Facile solvent-free synthesis of pure-phased AlN nanowhiskers at a low temperature

Pure hexagonal aluminum nitride (AlN) nanowhiskers have been successfully synthesized by directly reacting AlCl₃ with NaN₃ in non-solvent system at the low temperature of 450 °C for 24 h. The obtained products are characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and selected area electron diffraction, which show that the obtained products are hexagonal phase AlN nanowhiskers with width from 10 to 80 nm and length up to several micrometers. The influencing factors of the formation of AlN nanowhiskers were discussed and a possible growth mechanism for AlN nanowhiskers was proposed. Additionally, the study on the corresponding optical properties and catalytic properties is also carried out.     

Preparation, characterization, and electrochemical application of metal/metal ion loaded fullerene nanowhiskers

Ce-doped C₆₀ nanowhiskers were prepared by liquid–liquid interfacial precipitation method using C₆₀-saturated benzene and Ce-containing isopropyl alcohol solution. The optical microscopy and scanning electron microcopy images of the Ce-doped nanowhiskers revealed the formation of lengthy nanowhiskers with uniform diameter. The X-ray diffraction pattern of the as-prepared and heat-treated Ce-doped nanowhiskers elucidated the face-centered cubic crystalline nature and the formation of CeO₂ phase at 400 °C. Raman spectroscopic studies on the Ce-doped nanowhiskers revealed the polymerization of the C₆₀ molecules in the nanowhiskers. The diameter of the nanowhiskers was calculated from the transmission electron microscopy (TEM) image, and it varied in the range of 150–300 nm. The scanning TEM mapping analysis was shown to confirm the Ce doping and the location of the Ce ion doping in the nanowhiskers. The electrochemical characterization of the nanowhiskers does not show any sufficient response because of the poor electrical conductivity of the nanowhiskers.     

Preparation of nanoscale cellulose materials with different morphologies by mechanical treatments and their characterization

Rod-like cellulose nanowhiskers and spherical cellulose nanoparticles were prepared from wood-pulp-derived cellulose powder by mechanical refining processes such as high-pressure homogenization (HPH) and ball-milling (BM). The nanowhiskers obtained by the HPH method were found to be 200–500 nm long and 11–16 nm wide. The diameters of the nanoparticles were in the range 40–200 nm, depending on the BM time, and were reduced to 25–50 nm after extra HPH. By adjusting the BM time, cellulose nanoparticles having different polymorphs with similar morphologies were prepared. The X-ray diffraction patterns revealed the recrystallization of cellulose I (1 h of BM time) or cellulose II (4–8 h of BM time) in ball-milled nanoparticles after water washing and solvent exchange treatments. The nanowhisker widths derived from the specific surface areas (SSA) by adsorption methods such as Congo red dye, nitrogen, and water vapor, sorptions were in agreement with those obtained from transmission electron microscopy and atomic force microscopy images. Similar SSA values were obtained for micro- and nano-scale cellulose materials using water vapor adsorption methods, and the SSAs of nanoparticles obtained by different adsorption methods are also discussed.     

A Polyethylene Nanocomposite Prepared via In‐Situ Polymerization

A novel organic/inorganic nanocomposite of polyethylene (PE) was prepared via in‐situ coordination polymerization. The Ziegler‐Natta catalyst was first supported on the surface of silicate nanowhiskers to subsequently initiate the polymerization of ethylene on the surface of these nanowhiskers. The nanowhiskers were encapsulated by polyethylene and became reinforcement fibers of the composite. The strong interaction between the uniformly dispersed nanowhiskers and the resin matrix resulted in the formation of a kind of organic/inorganic network providing good mechanical properties.     

Photoluminescence properties of SnO2 nanowhiskers grown by thermal evaporation

SnO₂ nanowhiskers were synthesized by thermal oxidation with and without a gold film as a catalyst. The SEM images reveal wire-like and rod-shaped nanowhiskers about several hundred micrometers in length and 100 nm in diameter. The three observed Raman peaks at 474, 632, and 774 cm⁻¹ indicate the typical rutile phase which is in agreement with the X-ray diffraction results. The photoluminescence properties were measured at room temperature. The peaks at 342 nm corresponding to the excitation transitions from the conduction band to the valence band of the SnO₂ nanowhiskers were not observed. However, a strong emission band at 600 nm was detected indicating the existence of oxygen vacancies in both samples. A new emission band at 398 nm was also observed in the sample with the gold film and it could be attributed to the near band-edge emission.     

