Mechanical and oxygen barrier properties of films prepared from fibrillated dispersions of TEMPO-oxidized Norway spruce and Eucalyptus pulps

TEMPO-oxidized cellulose nanofibers (TOCN) were obtained from commercial Norway spruce and mixed Eucalyptus cellulose pulps using TEMPO/sodium bromide (NaBr)/sodium hypochlorite (NaClO) system at pH 10 and 22 °C. After reaction, the fibrillated TEMPO-oxidized celluloses were used for preparation of self-standing films and casting of laminate films on 50 μm thick polyethylene terephthalate. Significant differences between N. spruce and Eucalyptus TOCN were registered. The tensile strength of the films showed a maximum value for spruce samples oxidized with addition of 10 mmol g⁻¹ of NaClO. Oxygen permeability decreased with increasing oxidation levels, being lower for N. spruce TOCN compared to Eucalyptus.     

All-cellulose nanocomposites by surface selective dissolution of bacterial cellulose

All-cellulose nanocomposites using bacterial cellulose (BC) as a single raw material were prepared by a surface selective dissolution method. The effect of the immersion time of BC in the solvent (lithium chloride/N,N-dimethylacetamide) during preparation on the nanocomposite properties was investigated. The structure, morphology and mechanical properties of the nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, and tensile testing. The optimum immersion time of 10 min allowed the preparation of nanocomposites with an average tensile strength of 411 MPa and Young’s modulus of 18 GPa. With the longest immersion time of 60 min, the prepared composite sheet turns to express a very high toughness characteristic possessing a work-to-fracture as high as 16 MJ/m³. These biobased nanocomposites show high performances thanks to their unique structure and properties.     

Cellulose nanofibrils as filler for adhesives: effect on specific fracture energy of solid wood-adhesive bonds

Cellulose nanofibrils were prepared by mechanical fibrillation of never-dried beech pulp and bacterial cellulose. To facilitate the separation of individual fibrils, one part of the wood pulp was surface-carboxylated by a catalytic oxidation using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as a catalyst. After fibrillation by a high pressure homogenizer, the obtained aqueous fibril dispersions were directly mixed with different urea–formaldehyde-(UF)-adhesives. To investigate the effect of added cellulose filler on the fracture mechanical properties of wood adhesive bonds, double cantilever beam specimens were prepared from spruce wood. While the highest fracture energy values were observed for UF-bonds filled with untreated nanofibrils prepared from wood pulp, bonds filled with TEMPO-oxidized fibrils showed less satisfying performance. It is proposed that UF-adhesive bonds can be significantly toughened by the addition of only small amounts of cellulose nanofibrils. Thereby, the optimum filler content is largely depending on the adhesive and type of cellulose filler used.     

On the use of plant cellulose nanowhiskers to enhance the barrier properties of polylactic acid

Polylactic acid (PLA) nanocomposites were prepared using cellulose nanowhiskers (CNW) as a reinforcing element in order to asses the value of this filler to reduce the gas and vapour permeability of the biopolyester matrix. The nanocomposites were prepared by incorporating 1, 2, 3 and 5 wt% of the CNW into the PLA matrix by a chloroform solution casting method. The morphology, thermal and mechanical behaviour and permeability of the films were investigated. The CNW prepared by acid hydrolysis of highly purified alpha cellulose microfibers, resulted in nanofibers of 60–160 nm in length and of 10–20 nm in thickness. The results indicated that the nanofiller was well dispersed in the PLA matrix, did not impair the thermal stability of this but induced the formation of some crystallinity, most likely transcrystallinity. CNW prepared by freeze drying exhibited in the nanocomposites better morphology and properties than their solvent exchanged counterparts. Interestingly, the water permeability of nanocomposites of PLA decreased with the addition of CNW prepared by freeze drying by up to 82% and the oxygen permeability by up to 90%. Optimum barrier enhancement was found for composites containing loadings of CNW below 3 wt%. Typical modelling of barrier and mechanical properties failed to describe the behaviour of the composites and appropriate discussion regarding this aspect was also carried out. From the results, CNW exhibit novel significant potential in coatings, membranes and food agrobased packaging applications.     

