Melt‐blending of unmodified and modified cellulose nanocrystals with reduced graphene oxide into PLA matrix for biomedical application

In this article, we successfully fabricated the bionanocomposites using cellulose nanocrystals (CNCs) and reduced graphene oxide (rGO) reinforced into biodegradable polylactic acid (PLA) matrix through melt‐mixing method. Due to the affinity difference between hydrophilic CNC and hydrophobic PLA, the surface modification of CNC was employed using quaternary ammonium salts (CTAB) as a surfactant. The nanocomposites were developed using different blend ratios of CNC/modified CNC (1, 2, and 3) wt% and (0.5 wt%) rGO into the polymer matrix. The morphology of CNC, q‐CNC (modified CNC), and nanocomposites were inspected by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is demonstrated from tensile tests that, the nanocomposite with 1 wt% CNC and rGO showed maximum tensile strength compared with PLA and its nanocomposites. Moreover, the nanocomposite with 1 wt% CNC and rGO was also having maximum thermal stability. From cytotoxicity evaluation, it is observed that all the nanocomposites are nontoxic and cytocompatible to HEK293 cells. In addition to this, the nanocomposite with q‐CNC showed enhanced barrier properties compared with PLA and PLA/CNC/rGO nanocomposite. The results obtained from different characterizations showed that the incorporation of surfactant onto CNC improved the dispersion in PLA but at the same time deteriorated the PLA matrix.     

Tensile,thermal, and antibacterial characterization of composites of cellulose/modified Pennisetum purpureum natural fibers with in situ generated copper nanoparticles

Eco-friendly all cellulose composites were developed using cellulose as matrix and nanocomposite (in situ generated copper nanoparticles modified Napier Grass Fibers (NGFs)) as fillers for the antibacterial applications. The content of the nanocomposite filler was increased from 1?wt.% to 5?wt.% in the cellulose matrix. All these composites were characterized by Scanning Electron Microscopy (SEM), Tensile, Thermo Gravimetric Analysis (TGA), and antibacterial tests. SEM-EDX analysis revealed the in situ generation of copper nanoparticles on the surface of the films. Further, all cellulose composites showed good thermal stability. A minimum of 30% increase in char residue was observed in all cellulose nanocomposites compared to matrix. Antibacterial analysis indicated an excellent clear zone formation against both Gram Negative (Escherichia coli) and Gram Positive (Staphylococcus) bacteria. Hence, all these cellulose nanocomposite films can be considered as antibacterial packaging and dressing materials in medical field.     

Studies on Non-natural Deoxyammonium Cellulose

Summary: Ammonium group containing cellulose derivatives are prepared from homogeneously synthesized cellulose p-toluenesulfonic acid esters (tosyl cellulose) by conversion with sodium azide and subsequent reduction of the azido moiety applying NaBH₄/CoBr₂/2,2′-bipyridine as reagent. Regarding the tosylation, cellulose samples of different degree of polymerization and hemicellulose content possess a different reactivity. The deoxyamino cellulose is water soluble in the protonated state. Elemental analysis, FTIR- and NMR spectroscopy were carried out to analyze the degree of substitution and functionalization pattern. It was also studied to synthesize deoxyazido celluloses without isolation of the tosyl cellulose. However, a predominant formation of deoxychloro moieties occurs.     

Molecular Engineering of Fracture Energy Dissipating Sacrificial Bonds Into Cellulose Nanocrystal Nanocomposites

Even though nanocomposites have provided a plethora of routes to increase stiffness and strength, achieving increased toughness with suppressed catastrophic crack growth has remained more challenging. Inspired by the concepts of mechanically excellent natural nanomaterials, one‐component nanocomposites were fabricated involving reinforcing colloidal nanorod cores with polymeric grafts containing supramolecular binding units. The concept is based on mechanically strong native cellulose nanocrystals (CNC) grafted with glassy polymethacrylate polymers, with side chains that contain 2‐ureido‐4[1H]‐pyrimidone (UPy) pendant groups. The interdigitation of the grafts and the ensuing UPy hydrogen bonds bind the nanocomposite network together. Under stress, UPy groups act as sacrificial bonds: simultaneously providing adhesion between the CNCs while allowing them to first orient and then gradually slide past each other, thus dissipating fracture energy. We propose that this architecture involving supramolecular binding units within side chains of polymer grafts attached to colloidal reinforcements opens generic approaches for tough nanocomposites.     

