The origin of the narrow particle size distributions obtained in the oleic acid-based synthesis of hexagonal phase β-NaREF(4) nanocrystals (RE = Sm, Eu, Gd, Tb) has been investigated. Compared to the standard synthesis, the growth conditions were simplified by using small purified particles of either α-NaREF(4) (cubic phase) or β-NaREF(4) (hexagonal phase) as single-source precursors, thereby avoiding the complications arising from the simultaneous presence of molecular educts and intermediately formed small particles. The study shows that α-phase as well as β-phase particles grow by Ostwald-ripening but narrow particle size distributions of the β-NaREF(4) product particles are only obtained when α-phase precursor particles are employed. Since the small particles are also formed as intermediate products in the standard synthesis of β-NaSmF(4), β-NaEuF(4), β-NaGdF(4) and β-NaTbF(4) particles, their crystal phase is an important parameter to obtain a narrow size distribution in these systems.

Rare earth phosphates have recently been investigated as a potential ceramic material in view of their high-temperature phase stability, high melting point, low thermal conductivity, optical, fluorescence, and catalytic properties, and layered structural features. The present work describes a method for synthesizing nanocrystalline cerium phosphate starting from cerium nitrate and orthophosphoric acid by sol-gel process involving controlled precipitation followed by electrostatic stabilization (peptization) using nitric acid and deagglomeration of sol particles using ultrasonication. Average particle size of cerium phosphate in the precursor sol is 50 nm. Dehydroxylation of the precursor gel was studied by thermal analysis and FTIR spectrum. The transformation of low-temperature rhabdophane phase to hexagonal and further to monoclinic monazite type at 800 °C is evidenced from the XRD pattern. Cerium phosphate had crystallite size of 10 nm and excellent thermal phase stability up to 1700 °C as observed from XRD data. Specific surface area of 98 m 2 /g was obtained for precursor gel calcined at 400 °C. The nanosize cerium phosphate has been sintered at 1300 °C to ∼99% density with an average grain size of 1 µm as observed from SEM micrographs.

Synthesis of rod‐shaped nanocrystalline lanthanum phosphate with an average length of 40 nm even after calcination at 400 °C has been realized through a room‐temperature aqueous sol–gel process. The sol is characterized by particle‐size, zeta‐potential, and viscosity measurements. Gelation of the sol is induced by ammonia. The lanthanum phosphate phase‐formation process is followed by thermal, Fourier‐transform IR, and X‐ray diffraction analysis. Transmission electron microscopy shows that the sol and gel particles have a rod‐shaped morphology and comparable particle sizes. Using the Scherrer equation a crystallite size of 11 nm is obtained for the gel powder calcined at 400 °C and Brunauer–Emmett–Teller (BET) nitrogen‐adsorption analysis showed a high specific surface area of 100 m2 g–1. Ammonia temperature‐programmed desorption measurements show that the density of Lewis acid sites is four times higher than ever reported in the case of lanthanum phosphates. The catalytic activity of the above sample is demonstrated by using it as a Lewis‐acid catalyst in an acetal‐formation reaction with a very good yield of 85 %. The sol is used to develop nanocoatings on a glass surface and the morphology of the coatings is investigated using atomic force microscopy and scanning electron microscopy. The microstructure of the coating confirmed the rod‐shaped nature of the sol particles. The coating was uniform with a thickness of about 55 nm.

Doped nanocrystals of NaYF(4) and NaGdF(4) are currently studied as upconversion luminescence markers and magnetic resonance imaging contrast agents. An EPR investigation on the growth mechanism of NaYF(4):Gd and NaGdF(4) nanocrystals showed that these nanomaterials grow in the standard oleic acid-based reaction medium by a dissolution/recrystallization mechanism and not by the aggregation or oriented attachment of smaller particles.

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Though Pr3+ doped LiYF4 (LiYF4:Pr3+) bulk crystals are a well-known laser gain material with several radiative transitions, their nanocrystal counterparts have not been investigated with regards to these. Through downsizing...

"Quat-primer" polymers bearing cationic groups were investigated as a surface modifier for Tb-doped cerium phosphate green-emitting fluorescent nanorods (NRs). The NRs were synthesized by a microwave process without using any complex agents or ligands and were characterized with different analytical tools such as X-ray diffraction, transmission electron microscopy, and fluorescence spectroscopy. Poly(ethyleneimine) partially quarternized with glycidyltrimethylammonium chloride was synthesized separately and characterized in detail. (1)H and (13)C NMR spectroscopic studies revealed that the quaternary ammonium group was covalently attached to the polymer. UV-vis spectroscopy was used to examine the stability of the colloidal dispersions of the bare NRs as well as the modified NRs. ζ potential, thermogravimetric analysis, and atomic force microscopy studies were carried out to confirm that the positively charged Quat-primer polymer is adsorbed on the negatively charged surface of the NRs, which results in high dispersion stability. Emission spectra of the modified NRs indicated that there was no interference of the Quat-primer polymer with the fluorescence behavior.

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol-gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log-log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.