Morphology control of poly(lactic) acid/polypropylene blend composite by using silanized cellulose fibers extracted from coir fibers

The objective of this work is the use of cellulose fibers extracted from coir fibers as Janus nanocylinders to suppress the phase retraction and coalescence in poly(lactic) acid/polypropylene bio-blend polymers via prompting the selective localization of cellulose fibers at the interface using chemical modification. The untreated and modified cellulose fibers extracted from coir fibers using a silane molecule (tetraethoxysilane) were used as reinforcement and as Janus nanocylinder at two weight contents (2.5 wt% and 5 wt%) to manipulate the morphology of the bio-blends. Their bio-composites with PLA-PP matrix were prepared via melt compounding (at PLA/PP: 50/50). The treatment effect on component interaction and the bio-composites properties have been studied via Scanning electron microscopy, infrared spectroscopy, and differential calorimetry analysis. The mechanical and rheological properties of nanocomposites were similarly assessed. Young's modulus and tensile strength of PLA-PP nanocomposites reinforced by silanized cellulose fibers show a great enhancement as compared to a neat matrix. In particular, there was a gain of 18.5% in Young's modulus and 11.21% in tensile strength for silanized cellulose fiber-based bio-blend composites at 5 wt%. From the rheological point of view, it was found that the silanized cellulose fibers in PLA-PP at both fibers loading enhances the adhesion between both polymers leading to tuning their morphology from sea-island to the continuous structures with the appearance of PLA microfibrillar inside of bio-composites. This change was reflected in the relaxation of the chain mobility of the bio-blend composites.

     

Nanocomposites prepared by in situ enzymatic polymerization of phenol with TEMPO-oxidized nanocellulose

The objective of this study was to prepare nanocomposites based on polyphenols and nanocellulose fibers using relatively benign processing. To accomplish this, phenol was polymerized using horseradish peroxidase in the presence of TEMPO-oxidized nanocellulose. The polyphenol-nanocellulose composite was insoluble in organic solvents but the individual components were soluble. SEM imaging of fracture surfaces of polyphenol, nanocellulose, and composite indicated brittle failure in polyphenol and nanocellulose but ductile failure in the composite pointing to a potential synergistic effect from the addition of the components. Polyphenol existed as spherical or near-spherical “clusters” that were ca. 10 μm in the absence of nanocellulose and ca. 0.1 μm in the presence of nanocellulose. The observed change in structure corresponded to changes in the thermal stability because the composite was more thermally stable than the components. FT-IR analysis of polyphenol-nanocellulose composites showed physical and chemical interactions between the fiber and matrix. This study is a significant improvement in forming nanocomposites without the intensive processing usually required for dispersion.     

Obtaining nanocomposites of polyamide 6 and cellulose whiskers via extrusion and injection molding

Nanocomposites of polyamides with cellulose whiskers are difficult to obtain by conventional processing of extrusion and injection molding because of the low thermal stability of the cellulosic nanostructures and the relatively high processing temperature of polyamides, which is higher than the temperature of thermal degradation of cellulose whiskers. Thus, in this study cellulose whiskers were coated with polyamide 6 (PA6) in order to increase their thermal stability and prevent the formation of agglomerates. This coating on cellulose whiskers allows their application to obtain nanocomposites with polyamides, whose processing temperatures are relatively high, around 250 °C. Cellulose whiskers (CWs) were obtained from cotton fibers by acid hydrolysis. The freeze-dried CWs were coated with PA6 by dispersing them in formic acid; PA6 was solubilized in this suspension. The cellulose-coated whiskers (CCWs) were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electron microscopy (SEM-FEG) and infrared spectroscopy. SEM-FEG and TG results showed that the PA6 coating on CWs prevented high agglomeration of dried CWs and promoted an increase in their thermal stability from 180 to 280 °C, allowing the use of CCWs to obtain nanocomposites with PA6 using conventional processing routes, such as extrusion and injection molding, at appropriate processing temperatures. In this way, 1 wt% CCWs was used to prepare nanocomposites with PA6. The PA6 + 1CW nanocomposites were compared to neat PA6 without CWs. The samples were characterized by tensile tests and DSC, and the results showed that the PA6 coating on CWs was effective in raising the thermal stability of CWs, improving the dispersion of CWs in the matrix of PA6, resulting in a 45 % increase in the elastic modulus of the nanocomposite with only 1 wt% of coated cellulose whiskers in comparison to neat PA6.     

