Preparation Of Nanocomposite Materials Research Articles

Boosting the photocatalytic activity of ZnO-NPs through the incorporation of C-dot and preparation of nanocomposite materials

Due to their applications in cosmetology, medicine, antibacterial and other fields, zinc oxide nanoparticles (ZnO-NPs) are among the nanoscale materials experiencing exponential growth. In contrast, pure ZnO-NPs have been reported to have a very large energy bandgap, a large exaction binding energy, electron-hole recombination, no visible light absorption, and poor photocatalytic activities, which limit their potential uses. ZnO-NPs can be further extended through the incorporation of trace amounts of carbon materials to engulf these problems. We investigate the photocatalytic degradation of methylene blue (MB) dye with pure ZnO-NPs infused with a limited amount of carbon dot (C-dot) materials. Consequently, adding 10% C-dot to ZnO-NPs reduced their energy bandgap from 3.1 to 2.8 eV and significantly increased their photocatalytic activity. MB was almost completely degraded (98.4%) after 60 min when 50 mg of C-dot-incorporated ZnO-NPs were added. By comparison, the nanocomposite's photocatalytic activity exceeded that of pure ZnO-NPs by more than 50%. A surface charge and stability improvement are responsible for the extraordinary photocatalytic improvement. As far as we know, this is the best-ever photocatalytic improvement achieved by incorporating a trace amount of C-dot material into pure ZnO-NPs.

Extraction of keratin from wool and its use as biopolymer in film formation and in electrospinning for composite material processing

Keratin is one of the most important protein materials and can act as a sustainable biopolymer for manifold applications. This paper reports on a sustainable extraction method for keratin from wool fiber materials. The use of this extracted keratin for polymer film preparation and preparation of nano-composite materials by electrospinning is investigated. The preparation of keratin films is done in combination with the both biopolymers alginate and pectin. Keratin nanofibers are prepared in combination with the polymer polyacrylonitrile PAN. A view on antibacterial properties of the prepared films is given. As further analytic methods, Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetry, and scanning electron microscopy (SEM) are used. Finally, the preparation of new keratin containing materials is described, which may be used in future for biomedical applications.

Assembly of Anisotropic Nanocellulose Films Stronger than the Original Tree.

Natural structural materials frequently consist of multimaterial nanocomposites with complex superstructure giving rise to exceptional mechanical properties, but also commonly preventing access to their synthetic reproduction. Here we present the spin-assisted layer-by-layer assembly of anisotropic wood-inspired films composed of anionic cellulose nanofibrils and cationic poly(vinyl amine) possessing a tensile strength that exceeds that of the wood from which the fibers originate. The degree of orientation of the nanofibrils was studied by atomic force microscopy and depends strongly on the distance from the center of the spun surface. The nanofibrils are preferentially aligned in the direction of the shear flow, and consequently, the mechanical properties of such films differ substantially when measured parallel and perpendicular to the fibril orientation direction. For enabling a diversity of bioinspired applications including sensing, packaging, electronics, or optics, the preparation of nanocomposite materials and devices with anisotropic physical properties requires an extreme level of control over the positioning and alignment of nanoscale objects within the matrix material.

Tuning the Solubility Parameters of Carbon Nanotubes by Means of Their Adducts with Janus Pyrrole Compounds.

The solubility parameters of multiwalled carbon nanotubes (CNTs) was tuned via their chemical modification with pyrrole compounds (PyCs), by means of a simple and sustainable methodology. PyCs were synthesized with high atom efficiency through the Paal–Knorr reaction of primary amines with 2,5-hexanedione, in the absence of solvents and catalysts. Methylamine, 1-dodecylamine, 2-amino-1,3-propanediol, and 3-(triethoxysilyl)propan-1-amine were selected. PyCs are characterized by two moieties, the pyrrole ring and the substituent of the nitrogen atom, and can be considered as Janus molecules. The functionalization of CNTs occurred with a high yield by simply heating CNTs and PyC. The whole reaction pathway did not produce any waste and was characterized by a carbon efficiency up to almost 100%. Thanks to the variety of PyC chemical structures, the CNT solubility parameter was modified in a pretty broad range of values, in the expected direction. Stable CNT dispersions were prepared in different solvents. From the aqueous dispersion, coating layers were prepared with high electrical conductivity, larger with respect to a top commercial product. The “pyrrole methodology” reported here is based on one reaction and allows almost infinite variations of the CNT solubility parameter, thus promoting their compatibility with target matrices and allowing the preparation of nanocomposite materials with improved properties. This work thus paves the way for a highly efficient exploitation of CNTs.

