An onset coarsening-coalescence event based on the incubation time of cylindrical mesopore formation and a significant decrease of specific surface area by 50% relative to the dry pressed samples was determined by N2 adsorption-desorption hysteresis isotherm for cassiterite SnO2 nanoparticles (rutile-type structure with bimodal size distribution). In the temperature range of 800-1100oC, the nanoparticles underwent onset sintering coupled with coarsening-coalescence without appreciable polymorphic transformation or decomposition of SnO2. The apparent activation energy of such a rapid process for SnO2 nanoparticles was estimated as 75 ¡Ó 5 kJ/mol, respectively. The minimum temperature for sintering/coarsening/coalescence of the SnO2 nanoparticles is 735oC based on the extrapolation of steady specific surface area reduction rates to null. PLA fragmentation of cassiterite SnO2 powder (rutile type, 20-50 nm in size) in water was conducted under Q-switch mode (532 nm, 400 mJ per pulse) having laser focal point fixed at 5, 10, 15 and 20 mm beneath the water level for an accumulation time of 5, 15, 20 and 30 min at 10 Hz. The 532 nm laser incidence suffered little water absorption and was effective to produce cassiterite nanocondensates as small as 5 nm in diameter and occasional nanocondensates of £\-PbO2-type structure more or less in coalescence. The combined effects of nanosize, internal compressive stress and H+ and Sn2+ co-signature in the lattice may account for a lower minimum band gap.

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Pulsed laser ablation ¡]PLA¡^in single shot on polycrystalline Ti thin foil ca. 20

The H-type Nb2O5 powders (monoclinic structure with (101) crystallographic shear plane) submicron to micrometers in size were subjected to pulsed laser ablation fragmentation in water (PLAL) with optional NaCl addition in order to study the structure change of the resultant Nb2O5 nanoparticles by x-ray diffraction and electron microscopy. The Nb2O5 nanoparticles via such a dynamic PLAL fragmentation process turned out to be H-type relic and newly formed T-type (an orthorhombic high-pressure phase), TT-type (a pseudohexagonal high-pressure phase) and a nonstoichiometric amorphous phase which coexist within a faceted nanoparticle (down to ca. 5 nm) or coalesced with each other. The composite Nb2O5 nanoparticles were protonated and imposed with a considerable internal compressive stress to modify the structure units and band structure as indicated by vibrational (Raman and FTIR) spectra and uv-visible absorption spectrum of the darkened colloidal solution indicating a stepwise minimum band gap lowering down to stepwise 3.0¡Ó0.1 eV and 2.5¡Ó0.1eV. NaCl spiking in water did not cause appreciable change on the phase behavior of Nb2O5 powders upon PLAL.

An onset coarsening-coalescence event based on the incubation time of cylindrical mesopore formation and a significant decrease of specific surface area by a certain fraction relative to the dry pressed samples was determined by N2 adsorption-desorption hysteresis isotherm for amorphous SiO2 nanoparticles (ca. 40 nm in size). In the temperature range of 1150-1300oC, the nanoparticles with binder (PVA) additive underwent onset sintering coupled with coarsening-coalescence without appreciable crystallization. The apparent activation energy of such a rapid process for amorphous SiO2 nanoparticles was estimated as 177 ¡Ó 31.5 kJ/mol, based on 30% change of specific surface area. As a comparison, in much lower temperature range of 600-900oC, the amorphous Zn2SiO4 nanoparticles underwent onset sintering coupled with coarsening-coalescence accompanied more or less with the formation of ZnO The apparent activation energy of such a rapid process for a amorphous Zn2SiO4 was estimated as 105 ¡Ó 3.8 kJ/mol based on 50% change of specific surface area. The minimum temperatures for sintering/coarsening/coalescence of the amorphous SiO2 and Zn2SiO4 are 1120¢J and 635oC, respectively based on the extrapolation of steady specific surface area reduction rates to null. PLA fragmentation of amorphous and nearly spherical SiO2 nanoparticles (40 nm in size) in water (i.e. PLAL process) with optional NaCl addition was conducted under Q-switch mode (532 nm, 400 mJ per pulse) having laser focal point fixed at ca. 10 mm beneath the water level for an accumulation time of 20 and 30 min at 10 Hz. The 532 nm laser incidence suffered little water absorption and was effective to produce irregular shaped amorphous nanocondensates as small as 10nm~20nm in diameter with accompanied change of medium range order (MRO) as indicated by single rather than two broad x-ray diffractions at low 2theta angle. Whereas the Na+ uptake in the amorphous silica from the salty water account for a lower wave number of FTIR bands. The combined effects of nanosize, MRO change and H+ -signature may cause a lower minimum band gap of the amorphous products (analogous to opal-A) which become partially crystallized as £]-cristobalite (analogous to opal-CT) with additional £\-tridymite when Na+ is present.

The specific surface area reduction and pore size distribution coupled with N2 adsorption-desorption hysteresis isotherm were studied in the temperature range of 1400-1550¢J for periclase MgO powder having 0.1£gm in size and with face-centered cubic structure. The apparent activation energy of such a rapid coarsening-coalescence process for MgO powder was estimated as 181¡Ó3kJ/mol. The minimum temperature for sintering/coarsening/coalescence of submicron MgO particles was estimated to be near 1300¢J based on the extrapolation of steady specific surface area reduction rates to zero. Pulsed laser ablation (PLA) of periclase MgO powders in water was conducted under Q-switch mode and specified water height and water depth (10 mm) for an accumulation time of 5 and 20 minutes at 10 Hz. Such a PLA process has successfully synthesized nanosized and protonated MgO particles from Mg(OH)2 and lamellar precusors, implying the three phases may co-exist at high pressure and temperature conditions upon dynamic shock loading. A significant internal compressive stress up to 10 GPa was built up for the MgO but not the readily relaxed Mg(OH)2 nanocondensates. The lamellae-derived Mg(OH)2 tended to undergo a dehydroxylation process to become MgO following a specific crystallographic relationship, i.e. lamellar basal layer parallel to Mg(OH)2(0001) and MgO(111). The minimum band gap of the colloidal solution of MgO/Mg(OH)2/lamellae was lowered to ca. 5.2eV after the PLA process.