Synthesis of soluble and meltable pre‐ceramic polymers for Zr‐containing ceramic nanocomposites

Polymer‐derived methods are one of the most important tools for the synthesis of ceramics with a finely dispersed microstructure. In this study, a soluble and meltable ZrC/C pre‐ceramic polymer, P‐DACZ, (which would later exhibit a high ceramic yield of 71 wt%) was synthesized via radical polymerization. By adding low molecular weight polycarbosilane in any proportion during the radical polymerization process of P‐DACZ, a soluble and meltable ZrC/SiC/C pre‐ceramic precursor, PCS‐DACZ (which would later exhibit a high ceramic yield of >80 wt%) was synthesized. After annealing at 1400 °C under an argon flow, the precursors converted into bulk ZrC/C and ZrC/SiC/C ceramic nanocomposites. The ZrC nanoparticles could resist any grain growth when heat‐treated at temperatures above 1800 °C because the C or SiC matrix prevented long‐range atomic diffusion of zirconium. Such ceramic nanocomposites would be suitable for structural and (multi)functional applications at harsh environments with high temperatures.     

Nanoperlite effect on thermal,rheological, surface and cellular properties of poly lactic acid/nanoperlite nanocomposites for multipurpose applications

In this study, poly lactic acid (PLA) based nanocomposites containing perlite nanoparticles were prepared by melt mixing method. Various characterization techniques were employed to evaluate the performance PLA/nanoperlite nanocomposites. The nanocomposites were characterized via FTIR to investigate the functional groups and chemical structure of the nanocomposites. Thermal properties of the nanocomposites, examined by DSC, showed that the increase of nano-perlite content in the PLA matrix reduces the crystallinity and melting temperature of the nanocomposites. The rheological studies indicated that both of storage and loss modulus are increased when the nanoperlite is added up to 5 wt%. However, the modulus is reduced in samples containing more than 5 wt% nanoparticle due to their agglomeration. The in-vitro degradation studies of the nanocomposites at elevated and normal temperatures showed hydrolytic degradation around 13–15 months. The surface behavior results implied that the water contact angle values exhibit a reducing trend when the nanoperlite content increases up to 3 wt%, which can be related to the decreased crystallinity of PLA and also to the hydrophilic nature of perlite. Moreover, the adhesion of osteoblast cells and their viability on an electrospun scaffold, made of optimized sample, showed the initial implications of potential applications of the nanocomposites in bone regeneration and biomedical applications. These multipurpose nanocomposites can also be used for packaging applications.     

Structures and cyclization behaviors of gel-spun cellulose/polyacrylonitrile composite fibers

Polyacrylonitrile (PAN)/cellulose composite fibers have been produced by dry-jet gel spinning through their co-solution. The rheological properties of PAN/cellulose/dimethylacetamide/LiCl solutions containing different cellulose contents from 0 to 10 wt% were characterized, and 5 wt% PAN/cellulose composite solution shows the best solution homogeneity. During gel spinning, the cellulose forms elongated particles inside the gelation bath, and the particle diameters depend on the as-spun draw ratio. It was found that the glass transition of PAN fibers shifts to higher temperatures along with the increase of cellulose content, and the glass transition activation energy of PAN chains becomes higher when cellulose particles become smaller. Regardless the changes of cellulose amount (2–10 wt%) and particle diameter (7.1–1.4 μm), the cyclization activation energy of PAN/cellulose composite fibers is 13–17% lower than that of neat PAN fibers. Our experiments suggest that the addition of cellulose in PAN fibers has no direct effect on the cyclization reaction of PAN chains. Instead, the released by-products during the pyrolysis of cellulose at high temperature degradation affect the cyclization reaction of PAN chains.     