Synthesis and evaluation of new radical photoinitiators bearing trialkoxysilyl groups for surface immobilization

Photoinitiators, which can be readily immobilized on surfaces, e.g. on the surface of nanoparticles, have gained considerable attention of both scientists and engineers. The main reason for this interest is that immobilized initiators lead to a covalent linkage between the surface and the resulting polymer chain. Thus, immobilized photoinitiators are expected not to migrate out of the polymer network, which reduces potential health risks. This paper describes the synthesis of a range of short- and long-wavelength absorbing photoinitiators bearing trialkoxysilyl units. The synthesis starts from commercially available products, Irgacure 2959 or Irgacure TPO-L, and takes 1–4 steps. While some of the reported initiators were previously sparsely described in patents, but lack a systematic study, others are reported for the first time. Both free and immobilized initiators were characterized and tested with regard to their efficiency in acrylic and thiol-ene systems. The findings confirm the good applicability of the nanoparticle-immobilized photoinitiators in the preparation of nanocomposite materials.

Synthesis and Characterization of Ag-TiO<sub>2</sub> Nanocomposites for Possible Use as Biocide

Currently nanoparticles are being widely used because they have large surface area and pronounced effect relative to the properties of the material. Silver and Titanium Dioxide nanoparticles, for example, have pronounced biocidal effects, since they can inactivate certain enzymes and alter the DNA synthesis of some microorganisms. It is expected that a composite of the nanoparticles of the two metals can further increase the biocide power. This way, the study of the synthesis and characterization of nanocomposites becomes highly relevant. The aim of this work was to synthesize Ag-TiO2 nanocomposites and to characterize them in order to contribute to the understanding of the preparation of nanocomposite materials. In this study, we used a sol-gel method, which makes use of a reduction reaction using sodium citrate as the reducing agent, and titanium butoxide, acetic acid and silver nitrate as starting material. After being synthesized, the nanocomposite was analyzed with the techniques of Scanning Electron Microscopy coupled to energy dispersive X-ray detector (SEM / EDS) and X-ray Diffraction.

Preparation of amphoteric nanocomposite hydrogel under supercritical carbon dioxide and its fast-swelling behaviours

Supercritical carbon dioxide (scCO2) has been widely used in preparation of nanocomposite materials. However, so far there has been no report on preparation of nanocomposite hydrogels by intercalation of hydrophilic monomers into clay under scCO2 condition. In this paper, the fast-swelling amphoteric nanocomposite hydrogels were prepared via the free radical polymerisation of acrylic acid (AA) and N-[3-(dimethylamino) propyl] methacrylamide (DMAPMA) in the presence of clay under scCO2 condition. The composition of the hydrogel was determined by element analysis and Fourier transform infrared spectroscopy (FTIR). Transmission electron microscopy (TEM) and X-ray diffraction (XRD) results illustrated that the clay layers became disordered after intercalation by AA and DMAPMA under scCO2 condition. The swelling kinetics and deswelling characteristics were tested. The results indicated that the hydrogels presented marked swelling rate in deionised or saline water and fast deswelling rate in alcoholic solution.

