Preparation and characterization of magnetic γ-Al2O3 ceramic nanocomposite particles with variable Fe3O4 content and modification with epoxide functional polymer
Introduction
Alumina (Al2O3) is one of the most widely used hard ceramic oxide possessing properties like chemical inertness, high melting point, non-volatility, resistance to oxidation and corrosion, high thermal conductivity, biocompatibility and high dielectric constant [1], [2], [3], [4], [5], [6]. As such nano-crystalline Al2O3 finds wide range of applications in ceramics, refractories, abrasives, optics, catalysts, effective absorbents, ionic conductors, filtering and emulsification membranes, coatings and insulating aerogels [7], [8], [9]. Al2O3 is also recognized as the first clinical bioceramics and has been studied for applications in bone curing [10], blood pump [11], protector for oral surfaces [12], detection and separation of DNA [13], and component of dental and orthopedic [3].
The properties of Al2O3 particles are believed to be dependent on the particle size, morphology, surface and phase homogeneity and these can be controlled by selecting a proper synthetic route. Nanocrystalline Al2O3 exists in a wide range of polymorphs (α, χ, η, δ, κ, θ, γ, ρ). Among all of them, γ-Al2O3 nanocrystals are particularly important nanoscale materials, because γ-Al2O3 possesses desirable surface properties such as high surface area, thermal, mechanical and chemical stability, Lewis acid material and porosity [14], [15], [16]. These properties make them useful in high-temperature catalyst or catalytic support, coating formulation, composite reinforcing materials, sorbent and membrane [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27].
Recently researchers are showing much interest on the fabrication of inorganic-organic hybrid composites as they provide useful properties of both matrix components. By the proper selection of polymer segment one can tune the properties of hybrid composite materials suitable for applications in electronics, optics, photoconductors, biomaterials and filters for pollutant removal. Another fact is that bare inorganic nanoparticles often tend to aggregate with each other due to huge surface area and high large surface free energy [28]. One way to improve the colloidal stability by breaking the agglomerates is the formation of inorganic-organic hybrid composites. However, the most serious challenge in designing such composite materials is the poor compatibility between inorganic and organic materials [29].
So far only few researches are available on the preparation of inorganic-organic hybrid composite materials from Al2O3 nanoparticles. Khabibullin et al. reported the grafting of poly(methyl methacrylate) brushes from α-Al2O3 nanoparticles via surface initiated atom transfer radical polymerization [30]. Popat et al. modified the surface of porous Al2O3 with poly(ethylene glycol) (PEG) to design targeted drug delivery system [31]. First the surface of porous Al2O3 was hydroxylated, then reacted with silane coupled PEG. Conversely another group modified α-Al2O3 particles with silane coupling agent prior to the ultrasonic irradiation in presence of monomer to prepare poly(amide-imide)/α-Al2O3 composite nanostructure. Jackson et al. reported the formation of epoxy monolayer on Al2O3 particles via self-assembly and curing of epoxy fluids in presence of 10 µm sized Al2O3 particles [32]. In a mere similar approach ultrathin polypyrrole film was developed on Al2O3 particles using hexanoic acid as a template [33].
The objective of this investigation is aimed at preparing new type of epoxide functional magnetic inorganic/organic hybrid nanocomposite particles using γ-Al2O3 particles as the starting core material. The synthesis is depicted in Scheme 1. The presence of epoxide functionality is expected to add advantages like improved hydrophilicity, colloidal stability and biocompatibility for immobilization of enzymes, other proteins and nucleic acids and other sensitive compounds like reactive dyes, diamines and fluorescent compounds [34], [35]. Magnetic nature would make them useful for information storage, color imaging, magnetic refrigeration, ferrofluids, separation technology, extraction and concentration of biomolecules in the biomedical field, for oil recovery, for environmental purpose, as contrast agents in magnetic resonance imaging, as mediator in hyperthermia, or as carrier for guided drug delivery [36], [37], [38], [39], [40], [41]. Here γ-Al2O3 particles were first prepared by sol-gel technique from saturated aqueous solution of aluminium nitrate [42]. Magnetic γ-Al2O3 nanocomposite particles were then prepared by simple co-precipitation of variable amounts of Fe2+ and Fe3+ from their alkali aqueous solutions. Prior to the seeded polymerization of epoxide functional glycidyl methacrylate (GMA) magnetic γ-Al2O3/Fe3O4 nanocomposite particles were modified with silica (SiO2) layer to improve the adhesion as well as compatibility between inorganic and organic components.
Section snippets
Chemicals and instruments
GMA of monomer grade purchased from Fluka, Chemika, Switzerland was passed through activated basic alumina column to remove inhibitors. Aluminium nitrate nonahydrate Al(NO3)3,9H2O and urea both from E-Merck, Germany, sodium dodecyl sulphate (SDS), cetyl trimethyl ammonium bromide (CTAB) both from Fluka, Biochemica, Switzerland were used as anionic and cationic surfactants. 2,2′-Azobis(2-amidinopropane)dihydrochloride (V-50) from LOBA Chem. India, was recrystallized from distilled water and
Results and discussion
The morphology and size distribution of γ-Al2O3 nanoparticles were evaluated by SEM and TEM images as shown in Fig. 1. It is worthwhile to mention that before characterization particles were washed to avoid the presence of impurities. Interestingly γ-Al2O3 particles possess some peculiar hexagonal flake shaped morphology ranging in from 100 to 400 nm. The presence of some spherical, cubic as well as tetragonal flake shaped particles cannot be ruled out as images only represent a portion of the
Conclusion
A simple and efficient four-step approach is demonstrated for the controlled preparation of magnetic epoxide functional γ-Al2O3 ceramic nanocomposite particles named as γ-Al2O3/Fe3O4/SiO2/PGMA. Porous γ-Al2O3 particles prepared by sol-gel technique exhibited flake shaped morphology. The surface of γ-Al2O3 particles was modified by precipitation of magnetic iron oxide nanoparticles. The increase in iron oxide content produced hair like orientation of Fe3O4 nanoparticles grown from the surface of
Acknowledgments
Author (HA) acknowledges the contribution from Central Science Laboratory, Rajshahi University for instrument support.
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