Compression molded wood pulp biocomposites: a study of hemicellulose influence on cellulose supramolecular structure and material properties

In this study, the importance of hemicellulose content and structure in chemical pulps on the property relationships in compression molded wood pulp biocomposites is examined. Three different softwood pulps are compared; an acid sulfite dissolving grade pulp with high cellulose purity, an acid sulfite paper grade pulp and a paper grade kraft pulp, the latter two both containing higher amounts of hemicelluloses. Biocomposites based the acid sulfite pulps exhibit twice as high Young’s modulus as the composite based on paper grade kraft pulp, 11–12 and 6 GPa, respectively, and the explanation is most likely the difference in beating response of the pulps. Also the water retention value (WRV) is similarly low for the two molded sulfite pulps (0.5 g/g) as compared to the molded kraft pulp (0.9 g/g). The carbohydrate composition is determined by neutral sugar analysis and average molar masses by SEC. The cellulose supramolecular structure (cellulose fibril aggregation) is studied by solid state CP/MAS ¹³C-NMR and two forms of hemicellulose are assigned. During compression molding, cellulose fibril aggregation occurs to higher extent in the acid sulfite pulps as compared to the kraft pulp. In conclusion, the most important observation from this study is that the difference in hemicellulose content and structure seems to affect the aggregation behaviour and WRV of the investigated biocomposites.     

New insights into the material chemistry of polycaprolactone-grafted cellulose nanofibrils/polyurethane nanocomposites

Polycaprolactone (PCL) was grafted to TEMPO-oxidized nanocellulose (TONCs) through a classical ring-opening polymerization reaction mediated by the surface TONC hydroxyl and carboxyl groups. The PCL increased the thermal stability and hydrophobicity without compromising the crystallinity. When TONCs and PCL-grafted TONCs (PTONC) were compared with respect to their perfusion within a segmented polyurethane matrix (CLPU), PTONC dispersed far better as evidenced by increased storage modulus and Young’s modulus. The mechanical strength of the PTONC nanocomposites was nearly that of unmodified TONCs while at a low content (<3 wt%). Furthermore, PTONC in CLPU promoted micro-phase separation of the matrix leading to a smaller decrease in loss factor and elongation at break for the nanocomposites, highly superior to unmodified TONCs. Thus, PTONC as a reinforcement agent enhanced the mechanical properties and ductility of CLPU.     

Cellulose II nanoelements prepared from fully mercerized, partially mercerized and regenerated celluloses by 4-acetamido-TEMPO/NaClO/NaClO2 oxidation

A softwood bleached kraft pulp (SBKP) and cotton lint cellulose were fully or partially mercerized, and these along with celluloses and commercially available regenerated cellulose fiber and beads were oxidized by 4-acetamido-TEMPO/NaClO/NaClO₂ at 60 °C and pH 4.8. Weight recovery ratios and carboxylate contents of the oxidized celluloses were 65–80% and 1.8–2.2 mmol g⁻¹, respectively. Transparent and viscous dispersions were obtained by mechanical disintegration of the TEMPO-oxidized celluloses in water. These aqueous dispersions showed birefringence between cross-polarizers, indicating that mostly individualized cellulose nanoelements dispersed in water were obtained by these procedures. Transmission electron microscopy observation showed that the cellulose nanoelements prepared from mercerized SBKP, repeatedly mercerized SBKP, mercerized cotton lint cellulose, regenerated cellulose beads and 18% NaOH-treated SBKP, i.e. partially mercerized SBKP, had similar morphologies and sizes, 4–12 nm in width and 100–200 nm in length. The 18% NaOH-treated SBKP was converted to cellulose nanoelements consisting of both celluloses I and II.     

