Preparation of cellulose/multi-walled carbon nanotube composite membranes with enhanced conductive property regulated by ionic liquids

Cellulose/multi-walled carbon nanotubes (MWCNTs)- composite membranes applied in electrochemical and biomedical fields were prepared using 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDEP) as solvent in this study. With the increasing of MWCNTs amount, the membrane conductivity increased, and the conductivity reached 9.1 S/cm as the mass ratio of MWCNTs to cellulose being 2:1. The additions of sodium dodecyl sulfate (SDS), 1-hexadecyl-3-methylimidazolium bromide (C₁₆mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF₄) efficiently improved the conductivity, mechanical property, and thermal stability by promoting the dispersion of MWCNTs. When the mass ratio of C₁₆mimBr to MWCNTs changed from 0 to 0.3:1, the conductivity increased from 0.08 S/cm to 0.14 S/cm, and the tensile strength increased from 13.3 MPa to 17.0 MPa. These results indicate that the binary ionic liquids (ILs) system can regulate the properties of the composite membranes, and is a feasible approach for preparing cellulose/MWCNTs composite membranes with enhanced properties.     

Preparation and characterization of bacterial cellulose/hydroxypropyl chitosan blend as-spun fibers

In the work, N-methylmorpholine-N-oxide monohydrate (NMMO·H₂O) was used as a solvent to solve bacterial cellulose (BC) and hydroxypropyl chitosan (HPCS) together, and regenerated bacterial cellulose (RBC)/HPCS blend as-spun fibers were prepared by blending BC with HPCS via wet-spinning in the Lyocell process. Structure and properties of the blend as-spun fibers were characterized by different techniques, together with the antibacterial activity of the blend as-spun fibers against Staphylococcus aureus. Results revealed that HPCS was mixed with BC very well. The blend as-spun fibers showed a rough and folded surface morphology and an interior pore structure on the cross-section. Compared with pure RBC as-spun fibers, the blend as-spun fibers had lower degree of crystallinity and thermal stability. Although extension at break of the blend as-spun fibers was lower than the pure RBC as-spun fibers, their tensile strength and modulus had been enhanced obviously. The blend as-spun fibers were also found to exhibit excellent antibacterial activities against S. aureus.     

A study of mechanical behavior and morphology of carbon nanotube reinforced UHMWPE/Nylon 6 hybrid polymer nanocomposite fiber

We report a phenomenal increase in strength, modulus, and fracture strain of ultra high molecular weight polyethylene (UHMWPE) fiber by 103 %, 219 %, and 108 %, respectively through hybridizing this fiber with Nylon 6 as a minor phase and simultaneously reinforcing it with single-walled carbon nanotubes (SWCNTs). Loading of Nylon 6 and SWCNTs into UHMWPE was 20.0 wt% and 2.0 wt%, respectively. Hybridized fibers were processed using a solution spinning method coupled with melt mixing and extrusion. We claim that the enhancement in strain-to-failure of the nanocomposites is due to induced plasticity in the hybridized Nylon 6-UHMWPE polymers. The enhancement in strength and stiffness in the nanocomposites is attributed to the load sharing of the SWCNTs during deformation. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) studies showed that changes in percent crystallinity, rate of crystallization, crystallite size, alignment of nanotubes, sliding of polymer interfaces and strong adhesion of CNT/polymer blends were responsible for such enhancements.     

Development of transparent bacterial cellulose nanocomposite film as substrate for flexible organic light emitting diode (OLED) display

Nanocomposite film composed of bacterial cellulose (10-50 wt.%) and poly-urethane (PU) based resin was fabricated and utilized as a substrate for flexible organic light emitting diode (OLED) display. The performance of the nanocomposite satisfied the criteria for the substrate of OLED with an additional feature of flexibility. The visible light transmittance of the nanocomposite film was as high as 80%. Its thermal stability was stable up to 150 °C while its dimensional stability in terms of coefficient of thermal expansion (CTE) was less than 20 ppm/K. After OLED was fabricated on the substrate through thermal evaporation technique, the OLED performed highest current efficiency of 0.085 cd/A and power efficiency of 0.021 lm/W at 200 cd/m² while retained its flexible feature, suggesting that bacterial cellulose nanocomposite is a promising material for the development of substrate for flexible OLED display.     

