**2.3. NaNbO3 particles characterization**

hydrothermal synthesis. The influence exerted by the synthesis parameter in obtaining the particles with the best characteristics as well as the use of these particles in the fabrication of composite films with 0-3 connectivity, using PVDF as polymer matrix, are all presented and

NaNbO3 powders were obtained by microwave hydrothermal synthesis which was carried out beginning with NaOH (p. a. Quemis) and Nb2O5 (Alfa Aesar, 99%). In the reaction to form NaNbO3, the NaOH acts as a mineralizing agent and sodium source. The reaction was carried out in a Teflon vessel model XP-1500 (CEM Corp.), in a MARS-5 (CEM Corp.) microwave oven. The precursor suspensions were prepared with 0.696 g of Nb2O5 added to 30 mL of 8 mol.L–1 NaOH water solution. The suspension was then transferred into Teflon vessels which were placed inside a microwave furnace. The synthesis was carried out at 180°C with different conditions as given in Table 1. The obtained powders were thoroughly washed with distilled

**Microwave Power (W) Synthesis Time**

800 30 1000 30

The NbO7 decahedra and NbO6 octahedra resulted from the breaking up of the Nb2O5. The NbO7 and NbO6 are connected by corner forming Nb6O198– hexaniobate *Lindqvist* ion, which can provide different niobate compositions. These compositions are related to the different

In solution, the Nb6O198– ions incorporate Na+ ions forming Na2Nb2O6.nH2O microfibers, followed by structural rearrangement, releasing water molecules forming NaNbO3 structures

**Table 1.** Microwave hydrothermal synthesis conditions for obtaining NaNbO3 particles.

**2.2. Reaction Mechanism to form Na2Nb2O6.H2O and NaNbO3**

synthesis conditions used to obtain the materials.

[20,21,22].

**(minutes)**

> 30 60

water by centrifugation and finally dried at room temperature.

discussed.

**2. Experimental processing**

62 Ferroelectric Materials – Synthesis and Characterization

300

600

**2.1. NaNbO3 synthesis**

The obtained powders were characterized by X-ray powder diffraction using a rotatory anode diffractometer (Rigaku-RINT 2000) with divergent cleft of 0.25°, soller cleft of 2.5° of diver‐ gence in the 2θ range from 20° to 80° with 0.2 graus.min–1. The morphology of as-prepared samples was observed using a high-resolution field-emission gun scanning electron micro‐ scopy FE-SEM (GERMA JEOL JSM 7500F Field Emission Scanning Electron Microscopy). PL spectra were collected with a Thermal Jarrel-Ash Monospec 27 monochromator and a Hama‐ matsu R446 photomultiplier. The 350 nm exciting wavelength of a krypton ion laser (Coherent Innova) was used with the nominal output power of the laser kept at 550 mW. All measure‐ ments were performed at room temperature.

Figure 1 shows the diffraction powder patterns of X-ray obtained for the powder synthesis carried out at 300 W. Based on the results, it is observed that a pure orthorhombic crystalline structure of NaNbO3 is favored by a rise in the synthesis time period, which is in accordance with the JCPDS file nº 33.1270. For the 30 and 60 minute synthesis times, the obtained product consisted of Na2Nb2O6.nH2O. When the synthesis times are increased to 120 and 180 minutes, the products are a mixture of Na2Nb2O6.nH2O and orthorhombic NaNbO3 and a diffractogram peak attesting to the decreasing of Na2Nb2O6.nH2O until it disappears following 240 minutes of synthesis indicating the formation of orthorhombic NaNbO3 pure phase.

The presence of microwave enables the obtaining of NaNbO3 crystalline phase in a short synthesis time and this time can be even smaller when the power of microwave is increased. Figure 2 shows the X-ray diffraction of products obtained using a higher power above 300 W. Using 600 W for 30 minutes, peaks related to Na2Nb2O6.nH2O were observed and a pure orthorhombic NaNbO3 was seen using 600 W for 60 minutes. By increasing the power to 800 or 1000 W, it is worth noting that the time for obtaining the orthorhombic NaNbO3 pure phase was found to decrease to 30 minutes.