A novel approach for the formation of Mg(OH)2/MgO nanowhiskers on magnesium: Rapid anodization in chloride containing solutions

In the present work we report on the electrochemical formation towards layers of multiscale MgO nanowhiskers by a two step approach. First, metallic magnesium was anodized under “high-voltage”-conditions in chloride containing ethanol/water mixtures. This results within seconds in the formation of dense areas of magnesium hydroxide nanowhiskers on the surface. The individual as-grown whiskers have a needle tip shape, and a length depending on the growth time of up to 20 μm. The whiskers can be transformed to MgO by a thermal annealing process. To gain more insight into this very rapid growth process, the paper describes the influences of the key parameters of the anodization (pH, ion-concentration, electrolyte composition) and the effect of the thermal treatment on the morphology. All steps were characterized using SEM, EDX, XRD and XPS measurements.     

Development of electrospun EVOH fibres reinforced with bacterial cellulose nanowhiskers. Part I: Characterization and method optimization

In the present study, hybrid electrospun EVOH fibres reinforced with bacterial cellulose nanowhiskers (BCNW) were developed and characterized. The nanowhiskers, obtained by sulphuric acid digestion of native bacterial cellulose mats generated by Gluconacetobacter xylinum, were morphologically characterized by SEM and optical microscopy with polarized light and revealed a highly crystalline structure of nanofibrils aggregates. XRD analyses suggested a crystalline structure corresponding to the cellulose I allomorph. It was also confirmed by means of FT-IR spectroscopy that amorphous regions were preferentially digested by the acid treatment, whereas TGA analyses showed a decrease in the thermal stability of the nanowhiskers most likely due to incorporation of sulphate groups and the inherent acidity remaining in the filler even after extensive washing cycles. A method was developed for improving the incorporation of BCNW within the EVOH electrospun fibres, consisting on the addition of the BCNW in the form of a centrifuged precipitate, versus the most conventionally employed freeze-dried nanowhiskers. DSC analyses showed a significant increase in the glass transition temperature of the composites during the second heating run, which may be related to the acidic character of the nanofiller. Finally, sonication was seen to enhance interfacial interaction but to reduce the incorporation of the filler in the matrix in the case of the centrifuged material.     

低温液相制备金红石型TiO2纳米晶须

目前，已有多种控制TiO2形貌及晶须生长的方法，如模板合成、超分子组装、声化学合成液相法及固相合成等，其中，液相法是最为廉价和简单的方法．为此，近期采用低温液相法合成金红石型TiO2受到了极大的关注．本文在以前工作的基础上，采用改进的实验方法通过在低温陈化一定浓度的TiCl4水溶液直接获得了金红石型TiO2纳米晶须，并对产物进行了初步表征．     

Grafting of model primary amine compounds to cellulose nanowhiskers through periodate oxidation

This study demonstrates regioselective oxidation of cellulose nanowhiskers using 2.80–10.02 mmols of sodium periodate per 5 g of whiskers followed by grafting with methyl and butyl amines through a Schiff base reaction to obtain their amine derivatives in 80–90 % yield. We found a corresponding increase in carbonyl content (0.06–0.14 mmols/g) of the dialdehyde cellulose nanowhiskers with the increase in oxidant as measured by titrimetric analysis and this was further evidenced by FT-IR spectroscopy. Grafting of amine compounds to the oxidized cellulose nanowhiskers resulted in their amine derivatives, which are found to be partially soluble in DMSO. Therefore, the reduction reaction between amines and carbonyl groups was confirmed through ¹³C NMR spectra, which was also supported by copper titration, XPS, and FT-IR spectroscopy. Morphological integrity and crystallinity of the nanowhiskers was maintained after the chemical modification as studied by AFM and solid-state ¹³C NMR, respectively.     

纳米纤维素晶须的表面醋酸酯化改性及复合材料的力学性能

采用硫酸水解法制备纳米纤维素晶须, 再以冰醋酸为分散介质, 浓硫酸为催化剂, 醋酸酐为酯化剂对纳米纤维素晶须进行不同程度醋酸酯化改性, 得到醋酸酯化的纳米纤维素. 采用红外光谱(FTIR)、 X射线光衍射(XRD)、 透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对改性产物进行分析和表征. 结果表明, 改性纳米纤维素晶须中醋酸酯基的平均取代度过小或过大时均不适宜用作复合材料的增强相. 当改性纳米纤维素晶须中醋酸酯基的平均取代度为0.05时, 醋酸酯化反应只发生在纳米纤维素晶须的表面. 此时, 晶须能在丙酮中稳定悬浮, 表现出流动双折射现象, 并保持了改性前纳米纤维素晶须的棒状形态和高结晶度. 将这种改性后的纳米纤维素晶须作为增强相与醋酸纤维素通过溶液浇铸法制成纳米复合膜, 结果显示, 与空白醋酸纤维素膜相比, 添加改性纳米纤维素晶须后, 纳米复合膜的拉伸强度、 杨氏模量和断裂伸长率都得到了提高. 在玻璃化转变区间纳米复合膜储能模量的降低幅度小于空白膜.     