Novel nanocomposite materials for efficient and selective mercury ions capturing from wastewater

This work explored the particulate ligand impregnated highly ordered mesoporous silica based optical nanocomposite material for the sensitive and selective detection and removal of mercury (Hg(II)) from polluted water solutions. The ligand of N,N-disalicylidene-4,5-dimethyl-phenylenedene was prepared and successfully anchored onto the highly ordered mesoporous silica by the indirect approach in the preparation of nanocomposite materials. The materials were produced an optical color signal that was easily generated and transduced even at trace levels of Hg(II) ions. Considering the environmental factors, the nanocomposite materials were solvent-free systems for sensitive Hg(II) ions detection system. Adding of Hg(II) ions, the nanocomposite materials generated absorption peak and enhance the selective chromogenic behavior toward Hg(II) ions from pale yellow to dark read, which could be easily visualized by the naked eye. The ability to remove Hg(II) ions by the materials was performed relatively to different experimental parameters such as solution pH, reaction time, initial metal ions concentration and different competing metal ions. The Hg(II) ions adsorption reached an equilibrium within short time and the maximum monolayer adsorption capacity was 179.74mg/g. Also the foreign ions did not any significant affect for selective Hg(II) ions removal from water solutions under the optimum conditions. The elution was performed and the regeneration was possible during the elution operation. In addition, the nanocomposite materials could to reuse in several cycles without loss of structural ordering, permitting the reusability for further selective detection and separation of Hg(II) ions from water. In terms of the sensitivity and selectivity, the nanocomposite material is a promising candidate employed for in situ environmental pollution incidents, especially competent for the detection and removal of Hg(II) ions with an extremely high efficiency.

In Situ Controlled Synthesis of Thermosensitive Poly(N‐isopropylacrylamide)/Au Nanocomposite Hydrogels by Gamma Radiation for Catalytic Application

Thermosensitive poly(N-isopropylacrylamide) (PNIPAM)/Au nanoparticle (NP) nanocomposite hydrogels are synthesized by in situ γ-radiation-assisted polymerization of N-isopropylacrylamide monomer aqueous solution in the presence of HAuCl₄·4H₂O. In this reaction, the PNIPAM hydrogels and the Au NPs are formed simultaneously, thus demonstrating an easy and straightforward synthetic strategy for the preparation of a uniform nanocomposite. The results suggest that increasing the monomer content during the preparation of nanocomposite materials can increase the sizes of Au NPs. The effects of irradiation dose and concentration of HAuCl₄·4H₂O on the optical and thermal properties of the hydrogel are also investigated. The PNIPAM/Au nanocomposite hydrogels act as an excellent catalyst for the conversion of o-nitroaniline to 1,2-benzenediamine, and the catalytic activity of the composite hydrogel can be tuned by the volume transition of PNIPAM. The in situ polymerization of monomer and reduction of metal ions initiated by a "clean" and "green" γ-radiation technique can be extended to the efficient synthesis of other nanocomposite materials.

Preparation and characterization of nano hydroxyapatite/polymeric composites materials. Part I

The present study is focused on preparation of nano composite materials and the effect of citric acid on their different properties. The formation of nano HA and its interaction with chitosan (C), gelatin (G) polymers and citric acid (CA) materials were studied. The Fourier Transformed Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), transmission electron microscope (TEM), and scanning electron microscope (SEM) were used to characterize these composite materials. The compressive strength (CS) was also measured to know the reinforcement of the prepared composites. The results show that carboxylic and amino groups play crucial role for HA formation on chitosan–gelatin polymeric matrix in the presence of citric acid (CA). The formation of nano HA particles and its average size of crystallite is increased with increase of CG content and decreased with addition of CA. Also, the HA formation and binding strength between its particles are improved into the composites especially with CA. The nano-composites containing the best ratio of nHA (70%) with CA (0.2 M) are promising for medical applications in the future.