In-situ preparation of multi-walled carbon nanotube (MWNT)/cellulose nanocomposites and their physical properties

The multi-walled carbon nanotube (MWNT)/cellulose nanocomposites were prepared by using monohydrated Nmethylmorpholine-N-oxide (NMMO) as a solvent for dispersing the acid-treated MWNTs (A-MWNTs) as well as for dissolving the cellulose. The A-MWNTs were well dispersed in both monohydrated NMMO and the nanocomposite films. The nanocomposite films were prepared by a film-casting method onto a glass plate. The tensile strain at break, Young’s modulus, and toughness of nanocomposite films increased by ～5, ～2 and ～12 times, respectively at ? (A-MWNT content in the nanocomposite)=0.8 wt%, as compared to those of the pure cellulose film. The thermal degradation temperature of the nanocomposite films also increased from 329 to 339 oC by incorporation of 1 wt% A-MENTs. The electric conductivities of the A-MWNT/cellulose nanocomposites at ? =1 and 10 wt% were 2.09×10^?5 and 3.68×10^?3 S/cm, respectively. The transmittances were 86, 69 and 55 % at 550 nm for 0.4, 0.8 and 1 wt% nanocomposite films, respectively. Thus, these nanocomposites are promising materials in terms of all the properties studied in this paper and can be used for many applications, such as toughened cellulose fibers, transparent electrodes, etc.     

Electrospinning and microwave absorption of polyaniline/polyacrylonitrile/multiwalled carbon nanotubes nanocomposite fibers

Electrical conductive nanocomposite fibers were prepared with polyaniline (PANI), polyacrylonitrile (PAN) and multi-walled carbon nanotubes (MWCNTs) via electrospinning. The morphology and electrical conductivity of the PANI/PAN/MWCNTs nanocomposite fibers were characterized by scanning electron microscope (SEM) and Van De Pauw method. Electrical conductivity of nanocomposite fibers increased from 1.79 S·m^?1 to 7.97 S·m^?1 with increasing the MWCNTs content from 3.0 wt% to 7.0 wt%. Compared with PANI/PAN membranes, the mechanical property of PANI/PAN/MWCNTs nanocomposites fiber membranes decreased. The microwave absorption performance of composite films was analyzed using waveguide tube, which indicated that with the thickness increasing the value of R_L reduced from ?4.6 to ?5.9 dB.     

Morphology and properties of polyacrylonitrile/single wall carbon nanotube composite films

Composite films were prepared by casting the solution of polyacrylonitrile (PAN) and single wall nanotube (SWNT) in DMF subsequent to sonication. The SWNTs in the films are well dispersed as ropes with 20–30 nm thickness. Moreover, AFM surface image of the composite film displays an interwoven fibrous structure of nanotubes which may give rise to conductive passways and lead to high conductivity. The polarized Raman spectroscopy is an ideal characterization technique for identification and the orientation study of SWNT. The well-defined G-peak intensity at 1580 cm⁻¹ shows a dependency on the draw ratio under cross-Nicol. The degree of nanotube orientation in the drawn film was measurable from the sine curve obtained by rotating the drawn film on the plane of cross-Nicol of polarized Raman microscope. The threshold loading of SWNT for electrical conductivity in PAN is found to be lower than 1 wt% in the composite film. The electrical conductivity of the SWNT/PAN composite film decreased with increasing of draw ratio due to the collapse of the interwoven fibrous network of the nanotubes with uniaxial orientation.     

A flexible nanocomposite membrane based on traditional cotton fabric to enhance performance of microbial fuel cell

A flexible and stretchable three-dimensional nanocomposite membrane based on traditional cotton fabric is a promising alternative for proton exchange membrane because it has the capability of transferring protons, is inexpensive, and also have higher current density compared to Nafion membranes in microbial fuel cells. The obtained results showed that the highest power and current of PVAc-g-PVDF-coated cotton fabric were 400±10 mW/m² and 92 mA/m², respectively. However, maximum generated power and current for Nafion-117 were 300±10 mW/m² and 60 mA/m², respectively. The highest proton conductivity of PVAc-g-PVDF-coated cotton fabric was (1.5±0.2)×10^-2 S/cm at 25 °C and lowest glucose permeability was (12±1)×10^-6 cm²/s after Mg²⁺ ions adsorption. Furthermore, the highest COD removal (85±3 %) and CE (11.2 %) were obtained from PVAc-g-PVDF-coated cotton fabric. The coated cotton fabric can provide a novel route for low-cost production of high-performance flexible proton exchange materials from the natural fabrics.     