Polyethylene/graphite nanocomposites obtained by in situ polymerization

The synthesis of polyethylene/graphite nanocomposites by in situ polymerization was achieved using the catalytic system Cp₂ZrCl₂ (bis(cyclopentadienyl)zirconium(IV) dichloride)/methylaluminoxane (MAO). Graphite with nano dimensions, previously treated with MAO, was added into the reactor as filler at percentages of 1, 2, and 5% (w/w). XRD analysis showed that the chemical and thermal treatments employed preserve the structure of the graphite sheets. The formation of graphite nanosheets and nanocomposites was confirmed by TEM and AFM. TEM micrographics showed that the polyethylene grew between the graphene nanosheets, giving intercalated and exfoliated graphite nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 692–698, 2010     

Thermal Degradation of Cellulose Nanocrystals Deposited on Different Surfaces

Thermal degradation of cellulose nanocrystals deposited on flat solid surfaces was monitored by AFM coupled with analysis of obtained images using image processor. The nanocrystals deposited on TiO₂ substrate showed different degradation patterns compared to those deposited on the nanosized layer of amorphous cellulose. The degradation was complete within 20 minutes at 300 °C. The nanocrystal deposited on amorphous cellulose resisted the heat treatment up to 120 minutes. Visual comparison and analysis of the AFM images clearly demonstrated the impact of temperature on the degradation rate of the nanocrystals deposited on TiO₂ substrate.     

Preparation and Characterization of Niobium Oxide Coated Cellulose Fiber

The Nb₂O₅/cellulose composite was prepared by reacting α-cellulose with NbCl_5-n(OC₂H₅)_n, in nonaqueous solvent, under nitrogen atmosphere and submitting the obtained material to hydrolysis. An increase in the crystallinity degree is observed in the composite material because the precursor reagent reacts with the amorphous phase of the cellulose fibers. Loadings between 4.5 and 16.0% of the oxide were achieved and in every case the oxide particles uniformly cover the fiber surface. Lewis and Brønsted acid sites were determined by using pyridine as the basic molecular probe.     

Design of a Heterogeneous Catalyst Based on Cellulose Nanocrystals for Cyclopropanation: Synthesis and Solid‐State NMR Characterization

Heterogeneous dirhodium(II) catalysts based on environmentally benign and biocompatible cellulose nanocrystals (CNC‐Rh₂) as support material were obtained by ligand exchange between carboxyl groups on the CNC surface and Rh₂(OOCCF₃)₄, as was confirmed by solid‐state ¹⁹F and ¹³C NMR spectroscopy. On average, two CF₃COO^? groups are replaced during ligand exchange, which is consistent with quantitative analysis by a combination of ¹⁹F NMR spectroscopy and thermogravimetry. CNC‐Rh₂ catalysts performed well in a model cyclopropanation reaction, in spite of the low dirhodium(II) content on the CNC surface (0.23 mmol g^?1). The immobilization through covalent bonding combined with the separate locations of binding positions and active sites of CNC‐Rh₂ guarantees a high stability against leaching and allows the recovery and reuse of the catalyst during the cyclopropanation reaction.     

Non-Isothermal Crystallization of Poly (vinylidene fluoride)/Poly (methyl methacrylate)/Cellulose Nanocrystal Nanocomposites

Poly (vinylidiene fluoride) (PVDF)/poly (methyl methacrylate) (PMMA)/cellulose nanocrystal (CNC) nanocomposites were prepared by solution blending. Non-isothermal crystallization of PVDF/PMMA (70/30) blend and its composites was investigated using differential scanning calorimetry. It was found that the addition of CNCs played a positive role in both the crystallization rate and crystallization percentage. The addition of CNCs increased the initial crystallization temperature, peak crystallization temperature, and crystalline enthalpy. The Avrami index indicated that CNCs did not change the crystallization mechanism; while other parameters derived from Jeziorny theory and Mo's method, including Z _c , F(t), and α, further verified the positive role played by CNCs.     

Mechanical and shape‐memory properties of poly(mannitol sebacate)/cellulose nanocrystal nanocomposites

Polyesters based on polyols and sebacic acid, known as poly(polyol sebacate)s (PPS), are attracting considerable attention, as their properties are potentially useful in the context of soft‐tissue engineering applications. To overcome the drawback that PPSs generally display rather low strength and stiffness, we have pursued the preparation of nanocomposites based poly(mannitol sebacate) (PMS), a prominent example of this materials family, with cellulose nanocrystals (CNCs). Nanocomposites were achieved in a two‐step process. A soluble, low‐molecular‐weight PMS pre‐polymer was formed via the polycondensation reaction between sebacic acid and D‐mannitol. Nanocomposites with different CNC content were prepared by solution‐casting and curing under vacuum using two different profiles designed to prepare materials with low and high degree of crosslinking. The as‐prepared nanocomposites have higher stiffness and toughness than the neat PMS matrix while maintaining a high elongation at break. A highly crosslinked nanocomposite with a CNC content of 5 wt % displays a sixfold increase in Young's modulus and a fivefold improvement in toughness. Nanocomposites also exhibit a shape memory effect with a switch temperature in the range of 15 to 45 °C; in particular the materials with a thermal transition in the upper part of this range are potentially useful for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3123–3133     

Conductive Nanocomposites Based on Cellulose Nanofibrils Coated with Polyaniline-DBSA Via In Situ Polymerization

Summary: Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI-DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet-visible-near infrared (UV-Vis - NIR) and Fourier-transform infrared (FTIR) spectroscopies and X-ray diffraction (XRD). FTIR and UV-Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10⁻¹ S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X-ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils.     

Poly(ε-caprolactone) (PCL)/cellulose nano-crystal (CNC) nanocomposites and foams

Poly(ε-caprolactone) (PCL)/cellulose nanocrystal (CNC) nanocomposites were produced via twin-screw extrusion. Microcellular nanocomposite samples were produced with microcellular injection molding using carbon dioxide (CO₂) as physical blowing agent. The foaming behavior, physical properties, thermal properties, crystallization behavior, and biocompatibility were investigated. It was found that the CNCs interacted with the PCL matrix which led to a strong interface. The CNCs effectively acted as nucleation agents in microcellular injection molding. Both solid and foamed samples with higher levels of CNC content showed higher tensile moduli, complex viscosities, and storage moduli due to the reinforcement effects of CNCs. Furthermore, improvement in the foamed samples was more significant due to their fine cell structure. The addition of CNCs caused a reduction of the decomposition temperature and an increase in the glass transition temperature, crystallization temperature, and crystallinity of PCL. Moreover, the biocompatibility of the foamed nanocomposites with low CNC content was verified by 3T3 fibroblast cell culture.     

Rheological Behaviors in the Regimes from Dilute to Concentrated in Cellulose Solutions Dissolved at Low Temperature

Cellulose was dissolved rapidly in 9.5 wt.‐% NaOH/4.5 wt.‐% thiourea aqueous solution pre‐cooled to ?5 °C to prepare cellulose solution with different concentrations. The rheological properties of the cellulose solutions in wide concentration regimes from dilute (0.008 wt.‐%) to concentrated (4.0 wt.‐%) at 25 °C were investigated. On the basis of data from the steady‐shear flow test, the critical overlap (c*), the entanglement (c_e) and the gel (c_g) concentrations of the cellulose solution at 25 °C were determined, respectively, to be 0.10 wt.‐%, 0.53 wt.‐% and 2.50 wt.‐%, in accordance with the results of storage modulus (G′) versus c by dynamic test. Moreover, the Cox‐Merz deviation at relatively low concentrations was in good agreement with the micro‐gel particles in dilute regime. As the cellulose concentration increased, a homogeneous 3‐dimensional network formed in the cellulose solution in the concentrated regime, and further increasing of the concentration led to micro‐phase separation as determined by the time‐temperature superposition (tTS). So far, this complex cellulose solution has been successfully described by the concentration regime theory for the first time, and the relatively molecular morphologies in each regime have been determined, providing useful information for the applications of the cellulose solution systems.