Extraction and characterization of cellulose nanowhiskers from <Emphasis Type="Italic">Mandacaru</Emphasis> (<Emphasis Type="Italic">Cereus jamacaru</Emphasis> DC.) spines

Cellulose nanowhiskers were extracted from the spines of Mandacaru (Cereus jamacaru DC.), a cactus native to the Caatinga biome of northeastern Brazil, using sulfuric acid hydrolysis preceded by alkaline treatment and bleaching. Results showed that three bleaching steps were required to remove most of the non-cellulosic constituents of the spines that yielded 77.4% cellulose. Nanowhiskers size decreased from about 400 to 260 nm when extraction time varied from 60 to 120 min, this was also evidenced by X-ray diffraction. Alkaline treated and bleached samples had lower thermal stability as compared to untreated spines due to removal of lignin and increased surface area. The amount of time samples were treated with sulfuric acid influenced the thermal stability and consequently the degree of crystallinity of the nanowhiskers. Cellulose nanowhiskers were obtained from Mandacaru spines providing a new renewable source of reinforcement with potential applications in nanocomposites.     

Preparation of cellulose I nanowhiskers with a mildly acidic aqueous ionic liquid: reaction efficiency and whiskers attributes

Cellulose I nanowhiskers were prepared in relatively high yield (48 ± 2 %) by single-stage hydrolysis of microcrystalline cellulose with an aqueous solution of 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO₄). This reaction occurred under mildly acidic reaction conditions with an [H⁺]/[AGU] ratio of 0.24 mol/mol, i.e., 2 orders of magnitude lower than with concentrated sulfuric acid. The nanowhiskers exhibited small width and width distribution and also smaller length than nanowhiskers obtained with concentrated acid. With a relatively low content of sulfur they also exhibited higher thermal stability than whiskers obtained with concentrated sulfuric acid. The lower solvating power of the aqueous ionic liquid compared to that of concentrated sulfuric acid likely contributes to the greater hydrolysis efficiency in the present system.     

Acetylation of Cellulose Nanowhiskers with Vinyl Acetate under Moderate Conditions

A novel and straightforward method for the surface acetylation of cellulose nanowhiskers by transesterification of vinyl acetate is proposed. The reaction of vinyl acetate with the hydroxyl groups of cellulose nanowhiskers obtained from cotton linters was examined with potassium carbonate as catalyst. Results indicate that during the first stage of the reaction, only the surface of the nanowhiskers was modified, while their dimensions and crystallinity remained unchanged. With increasing reaction time, diffusion mechanisms controlled the rate, leading to nanowhiskers with higher levels of acetylation, smaller dimensions, and lower crystallinity. In THF, a solvent of low polarity, the suspensions from modified nanowhiskers showed improved stability with increased acetylation.

     

The impact of cellulose structure on binding interactions with hemicellulose and pectin

Four cellulose substrates including highly crystalline cellulose nanowhiskers (CNWs) from Gluconacetobacter xylinus (cellulose Iα) or cotton (cellulose Iβ) and amorphous cellulose derived from CNWs (phosphoric acid swollen cellulose nanowhiskers, PASCNWs) were used to explore the interaction between cellulose and well-defined xyloglucan, xylan, arabinogalactan and pectin. The binding behavior was characterized by adsorption isotherm and Langmuir models. The maximum adsorption and the binding constant of xyloglucan, xylan and pectin to any CNWs were always higher than to PASCNWs derived from the same source. The binding affinity of xyloglucan, xylan and pectin to G. xylinus cellulose was generally higher than to cotton cellulose, showing that binding interactions depended on the biological origin of cellulose and associated differences in its structure. The surface area, porosity, crystal plane and degree of order of cellulose substrate may all impact the interactions.     

Nanoreinforced hemicellulose-based hydrogels prepared by freeze–thaw treatment

A novel hybrid hydrogel was prepared from hemicelluloses, polyvinyl alcohol, and chitin nanowhiskers by the freeze–thaw technique. The hydrogel was characterized by Fourier-transform infrared (FT-IR) spectrometry, scanning electron microscopy, X-ray diffraction analysis, cross-polarization (CP)/magic-angle spinning (MAS) ¹³C nuclear magnetic resonance (NMR), and swelling property and compressive strength measurements. Atomic force microscopy images of chitin implied that the size of whiskers reached nanometer level with average length of about 200 nm and width of 40 nm. The FT-IR and NMR results indicated that physical cross-linking rather than chemical reaction occurred during the gelation process. The mechanical properties of the hydrogels were significantly improved with increasing proportion of chitin nanowhiskers, with the highest compressive stress of 9.6 MPa being found for Gel-0.5. The results showed that the repeated freeze–thaw cycles induced physical cross-linking of packed chains by hydrogen bonds among the polymers, and the concentration of chitin nanowhiskers affected the hydrogel morphology and properties. It is suggested that hydrogels with good mechanical properties can be successfully prepared by this physical method, offering promise for tissue engineering applications.     