Directly-prelithiated carbon nanotube film for high-performance flexible lithium-ion battery electrodes

Carbon nanotube (CNT) films are very flexible and serve as active materials for lithium-ion batteries (LIBs). Hence, they have high potential as flexible free-standing electrodes for wearable batteries. However, nanocarbon materials such as CNTs and graphene are of limited use as electrodes because they have a large initial irreversible capacity due to the formation of a solid electrolyte interphase (SEI). Herein, we prelithiated the CNT films to make them available as electrodes for flexible batteries by reducing their irreversible capacity. The SEI is pre-formed through a direct prelithiation (DP) method that brings lithium metal into direct contact with CNT films in an electrolyte. As a result, the capacity of directly-prelithiated CNT film electrodes continues to increase to 1520 mAh/g until 350th cycle of charge/discharge and their initial irreversible capacity vanishes. The changes in the electrochemical properties of CNT film electrodes by DP treatment and their flexibility are investigated.     

Properties of polyacrylonitrile/single wall carbon nanotube composite films prepared in nitric acid

Nanocomposite films were prepared by casting the solution of polyacrylonitrile (PAN) and single wall nanotube (SWNT) in nitric acid subsequent to sonication. Even though SWNT shows good dispersion visually, the reinforcing effect was not satisfactory. The G-band Raman spectra of the drawn film clearly demonstrated that SWNTs in the film are well-oriented along the drawing axis of the film. The electrical resistivity of the film prepared using nitric acid was lower than that of the film using DMF. Thus, nitric acid is presumably more effective in dispersing nanotubes than DMF.     

Enhancement biocompatibility of bacterial cellulose membrane via laccase/TEMPO mediated grafting of silk fibroins

Silk fibroin (SF) has the characteristic of moisture penetrability and biocompatibility. To enhance the biocompatibility of bacterial cellulose (BC), silk fibroin is grafted onto BC membrane using laccase and 2,2′,6,6′-tetramethylpiperidine-N-oxyl (TEMPO). As the model compound of BC, cellobiose is incubated with laccase/TEMPO for disclosing the mechanism of enzymatic oxidation. The structure and property of the composite membranes of SF/BC are investigated by means of FTIR, XPS, DSC, and biocompatibility analysis. The results indicate that cellobiose might react with hexamethylenediamine and form Schiff bases. The concentration of amino group in SF solution noticeably decreased after laccase/TEMPO oxidation, indicating the occurrence of self-crosslinking of SF. After enzymatic grafting of SF, the content of atomic nitrogen on BC surface was increased compared to that of the control. Meanwhile, the composite membrane of SF/BC exhibits more satisfactory biocompatibility compared to BC, and it has potential applications in biomedical fields.     

Preparation and characterization of poly(2-hydroxyethyl methacrylate) grafted bacterial cellulose using atom transfer radical polymerization

The purpose of this study is to synthesize grafted Bacterial Cellulose (BC) nanofibers using Atom Transfer Radical Polymerization (ATRP) reinforced into poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel matrix. Nanofibers grafting polymerizations were conducted in the presence of the catalyst CuCl/CuBr and the initiator 2-bromoisobutyrylbromide (2-BiBr). Degrees of substitution (DS) of BC-macroinitiators were quantified using both elemental analysis and gravimetric method. FTIR results confirmed BC nanofibers’ surface modifications of both initiator and hydroxyethyl methacrylate (HEMA) grafts. X-ray spectroscopy further confirmed the increase in carbonyl content after PHEMA-grafting polymerization. Results of the gravimetric analysis showed an increase in the weight of the grafted BC upon increasing reaction time. Furthermore, the change in the swelling ratio percentages of the reinforced composites product (BC-MI-3-g-PHEMA-1.5) was considerably higher based on reaction time. Slight increase in the swelling ratio of BC-MI-3 nanofibers was observed after 48 hours to reach 31 %. Moreover, results of thermal gravimetric analysis (TGA) demonstrated that decomposition temperature at 50 % weight loss (T₅₀) decreased to 350 °C for BC-MI-3-g-PHEMA-1.5. These characteristics demonstrate potentials for applications in the biomedical fields including drug delivery and wound care.     