     

Reinforcing Poly(ethylene) with Cellulose Nanocrystals

The fabrication of nanocomposites of low‐density polyethylene (LDPE), one of the world's most widely used polymers, and cellulose nanocrystals (CNCs), which represent the world's most abundant bio‐based nanofiller, is reported. While the hydrophobic polymer and the hydrophilic filler seem to be intrinsically incompatible, this article shows that it is possible to kinetically trap homogeneous nanocomposites by a templating approach. An organogel is first prepared by exchanging the solvent of an aqueous CNC dispersion against acetone, impregnating the resulting organogel, in which the CNCs form a percolating network with a hot LDPE solution in toluene, and compression‐molding the resulting materials into thin films. At a filler content of 7.6% v/v, the resulting materials display a three‐ to four‐fold increase in strength and stiffness compared with the neat LDPE, which confirms that the CNC network could be largely maintained. It is also possible to reprocess these nanocomposites and dilute them with LDPE using conventional melt‐processing techniques.

     

Cellulose/iron oxide hybrids as multifunctional pigments in thermoplastic starch based materials

Cellulose/iron oxide hybrids were prepared by the controlled hydrolysis of FeC₂O₄ in the presence of vegetable and bacterial cellulose fibres as substrates. By varying the relative amount of FeC₂O₄ and NaOH, either hematite or magnetic iron oxides were grown at the cellulose fibres surfaces. This chemical strategy was used for the production of a number of materials, whose coloristic properties associated to their reinforcement role allowed their use as new hybrid pigments for thermoplastic starch (TPS) based products. The TPS reinforced materials were characterized by several techniques in order to evaluate: the morphology and the compatibility between the matrix and the fillers; the mechanical reinforcement effect of the cellulose/iron oxide pigments on TPS and the coloristic properties of the composites. All materials showed good dispersion and strong adhesion for the cellulose/iron oxide nanocomposites in the TPS matrix thus resulting in improved mechanical properties.     

Mechanical,thermal and barrier properties of pectin/cellulose nanocrystal nanocomposite films and their effect on the storability of strawberries (Fragaria ananassa)

In this work, two formulations of pectin/cellulose nanocrystals/glycerol nanocomposites were employed as packaging to extend storage life of strawberries. The effects of incorporating cellulose nanocrystals extracted from bleached Kraft wood pulp on the mechanical, thermal, and barrier properties of pectin‐based nanocomposites were evaluated. Nanocomposite films with different filler levels of cellulose nanocrystals (1, 2, 4 and 8% w/w) were prepared by casting. Compared with the neat film of pectin, improvements in the mechanical properties of the nanocomposites were observed, but these films became fragile. To improve the film flexibility, glycerol was added as a plasticizer and then new variations in the mechanical, thermal, and barrier properties of these nanocomposites were evaluated. The effects of nanocomposite films on storability of strawberries were compared with Poly vinyl chloride packaging films. The Poly vinyl chloride film and the nanocomposites showed similar behavior regarding weight loss by the strawberries, especially in the initial days of storage. The results show that pectin/cellulose nanocrystals/glycerol nanocomposites could be considered as a viable packaging alternative for replaced the Poly vinyl cloride film. Copyright © 2015 John Wiley & Sons, Ltd.     

The Effect of Flower-Like Magnesium Hydroxide Nanostructure on the Thermal Stability of Cellulose Acetate and Acrylonitrile–Butadiene–Styrene

Flower-like magnesium hydroxide (Mg(OH)₂) nanostructures were synthesized via a simple hydrothermal reaction at relatively low temperature. The Mg(OH)₂ nanostructures were then added to acrylonitrile–butadiene–styrene (ABS) and cellulose acetate (CA) polymers. The effect of Mg(OH)₂ nanostructures on the thermal stability of the polymeric matrixes has been investigated. The thermal decomposition of the nanocomposites shifts towards higher temperature in the presence of the Mg(OH)₂. The enhancement of thermal stability of nanocomposites is due to endothermically decomposition of magnesium hydroxide that releases of water and dilutes combustible gases. Nanostructures and nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), UL-94 test and limiting oxygen index (LOI) analysis.     