Effects of flower-like ZnO nanowhiskers on the mechanical, thermal and antibacterial properties of waterborne polyurethane

A novel waterborne polyurethane/flower-like ZnO nanowhiskers (WPU/f-ZnO) composite with different f-ZnO content (0-4.0 wt%) was synthesized by an in-situ copolymerization process. The f-ZnO consisting of uniform nanorods was prepared via a simple hydrothermal method. In order to disperse and incorporate f-ZnO into WPU matrix, f-ZnO was modified with γ-aminopropyltriethoxysilane. Morphology of f-ZnO in WPU matrix was characterized by scanning electron microscope. The properties of WPU/f-ZnO composites such as mechanical strength, thermal stability as well as water swelling were strongly influenced by the f-ZnO contents. It was demonstrated that appropriate amount of f-ZnO with good dispersion in the WPU matrix significantly improved the performance of the composites. The mechanical property was enhanced with an increase of f-ZnO content up to the optimum content (1 wt%) and then declined. Incorporation of f-ZnO enhanced the water resistance of the composites remarkably. It was amazing to observe that the thermal degradation temperatures of the composites initially decreased significantly and then leveled off with content increase of f-ZnO, which was different from the results of other WPU composite systems reported. Antibacterial activity of WPU/f-ZnO composite films against Escherichia coli and Staphylococcus aureus was also tested. The results revealed that the antibacterial activity enhanced with the increasing f-ZnO content, and the best antibacterial activity was obtained at the loading level of 4.0 wt% f-ZnO.     

De-sulfation of cellulose nanowhiskers and its effects on the dispersion behavior of graphene

The role of negative charges on cellulose nanowhiskers (CNWs) in the aqueous dispersion behaviors of graphene has been investigated. The sulfate groups were partially removed from the CNWs with sodium hydroxide solution. Both CNWs and desulfated cellulose nanowhiskers (D-CNWs) were applied in the aqueous dispersion process of graphene. The dispersing result was evaluated by ultraviolet-visible (UV-Vis) absorption spectra. It revealed the dispersing ability of D-CNWs became worse due to the removal of sulfate groups. It demonstrated the negative charged sulfate groups on CNWs played an important role in the graphene dispersing process.     

The transparency and mechanical properties of cellulose acetate nanocomposites using cellulose nanowhiskers as fillers

Cellulose nanowhiskers (CNWs) were chemically modified by acetylating to obtain acetylated cellulose nanowhiskers (ACNWs) which could be well dispersed in acetone. The chemical modification was limited only on the surface of CNWs which was confirmed by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Surface substitution degree of ACNWs was evaluated to be 0.45 through X-ray photoelectron spectroscopy (XPS). Fully bioresource-based nanocomposite films were manufactured by incorporation of ACNWs into cellulose acetate (CA) using a casting/evaporation technique. Scanning electron microscope (SEM) demonstrated that ACNWs dispersed well in the CA matrix, which resulted in high transparency of all CA nanocomposites. The tensile strength, Young’s modulus and strain at break of all CA nanocomposites exhibited simultaneous increase in comparison with neat CA matrix. At the content of 4.5 wt% ACNWs, the tensile strength, Young’s modulus and strain at break of the CA nanocomposite film were increased by 9, 39, and 44 % respectively.     

Anionic and cationic nanocomposite hydrogels reinforced with cellulose and chitin nanowhiskers: effect of electrolyte concentration on mechanical properties and swelling behaviors

Various nanocomposite gels were prepared using cellulose nanowhiskers (CNWs) or chitin nanowhiskers (ChNWs) as reinforcing fillers and hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), or chitosan as network polymers. The use of CNWs with low surface charge induced significant CNWs aggregations, which were well explained by depletion effect. Young's modulus E and swelling ratio Q of CNWs/HPC · CMC gels were highest at zero electrolyte concentration and decreased above 0.01 M electrolyte, whereas stress at break σ of the gels showed its minimum at zero electrolytes and increased with an addition of electrolytes. In the case of ChNWs/chitosan gels, maximum of E and Q was located at 0.01 M electrolyte concentration, and σ did not indicate clear tendency with electrolyte concentration. Although all gels indicated an increase in E and a decrease in Q with an increase in whisker content, the most remarkable changes were observed under an absence of electrolytes, whereas the changes under the presence of electrolytes were somewhat negligible. Copyright © 2014 John Wiley & Sons, Ltd.