polymer, HPEI formed rigid bridges between the MFC fibres. HPEI had low coverage and negative zeta potential at the optimum flocculation dosage, forming flocs of high strength. After breaking of flocs, total reflocculation was achieved because the high rigidity of polymer did not allow reconformation or flattening of the polyelectrolyte adsorbed on MFC surface. The lower molecular weight branched polymer, LPEI (2kDa) showed rapid total deflocculation, complete reflocculation and had maximum flocculation occurring at the point of zero charge. These characteristics correspond to a charge neutralisation mechanism. However, if the flocculation mechanism was purely charge neutralisation mechanism, the minimum gel point would be at the point of zero charge. Since this is not the case, this difference was attributed to the high polydispersity of the commercial LPEI used, allowing some bridges to be formed by the largest molecules, changing the minimum gel point. With the linear 80% charged 4MDa CPAM, bridging mechanism dominates since maximum flocculation occurred at the minimum gel point, negative zeta potential and low coverage required for maximum flocculation. Reflocculation was not possible as the long linear polymer reconformed on the MFC surface under a flat conformation. Flocculation with the linear 50% charged 13MDa CPAM happened by bridging with the minimum gel point and maximum flocculation corresponding to roughly half polyelectrolyte surface coverage on cellulose.

Dry, hydrophobic microfibrillated cellulose powder obtained in a simple procedure using alkyl ketene dimer

In order to produce dry and hydrophobic microfibrillated cellulose (MFC) in a simple procedure, its modification with alkyl ketene dimer (AKD) was performed. For this purpose, MFC was solvent-exchanged to ethyl acetate and mixed with AKD dissolved in the same solvent. Curing at 130 °C for 20 h under the catalysis of 1-methylimidazole yielded a dry powder. Scanning electron microscopy of the powder indicated loss in nanofibrillar structure due to aggregation, but discrete microfibrillar structures were still present. Water contact angle measurements of films produced from modified and unmodified MFC showed high hydrophobicity after AKD treatment, which persisted even after extraction with THF for 8 h. The hydrophobized MFC was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and X-ray analysis. In summary, strong indications for the presence of AKD on the surface of MFC before and after extraction with solvent were found, but only a very small amount of covalent β-ketoester linkages between the modification agent and cellulose was revealed.

Contact Antimicrobial Surface Obtained by Chemical Grafting of Microfibrillated Cellulose in Aqueous Solution Limiting Antibiotic Release.

Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the β-lactam antibiotic benzyl penicillin in aqueous medium to prepare antimicrobial films. Penicillin was grafted on the MFC surface using a suspension of these nanofilaments or directly on films. Films prepared from the penicillin-modified MFC were characterized by Fourier transform infrared spectroscopy, contact angle measurements, elemental analysis, and X-ray photoelectron spectroscopy and tested for antibacterial activity against the Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. Penicillin-grafted MFC films exhibited successful killing effect on Gram-positive bacteria with 3.5-log reduction whereas bacteriostatic efficiency was found in penicillin-grafted MFC suspension. The zone of inhibition test and leaching dynamic assay demonstrated that penicillin was not diffused into the surrounding media, thus proving that the films were indeed contact active. Thus, penicillin can be chemically bound to the modified substrate surface to produce promising nonleaching antimicrobial systems.

Different strategies for obtaining high opacity films of MFC with TiO2 pigments

The present study examines the production and characterization of opaque solid films made with microfibrillated cellulose (MFC) suspension and titanium dioxide (TiO2) nanoparticles. Three different strategies were investigated: a blend of (1) MFC and TiO2 (2) a premix in which TiO2 particles are used to favor the fibrillation step of MFC and (3) a sol–gel strategy in which TiO2 particles were directly generated onto the surface of MFC. The different process parameters have been optimized both for the production of MFC and the sol–gel reaction. Gel suspensions containing different ratios of TiO2 were morphologically and chemically characterized. In order to characterize the size and the nature of the particles, diffraction laser scattering, atomic force microscopy were used while the thermo gravimetric analysis and X-ray diffraction were used to investigate the degradation of MFC for all the three strategies. To highlight the level of dispersion of TiO2 within the MFC network, scanning electron microscopy in BSE mode has been employed. Finally, the transparence and the mechanical properties of solid films were measured by UV spectrophotometry and tensile tests, respectively. Very good TiO2 dispersion and high opacity MFC films have been achieved with a very low amount of TiO2. Thus, the best strategy that takes into account the easiest process for making the hybrids and leading to the high level of opacity with the lowest ratio of TiO2 is the premix strategy.

Investigation on the effect of cellulosic nanoparticles’ morphology on the properties of natural rubber based nanocomposites

Cellulose whiskers and microfibrillated cellulose (MFC) were extracted from the rachis of date palm tree and characterized. These cellulosic nanoparticles were used as reinforcing phase to prepare nanocomposite films using latex of natural rubber as matrix. These films were obtained by the casting/evaporation method. The properties of the ensuing nanocomposite films were investigated using differential scanning calorimetry, toluene and water uptake experiments, dynamic mechanical analysis and tensile tests. The stiffness of the natural rubber was significantly increased above its glass–rubber transition temperature upon nanoparticles addition. The reinforcing effect was shown to be higher for nanocomposites with MFC compared to whiskers. It was ascribed to the higher aspect ratio and possibility of entanglements of the former. The presence of residual lignin, extractive substances and fatty acids at the surface of MFC was also suggested to promote higher adhesion level with the polymeric matrix.

Chemical surface modifications of microfibrillated cellulose

Microfibrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization. The surface of the MFC was modified using different chemical treatments, using reactions both in aqueous- and organic solvents. The modified MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium (IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate, followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC surface as a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC.