Characterization of Nanoparticles by Solvent Infrared Spectroscopy.

The characterization of the surface chemistry of nanoparticles using infrared spectroscopy of adsorbed solvents is proposed. In conventional IR spectroscopy of nanomaterials the capability of characterizing the chemistry of the surface is limited. To overcome these limitations, we record IR spectra of different solvents inside a fixed bed of the nanopowder to be tested. Using water and different alcohols as solvents enables the characterization of the nanomaterial's surface chemistry via the molecular interactions affecting the hydrogen-bonding network in the solvent. Different ceramic nanopowders (titania, two different iron oxides, and iron oxide nanocrystallites embedded in a closed silica matrix) are studied using water, ethanol, and n-butanol as solvents. The OH stretching region of the IR spectra reveals characteristic differences in the surface chemistry of the nanoparticles. The proposed method is fast and straightforward, and hence, it can be a versatile tool for rapid screening.

In situ synthesis of photocatalytically active hybrids consisting of bacterial nanocellulose and anatase nanoparticles.

Bacterial nanocellulose (BNC) is an extraordinary biopolymer with a wide range of potential technical applications. The high specific surface area and the interconnected pore system of the nanofibrillar BNC network suggest applications as a carrier of catalysts. The present paper describes an in situ modification route for the preparation of a hybrid material consisting of BNC and photocatalytically active anatase (TiO(2)) nanoparticles (NPs). The influence of different NP concentrations on the BNC biosynthesis and the resulting supramolecular structure of the hybrids was investigated. It was found that the number of colony forming units (CFUs) and the consumption of glucose during biosynthesis remained unaffected compared to unmodified BNC. During the formation of the BNC network, the NPs were incorporated in the whole volume of the accruing hybrid. Their distribution within the hybrid material is affected by the anisotropic structure of BNC. The photocatalytic activity (PCA) of the BNC-TiO(2) hybrids was determined by methanol conversion (MC) under UV irradiation. These tests demonstrated that the NPs retained their PCA after incorporation into the BNC carrier structure. The PCA of the hybrid material depends on the amount of incorporated NPs. No alteration of the photocatalyst's efficiency was found during repeated PCA tests. In conclusion, the in situ integration of photocatalytically active NPs into BNC represents an attractive possibility to extend its fields of application to porous filtering media for drinking water purification and air cleaning.

Preparation of SrTiO3 nanocubes by CO2 laser vaporization (LAVA) and hydrothermal maturation.

SrTiO3 is of particular interest for numerous applications such as photocatalytic water splitting, as an electrode material for thermoelectrics or as piezoceramics for sensors. Here we report on an advanced CO2 laser vaporization (LAVA) method for the production of faceted, single-phase SrTiO3 nanoparticles with an average particle size of 35 nm. Starting from a coarse SrTiO3 raw powder, spherical SrTiO3 nanoparticles were obtained by a laser-induced gas-phase condensation process. The composition of the nanoparticles corresponds to that of the starting powder, as XRD and FT-IR measurements show. Further hydrothermal treatment at 275 °C for 4 hours leads to the formation of faceted nanocubes with increasing crystallite size, as demonstrated by TEM, HR-TEM and XRD measurements. During a final washing step in 0.1 M HCl, SrCO3 impurities were dissolved and thus single-phase SrTiO3 nanocubes were successfully obtained, as shown by FT-IR, XRD and TEM analyses. The presented process facilitates the production of single-phase, highly crystalline SrTiO3 nanopowders in sufficient quantities for subsequent use in a variety of applications, in particular for hydrogen production by photocatalytic water splitting.

New ZrO2/Al2O3 Nanocomposite Fabricated from Hybrid Nanoparticles Prepared by CO2 Laser Co-Vaporization.

Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1-x)Al(x)O(2-x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m(1/2)) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants.

Structure evolution of nanoparticulate Fe2O3.

The atomic structure and properties of nanoparticulate Fe2O3 are characterized starting from its smallest Fe2O3 building unit through (Fe2O3)n clusters to nanometer-sized Fe2O3 particles. This is achieved by combining global structure optimizations at the density functional theory level, molecular dynamics simulations by employing tailored, ab initio parameterized interatomic potential functions and experiments. With the exception of nearly tetrahedral, adamantane-like (Fe2O3)2 small (Fe2O3)n clusters assume compact, virtually amorphous structures with little or no symmetry. For n = 2-5 (Fe2O3)n clusters consist mainly of two- and three-membered Fe-O rings. Starting from n = 5 they increasingly assume tetrahedral shape with the adamantane-like (Fe2O3)2 unit as the main building block. However, the small energy differences between different isomers of the same cluster-size make precise structural assignment for larger (Fe2O3)n clusters difficult. The tetrahedral morphology persists for Fe2O3 nanoparticles with up to 3 nm in diameter. Simulated crystallization of larger nanoparticles with diameters of about 5 nm demonstrates pronounced melting point depression and leads to formation of ε-Fe2O3 single crystals with hexagonal morphology. This finding is in excellent agreement with the results obtained for Fe2O3 nanopowders generated by laser vaporization and provides the first direct indication that ε-Fe2O3 may be thermodynamically the most stable phase in this size regime.

Zirconia nanoparticles prepared by laser vaporization as fillers for dental adhesives.

Zirconia nanoparticles prepared by laser vaporization were incorporated into the primer or into the adhesive of a commercial adhesive system in order to evaluate its effect on bond strength to dentin. Zirconia nanoparticles (20-50nm) were prepared using a particular laser vaporization technique and incorporated into the primer (P) or into the adhesive (A) of the Adper Scotchbond Multi-Purpose (SBMP) system at 5, 10, 15 and 20wt.% by means of mechanical mixing (stirring) and ultrasonication. Control (unfilled) and experimental groups (filled) were applied, according to the manufacturer's instructions, onto flat mid-coronal human dentin. Composite crowns were built up, stored in distilled water for 24h at 37°C and cut into 0.65±0.05mm² beams following a non-trimming microtensile technique. Specimens were fractured in tension using a universal testing machine (Zwick) and examined by scanning electron microscopy for fractographic analysis. Microtensile bond strength (µTBS) data were analyzed using a two-way ANOVA and modified LSD test at α=0.05. Analysis of the nanofiller distribution and ultramorphological characterization of the interface were performed by transmission electron microscopy (TEM). Zirconia nanoparticle incorporation into the primer or into the adhesive of SBMP significantly increased µTBS to dentin. Filler concentration only affected µTBS significantly in the P group. Statistically significant differences between groups P and A occurred only at 20wt.% filler content, with a significantly higher µTBS in group P. TEM micrographs revealed nanoparticle deposition on top of a hybrid layer when incorporated into the primer, whereas they remained dispersed through the adhesive layer in group A. Zirconia nanoparticles incorporation into SBMP increased bond strength to dentin by reinforcing the interface adhesive layer. Nanofiller incorporation into the primer solution showed a tendency of increasing bond strength with increasing concentration. At high concentrations (20wt.%) nanofiller incorporation was more efficient in increasing bond strength if incorporated in the primer solution. Adding nanofillers to the primer and to the adhesive solutions resulted in different particle distributions at the interface.