Copper oxide-carbon nanotube (CuO/CNT) nanocomposite: Synthesis and photocatalytic dye degradation from colored textile wastewater

In this paper, CuO/CNT nanocomposite was synthesized and its photocatalytic dye degradation ability for colored textile wastewater was studied. The characteristics of the nanocomposite were investigated by XRD, SEM and FTIR. The photodegradation of Direct Red 31 (DR31) and Reactive Red 120 (RR120) by CuO/CNT in presence of H₂O₂ was investigated. Photocatalytic dye degradation was determined by UV-vis spectrophotometer. Effects of catalyst dosage, initial dye concentration and salt on photodegradation performance were studied. The photocatalytic dye degradation ability of pure CuO and CuO/CNT nanocomposite is 78 % and 89 % for DR31 and 70 % and 87 % for RR120, respectively. The results showed that CNT increased the photocatalytic activity of CuO. The presence of salt decreases dye degradation efficiency. The dye degradation kinetics by nanocomposite followed first-order kinetic model. The reaction rate at 0.005 g catalyst was 0.0137 and 0.0105 min^-1 for DR31 and RR120, respectively. It was found that the CuO/CNT nanocomposite as a photocatalyst could be used to degrade dyes from colored wastewater.     

Enhanced spinnability of carbon nanotube fibers by surfactant addition

A surfactant is used to enhance spinnability of carbon nanotube (CNT) fibers during direct spinning via chemical vapor deposition (CVD). In this study, the non-ionic surfactant, polysorbate, is used due to its good solubility in the CNT synthesis solution. The addition of the surfactant increased the specific strength and electrical conductivity of CNT fibers. Due to these enhanced properties, CNT fibers can be spun at higher speeds which results in lower linear density. These enhancements are due to the reduced agglomeration of iron catalysts during the synthesis of CNT fibers via CVD. This simple approach may create new applications for CNT fibers, such as for artificial muscles and power cables.     

Preparation and characterization of aminobenzyl cellulose by two step synthesis from native cellulose

Synthesis and structural characterizations of nitro- and aminobenzyl cellulose were carried out. Cellulose derivatives were synthesized by etherification. Nitrobenzylation produced 80 % yield by treating a mixture of microcrystalline cellulose, 4-dimethyl aminopyridine, and 4-nitrobenzyl chloride at 80 °C for 10 h. Nitrobenzyl cellulose was then reduced to aminobenzyl cellulose with 93 % yield using indium metal in ethanol and saturated aqueous ammonium chloride. In addition to their structural characterizations by FT-IR and ¹³C CP/MAS NMR, TGA will also be described. These reactions serve as models for future cotton fiber finishing technology with applications in flame resistance.     

Scalable preparation of multiscale carbon nanotube/glass fiber reinforcements and their application in polymer composites

The introduction of carbon nanotubes (CNTs) into conventional fiber to construct a hierarchical structure in polymer composites has attracted great interest owing to their merits of performance improvement and multiple functionalities. However, there is a challenge for realizing the scalable preparation of the multi-scale CNT-glass fiber (CNTGF) reinforcements in practical application. In this work, we present a simple and continuous method of the mass production of multiscale CNT-glass fiber (CNT-GF) reinforcements. Scanning electron microscopy and thermo gravimetric analysis indicated ~1.0 wt% CNTs were highly dispersed on the whole fiber surface through a facile surfactant-assisted process. Such hybrid CNT-GF fillers were found to effectively enhance the stiffness, strength and impact resistance of polypropylene polymer. Increased storage modulus, glass transition temperature and crystallization temperature of the composites filled with the CNT-GF fillers were also observed in the differential scanning calorimetry and dynamic mechanical analysis compared with the composites containing the pristine GF fillers. Fracture surface analysis revealed enhanced interfacial quality between CNT-GF and matrix, which is likely responsible for improved performance of the hierarchical polymer composites.     