Influence of water on cellulose-EMIMAc solution properties: a viscometric study

The influence of water on cellulose dissolved in 1-ethyl-3-methylimidazolium acetate (EMIMAc) is analysed by measuring steady state viscosity of dilute solutions. The goal is to determine: (a) the maximal water content allowing keeping cellulose dissolved (in dilute regime) and (b) the influence of water on solution flow and cellulose hydrodynamic properties. Mixing EMIMAc and water is exothermal and EMIMAc-water viscosity does not obey a logarithmic mixing rule suggesting strong interactions between the components. Newtonian flow of cellulose-EMIMAc-water solutions was recorded at water concentrations below 15 wt% and a shear thinning was observed for higher water content. It was suggested that above 15 wt% water cellulose is not completely dissolved: swollen aggregates form a sort of a “suspension” which is structuring under shear. Cellulose intrinsic viscosity showed a peak at 10 wt% water-90 wt% EMIMAc. It was hypothesised that the addition of water leads to the formation of large cellulose aggregates due to the preferential cellulose–cellulose interactions.     

Effect of high pressure treatment on structure and properties of cellulose in eucalypt pulps

Bleached acid sulphite and kraft Eucalyptus globulus pulps were subjected to treatment at high hydrostatic pressure (400 MPa during 10 min). The associated structural changes of cellulose were evaluated by X-ray scattering, solid-state NMR and infrared spectroscopy. The high pressure treatment promoted the growth of crystalline domains predominantly via lateral aggregation (cocrystallization) and, to some extent, due to the accretion of cellulose from noncrystalline domains (recrystallization). The treated pulps exhibited increment of the amount of strongly bound water and improved accessibility to amorphous domains. The high pressure treatment of dried sulphite pulp led to restoration, at least partially, of its swelling capacity thus diminishing the hornification features. Pressure treated dried sulphite pulp showed improved fibre bonding capacity at simultaneously increased bulk of the produced handsheets. The results obtained clearly showed the potential of high pressure treatments for the modification of cellulosic fibres in different applications.     

Thermal stability, smoke emission and mechanical properties of poly(vinyl chloride)/hydrotalcite nanocomposites

Poly(vinyl chloride)/hydrotalcite (PVC/HT) nanocomposites were prepared through vinyl chloride suspension polymerization in the presence of HT nanoparticles surface modified with alkyl phosphate (AP). The thermal stability, smoke emission and mechanical properties of PVC/HT nanocomposites were investigated. It was found that AP molecules were effectively absorbed by HT particles with no intercalation into the interlayer of HT. The dispersion morphologies of PVC/HT nanocomposites were observed by transmission electron microscopy showing that the majority of HT particles were dispersed in the PVC matrix in the nanoscale. The Congo Red measurement and thermogravimetric analysis showed that the thermal stability time, and the temperatures at 10% weight loss and at the maximum weight loss rate of PVC resins increased as the weight fraction of HT in the composite resins increased. The well-dispersed nano-sized HT showed an obvious smoke suppression effect on PVC. The maximum smoke density decreased about 1/3 and 1/2 when 2.5 wt% and 5.3 wt% nano-sized HT were incorporated into PVC, respectively. Furthermore, PVC/HT nanocomposites exhibited greater tensile strength and impact strength than the pristine PVC.     

Effect of processing conditions on gel formation in ternary cellulose acetate systems

A series of ternary systems composed of cellulose acetate (CA), N,N-dimethylacetamide (DMA), and water were prepared by varying the mixing temperature and order of component addition with increasing water content. The viscoelastic properties of the resulting ternary systems were measured using steady state and dynamic rheology. The CA/DMA/H₂O mixture formed physical gels at 17.5 and 19 wt% water concentrations after heating to 50 and 70/90 °C, respectively. Gel formation was characterized by the loss of a Newtonian plateau in the steady state as well as the transition of the elastic (G′) modulus becoming greater than the viscous (G″) modulus in the dynamic state. The order of component addition dramatically affected phase behaviour. Adding CA to the DMA/water solution resulted in lower moduli gels and the formation of a two-phase phase separated system at high nonsolvent contents in those prepared at low temperatures. The kinetics of phase separation was improved by subjecting the gels to a thermal treatment of 90 °C. In this case, the gels previously heated at 50 and 70° C showed a one-phase phase separated gel with higher viscous and elastic moduli.     