Novel Cellulose Derivatives Containing Metal (Cu,Fe, Ni) Oxide Nanoparticles as Eco-Friendly Corrosion Inhibitors for C-Steel in Acidic Chloride Solutions

Novel environmentally-friendly corrosion inhibitors based on primary aminated modified cellulose (PAC) containing nano-oxide of some metals (MONPs), for instance iron oxide nanoparticles (Fe₃O₄NPs), copper oxide nanoparticles (CuONPs), and nickel oxide nanoparticles (NiONPs), were successfully synthesized. The as-prepared PAC/MONPs nanocomposites were categorized using Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM), field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and selected area diffraction pattern (SAED) techniques. The data from spectroscopy indicated that successful formation of PAC/MONPs nanocomposites, as well as the TEM images, declared the synthesized PAC/Fe₃O₄NPs, PAC/CuONPs, and PAC/NiONPs with regular distribution with particle size diameters of 10, 23 and 43 nm, respectively. The protection performance of the as-prepared PAC and PAC/MONPs nanocomposites on the corrosion of C-steel in molar HCl was studied by the electrochemical and weight-loss approaches. The outcomes confirmed that the protection power increased with a rise in the [inhibitor]. The protection efficiency reached 88.1, 93.2, 96.1 and 98.6% with 250 ppm of PAC/CuONP, PAC/Fe₃O₄NPs, and PAC/NiONPs, respectively. PAC and all PAC/MONPs nanocomposites worked as mixed-kind inhibitors and their adsorption on the C-steel interface followed the isotherm Langmuir model. The findings were reinforced by FT-IR, FE-SEM and EDX analyses.     

Study of Ethyl Cellulose—Benzoic Acid Interactions in Matrices for Controlled Drug Release by DSC

The physical state of benzoic acid (BA) and its interaction with ethyl cellulose (EC) were examined in ethyl cellulose—benzoic acid matrices by Differential Scanning Calorimetry (DSC). The glass transition temperature (T_g) of EC of various matrices having BA in solid solution form (upto 27.7%) was reduced. The BA in matrices containing more than 38.9% drug exhibited distinct melting endotherms due to crystalline form. The peak temperatures of these endotherms were lowered and they broadened as the concentration was lowered. The solubility of BA increased at its melting point as compared to ambient temperature. The melting enthalpy of BA, when plotted as a function of its concentration yielded a straight line with intercept of 330 mg g^–1 of matrix. This is the solubility of BA in EC at its melting temperature. Fourier Transform Infra Red Spectroscopy (FTIR) investigations confirmed that hydrogen bonding occurred between EC and BA through hydroxyl groups.This revised version was published online in November 2005 with corrections to the Cover Date.     

Control of properties of nanocomposites bio-based collagen and cellulose nanocrystals

Collagen is an important biomaterial because it has many applications in the biomedical sector. However, the high hydrophilicity of collagen (COL) leads to easy swelling. Thus, controlling this property is highly desirable. In this work, cellulose nanocrystals (CNCs) dispersed in glycerol (GLI) were incorporated in the matrix collagen to tailor the hydrophilicity and mechanical properties. Study of the hydrophilicity of the bio-based nanocomposite was evaluated by contact angle measurement and thermogravimetric analysis. Mechanical analyses showed that CNCs are excellent reinforcing fillers to the collagen matrix. Synchrotron small-angle X-ray scattering was employed to investigate the nanostructures of COL/GLI/CNC nanocomposites and CNC water dispersion. CNC in concentrations up to 1 wt% presents an intermediate shape between a rod and a plane with a 9.34-nm radius of gyration (R _g). Bio-based nanocomposites present two different structural levels with two types of particles with very different R _gs. At the intermediate power-law regime, a large-scale mass fractal aggregate is observed. In the high-power-law regime, it is observed scattering from primary particles smaller than 1 nm. As the CNC concentration increases, the original particle distorts from a rod to a plate. The cytotoxicity assay indicates that the collagen and nanocomposites did not affect the cell viability of rat calvarial cells in vitro.