Preparation of nanocomposite materials from mercaptoacetate-modified platinum nanoparticles and a layered nickel hydroxyacetate salt

Nanocomposites were prepared by a very simple route from preformed platinum particles and a nickel layered hydroxide salt (LHS), these compounds being first synthesized separately by the polyol process. The nanoparticles were treated with mercaptoacetate before being brought into contact with the lamellar compound. XPS and IR spectroscopies give clear evidence for interactions between the platinum nanoparticles and the mercaptoacetate species. XRD, TEM and magnetic characterizations show that the structure of the nickel hydroxide layers is retained and that some of the LHS sheets contain incorporated nanoparticles.

Effect of the Organoclay Preparation on the Extent of the Intercalation/Exfoliation and the Barrier Properties in Polyamide-6/Montmorillonite Nanocomposites

This paper shows the importance of the clay surface chemistry in the preparation of nanocomposite materials. An Argentinean montmorillonite was used for preparing two modified clays. The filosilicate was intercalated with a quaternary ammonium salt derived from ε- caprolactam to obtain an organofilic material. The other modification was introduced by mixing the clay with hexadecyl trimethyl ammonium chloride. Thus, the polyamide 6 ability in dispersing clays was applied to prepare composites with the intercalated clays. The polyamide 6/clay dry composites with 3 wt % of filler were prepared by melt processing in a mixer chamber. Composites of polyamide 6/organoclay were characterized by X-ray diffraction, transmission and scanning electron microscopy and thermogravimetry. The barrier properties were determined by cyclohexane pervaporation. The results show that the dispersion and degree of delamination depend on a proper chemical treatment and the clay content influences the polyamide 6 nanocomposites solvent pervaporation resistance.

A new approach to synthesis of organic/inorganic nanocomposites

The possibility of preparation of nanocomposite materials with improved physicomechanical properties by polycondensation of spirocyclic silicates and diisocyanates was elucidated. The thermomechanical, spectral, and thermogravimetric properties of the resulting materials were examined.

Fe3O4–SiO2 nanocomposites obtained via alkoxide and colloidal route

The magnetic nanocomposite materials represent an important class of nanomaterials extensively studied nowadays due to their varied applications from medical diagnostic to storage information. The iron oxides in silica matrix systems are highly investigated. The sol-gel method is a suitable way of preparation of Fe3O4-SiO2 nanocomposite materials, since this method allowed the preparation of nanocomposite materials with narrow size distribution of magnetite in silica matrix. In the present work, nanocomposite materials in the Fe3O4-SiO2 system were prepared by sol-gel method via alkoxide and aqueous route. As SiO2 sources, tetraethoxysilan (TEOS) for the alkoxide route, as well as silica sol Ludox (30%) for the aqueous route, were used. This study shows the influence of the type of silica matrix on the structure, size, and distribution of the Fe3O4 nanoparticles in the Fe3O4-SiO2 systems. The gels were annealed at 550°C in order to consolidate the matrices. The structural characterization of the obtained materials via the two preparation routes was performed by DTA/TGA analysis, X-ray diffraction, IR and Mossbauer spectroscopy, Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED).

Towards controllable optical properties of silicon based nanoparticles for applications in opto-electronics

Size-dependent optical properties of laser-synthesized Si-based nanopowders were investigated by photo-luminescence (PL) and photo-luminescence excitation (PLE) spectroscopy on powder samples annealed in air in the 700–1000 °C temperature range. TEM analysis reveals that at increasing annealing temperature a progressive Si nanoparticle size reduction occurs as a consequence of crystalline core oxidation, and a corresponding blue-shift of the PL emission is observed. The subsequent step is the preparation of nanocomposite materials by nanopowders dispersion and integration into a continuous silica phase by sol–gel processing. Synthesis parameters are adjusted in order to preserve the PL red emission from Si nanostructures. An interesting application would consist in the Er incorporation into the nanocomposite glassy material aiming at the 1.54 μm Er emission sensitization by energy transfer from Si nanostructures to nearby Er ions. However, it was found that Si nanoparticles are completely oxidized at the processing temperatures (1400 °C) required to activate Er emission. Here we demonstrate that better and promising results can be achieved introducing in the sol–gel Si-based nanopowders withstanding higher temperatures.