Investigation of the electrical properties of XLPE/SiC nanocomposites

The interface between nanoparticles and the polymer matrix, which dominates the electrical properties of nanocomposites, can effectively improve the DC breakdown and suppress space charge accumulation in nanocomposites. To research the interface characteristics, XLPE/SiC nanocomposites with concentrations of 1 wt%, 3 wt% and 5 wt% were prepared. The DC breakdown, dielectric properties and space charge behavior were examined using pulsed electro-acoustic (PEA) equipment and a dielectric analyzer. The test results show that the nanocomposites with concentrations of 1 wt% and 3 wt% have higher DC breakdown field strength than neat XLPE. In contrast, there is a lower DC breakdown strength at a concentration of 5 wt%, possibly due to the agglomeration of nanoparticles. Nanoparticle doping increases the real and imaginary permittivities over those of neat XLPE. Furthermore, with increasing concentration, a larger increase in the permittivity amplitude was observed. Based on the space charge behavior, all nanocomposites could suppress space charge accumulation, but the nanocomposite with a concentration of 1 wt% exhibited the best effect. Meanwhile, heterocharge accumulation near electrodes was observed in neat XLPE and the nanocomposite with a concentration of 5 wt%. In contrast, homocharge accumulation near electrodes was observed in the nanocomposite with a concentration of 3 wt%. This phenomenon may be due to different amounts of shallow traps in nanocomposites with different concentrations, which might lead to differing electron or hole mobility.     

Catalytic effects of copper(II) chloride and aluminum chloride on the pyrolytic behavior of cellulose

The cellulose without and with catalyst (CuCl₂, AlCl₃) was subjected to pyrolysis at temperatures from 350 to 500 °C with different heating rate (10 °C/min, 100 °C/s) to produce bio-oil and selected chemicals with high yield. The pyrolytic oil yield was in the range of 37–84 wt% depending on the temperature, the heating rate and the amount of metal chloride. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil. The mixing cellulose with both metal chlorides results with a significant decrease of the liquid product. The non-catalytic pyrolysis of cellulose gives the highest mass yield of levoglucosan (up to 11.69 wt%). The great influence of metal chloride amount on the distribution of bio-oil components was observed. The copper(II) chloride and aluminum chloride addition to cellulose clearly promotes the formation of levoglucosenone (up to 3.61 wt%), 1,4:3,6-dianhydro-α-d-glucopyranose (up to 3.37 wt%) and unidentified dianhydrosugar (MW = 144; up to 1.64 wt%). Additionally, several other compounds have been identified but in minor quantities. Based on the results of the GC–MS, the effect of pyrolysis process conditions on the productivity of selected chemicals was discussed. These results allowed to create a general model of reactions during the catalytic pyrolysis of cellulose in the presence of copper(II) chloride and aluminum chloride.     

Effect of alkaline ultrasonic pretreatment on crystalline morphology and enzymatic hydrolysis of cellulose

In this study, ultrasound-assisted alkaline pretreatment is developed to evaluate the morphological and structural changes that occur during pretreatment of cellulose, and its effect on glucose production via enzymatic hydrolysis. The pretreated samples were characterized using scanning electron microscopy, infrared spectroscopy, and X-ray diffraction to understand the change in surface morphology, crystallinity and the fraction of cellulose Iβ and cellulose II. The combined pretreatment led to a great disruption of cellulose particles along with the formation of large pores and partial fibrillation. The effects of ultrasound irradiation time (2, 4 h), NaOH concentration (1–10 wt%), initial particle size (20–180 μm) and initial degree of polymerization (DP) of cellulose on structural changes and glucose yields were evaluated. The alkaline ultrasonic pretreatment resulted in a significant decrease in particle size of cellulose, besides significantly reducing the treatment time and NaOH concentration required to achieve a low crystallinity of cellulose. More than 2.5 times improvement in glucose yield was observed with 10 wt% NaOH and 4 h of sonication, compared to untreated samples. The glucose yields increased with increase in initial particle size of cellulose, while DP had no effect on glucose yields. The glucose yields exhibited an increasing tendency with increase in cellulose II fraction as a result of combined pretreatment.