Preparation of carboxymethyl cellulose superabsorbents from waste textiles

Production of superabsorbent polymers from cotton and viscose waste textiles was investigated. The cellulose wastes were carboxymethylated, crosslinked by divinylsulfone, and then converted to superabsorbent material using air-drying, freeze-drying, or air-drying after phase inversion. The separation of cellulose from synthetic polymers in the textile (polyester) was carried out by direct dissolution of cellulose in N-methylmorpholine-N-oxide (NMMO), or separation by dissolution in water after carboxymethylation of the textiles. The progress of the carboxymethylation reaction was evaluated by measurement of the degree of substitution (DS) of carboxymethyl cellulose (CMC). The DS values of 0.50–0.86 confirmed the prosperous substitution of hydrophilic carboxymethyl groups into the cellulosic chains. The water binding capacity and the swelling rate of the superabsorbents prepared under different conditions were measured. Under the best condition the superabsorbent obtained from waste textiles showed an ultimate water binding capacity of 541 g/g which was notably higher than that of the reference superabsorbent derived from cotton linter (470 g/g). The amount of absorbed water by this product exceeded that of the reference sample after 60 min immersion.     

Enhanced mechanical and dielectric properties of poly(vinylidene fluoride)/polyurethane/multi-walled carbon nanotube nanocomposites

Multi-walled carbon nanotubes (MWNTs) nanocomposites with the polymer matrix composed of blends of poly(vinylidene fluoride) (PVDF) and polyurethane (PU) were prepared via functionalization of 3,4,5-triflouroaniline (TFA) on MWNTs. The MWNTs/polymer nanocomposites showed a dominantly enhanced elongation due to incorporation of PU molecules in PVDF matrix and the improved MWNTs dispersion in the polymer matrix resulting from functionalization of MWNTs with TFA. The functionalization of TFA on MWNTs was confirmed by the measurements of Raman, FT-IR spectra, SEM, and TEM images. In addition, the dielectric constant of nanocomposites increased with an increase of TFA-functionalized MWNTs in PVDF/PU/MWNTs nanocomposites. The polymer blend nanocomposites incorporating MWNTs may be available as an alternative potential route for the actuator materials.     

A novel method for well-organized polystyrene-grafted multi-walled carbon nanotube bundles via self-assembly in tetrahydrofuran

Polystyrene (PS) grafted multi-walled carbon nanotubes (MWCNTs) were well-organized as bundles by a selfassembly method in tetrahydrofuran (THF). PS was synthesized by atom transfer radical polymerization and grafted to the surface of tubes through covalent bonds. Unmodified tubes agglomerated irregularly and precipitated instantly because of poor compatibility with THF. But soluble PS provides solvent-phobic MWCNTs with suspending stability and dispersibility in the dispersant. Therefore, MWCNT-g-PS has amphiphilic property in this selective solvent and owns ability to self-assemble. Scanning and transmission electron microscope images show that self-assemblies (SAs) are columnar with a tight and ordered head and a loose tail. Their length ranges from 15 to 25 µm while width from 1.5 to 4 µm. In these super structures, tubes are regular organized and parallel arranged. Because MWCNT-g-PS has a huge rigid rod-core and multi-flexible-armed structure in the suspension, a novel micro-phase separation model is proposed to explain this behavior. There are two kinds of micro-phase separation locating on two mutual perpendicular faces on tubes. Solvent-philic/solvent-phobic interaction plays a key role in self-assembly. Moreover, a balance between buoyancy and gravity on SAs decides whether this process is finished or not.     

Effect of aldehydes crosslinkers on properties of bacterial cellulose-poly(vinyl alcohol) (BC/PVA) nanocomposite hydrogels

The effects of the aldehydes crosslinkers on properties of the BC/PVA nanocomposite hydrogels were investigated. BC as the reinforcement and PVA as the matrix materials of the BC/PVA nanocomposite hydrogels, the hydrogels were prepared in coagulating bath of sodium sulfate and cross-linked with kinds of aldehydes. The hydrogels were characterized by Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), Equilibrium swelling ratio (ESR) tests, mechanical properties tests, thermo-gravimetric analysis (TGA) and X-ray diffraction (XRD) analysis. It was found that the dialdehyde (glyoxal, glutaraldehyde) crosslinkers were more efficient than monoaldehyde (formaldehyde, acetaldehyde) crosslinkers. The ESR, mechanical properties of the BC/PVA nanocomposite hydrogels were obviously influenced by aldehydes crosslinkers. However, their thermo stability and crystallinity were scarcely influenced. The nanocomposite hydrogels described in this study provides information for further development and optimization of a variety of nanofiber-polymer matrix composite hydrogels.