A Direct Route toward Assembly of Nanoparticle−Carbon Nanotube Composite Materials

The preparation of nanocomposite materials from carbon nanotubes (CNTs) and metal or metal oxide nanoparticles has important implications to the development of advanced catalytic and sensory materials. This paper reports findings of an investigation of the preparation of nanoparticle-coated carbon nanotube composite materials. Our approach involves molecularly mediated assembly of monolayer-capped nanoparticles on multiwalled CNTs via a combination of hydrophobic and hydrogen-bonding interactions between the capping/mediating shell and the CNT surface. The advantage of this route is that it does not require tedious surface modification of CNTs. We have demonstrated its simplicity and effectiveness for assembling alkanethiolate-capped gold nanoparticles of 2-5 nm core sizes onto CNTs with controllable coverage and spatially isolated character. The loading and distribution of the nanoparticles on CNTs depend on the relative concentrations of gold nanoparticles, CNTs, and mediating or linking agents. The composite nanomaterials can be dispersed in organic solvent, and the capping/linking shells can be removed by thermal treatment to produce controllable nanocrystals on the CNT surfaces. The nanocomposite materials are characterized using transmission electron microscopy and Fourier transform infrared spectroscopy techniques. The results will be discussed in terms of developing advanced catalytic and sensory nanomaterials.

Surface Initiated Polymerization (SIP) on Nanoparticle Surfaces: Demonstration of First Principles and Preparation of Nanocomposite Materials

ABSTRACTTo investigate the grafting of polymer chains onto nanoparticles (metal, semi-conductor, inorganic, etc) and nanostructured (patterned) surfaces, we have investigated anionic surface initiated polymerization (SIP) on a variety of surfaces. Understanding the surface chemistry issues involved is critical for future applications and protocols. SIP of polystyrene from Silicate and clay nanoparticles surfaces have been made by the living anionic polymerization method with 1,1-diphenylethylene (DPE) initiation sites attached to nanoparticle surfaces using chlorosilane and amino functional groups. Model studies were initially done on flat Si-wafer surface and recently with Au surfaces. For the nanoparticles, the grafted polymers were cleaved and characterized by FTIR, NMR, AFM, TGA and SEC. Polymers grafted from nanoparticle surfaces show higher polydispersity and lower molecular weight than those formed in solution. We observed that diffusion of the monomer, stability of the initiator attachment to the surface, and aggregation of the particles controls the properties of the grafted polymers on particle surfaces. On the other hand, the use of the anionic polymerization method on surfaces allows the possibility of combining a variety of polymers (organic) with various nanoparticle and surfaces (inorganic) for the preparation of hybrid nanocomposite materials.

Preparation of nanocomposite materials containing WS2, δ-WN, Fe3O4, or Fe9S10 in a silica aerogel host

Nanocomposite materials based on silica aerogel hosts have been produced using chemical vapour infiltration/decomposition methods and characterized by X-ray diffraction and electron microscopy. Amorphous tungsten in SiO2 aerogel was formed by the decomposition of W(CO)6 at 250 °C. Alternatively, reaction of this material with sulphur at 700 °C produced needle-shaped WS2 crystals with lengths ranging from 25–230 nm. Reaction of the W/SiO2 composite with anhydrous NH3 formed crystals of δ-WN with diameters of 1–5 nm. Fe(CO)5 is readily absorbed into the silica aerogel, forming an amorphous iron oxide/SiO2 composite after slow oxidation in air. Treatment of this material with additional Fe(CO)5 produced an Fe3O4/SiO2 aerogel composite. Fe3O4 particle sizes were 20–55 nm. After additional heat treatment, this composite exhibited soft ferromagnetic behaviour with a coercivity of ∼170 Oe. Fe9S10 crystals with diameters of 30–90 nm were formed by the reaction of the amorphous iron oxide/SiO2 composite with H2S at 900 °C.