According to Zhu et al [21], Na2Nb2O6.nH2O is a microporous metastable phase with fiber morphology resulting from NaNbO3 crystallization. The Na2Nb2O6.nH2O phase presents monoclinic crystalline structure belonging to the C*2/c* space group with lattice parameters *a* = 17.0511 Å, *b* = 5.0293 Å, *c* = 16.4921 Å e β=113.942 Å and are applied in SOMS, Sandia Octahedral Molecular Sieves [20]. The dehydration of Na2Nb2O6.nH2O promotes the formation of NaNbO3 perovskite phase which is energetically more stable [20].

Under hydrothermal conditions, NaNbO3 formation occurs as a result of the dissolution of Nb2O5 in NaOH environment, which is favored by the rise in synthesis time. While the Nb2O5 is dissolved, OH– ions are adsorbed on the Nb2O5 surface, thereby promoting the affinity between Nb=O and O-H bonds forming Nb=O⋅⋅⋅OH⋅⋅⋅O=Nb [23].

**Figure 1.** XRD patterns of particles obtained by microwave hydrothermal synthesis using 300 W at 180°C in different synthesis time.

**Figure 2.** XRD patterns of particles obtained by microwave hydrothermal synthesis using 600 W, 800 W and 1000 W at 180°C.

The morphological changes regarding the process are shown in Figure 3, where one can observe that the products presented different morphologies. It is noteworthy that for the 30 and 60 minutes synthesis times with 300 W of power, the samples were composed of Na2Nb2O6.nH2O structures with fiber-like shape (Figures 3 A–B). For the 120 and 180 minutes synthesis times, there is a mix of fiber and plate-like structures (Figure 3C), and when the synthesis time is increased to 240 minutes, only particles with cube-like morphology are observed (Figure 3D). These results confirm the XRD results (Figure 1) as it is possible to observe that given an increase in the synthesis time, the fiber morphology corresponds to the Na2Nb2O6.nH2O until the formation of orthorhombic NaNbO3 with a cubic shape [24,25].

Under hydrothermal conditions, NaNbO3 formation occurs as a result of the dissolution of Nb2O5 in NaOH environment, which is favored by the rise in synthesis time. While the

**Figure 1.** XRD patterns of particles obtained by microwave hydrothermal synthesis using 300 W at 180°C in different

**Figure 2.** XRD patterns of particles obtained by microwave hydrothermal synthesis using 600 W, 800 W and 1000 W at

between Nb=O and O-H bonds forming Nb=O⋅⋅⋅OH⋅⋅⋅O=Nb [23].

ions are adsorbed on the Nb2O5 surface, thereby promoting the affinity

Nb2O5 is dissolved, OH–

64 Ferroelectric Materials – Synthesis and Characterization

synthesis time.

180°C.

**Figure 3.** FE–SEM of particles obtained by microwave hydrothermal synthesis at 300 W. (A) 30 minutes; (B) 60 mi‐ nutes; (C) 120 minutes; (D) 180 minutes; (E) 240 minutes.

Using 600 W power, the particles obtained in the shortest time – 30 minutes – also presented fiber morphology, while presenting a cubic morphology after 60 minutes of synthesis (Figure 4 A–B). By increasing the power, the time to obtain the NaNbO3 cubic morphology decreases to 30 minutes, though the particles are clustered as can be seen in Figure 4 C–D.

The morphological evolution of NaNbO3 obtained by hydrothermal synthesis was extensively studied by Zhu et al [21]. NaOH breaks the octahedra corner sharing formed by Nb–O from Nb2O5 forming intermediaries octahedral edge sharing, which presents low crystallinity. The dissolution of intermediate gives NbO6 which promotes the growth of metastable compound with fiber shape. Finally, increasing the synthesis time, the fibers are dissolved and the NbO6 octahedral takes the form of NaNbO3 with a cubic shape.

**Figure 4.** FE–SEM of particles obtained by microwave hydrothermal synthesis using different powers.(A) 30 minutes and 600 W; (B) 60 minutes and 600 W; (C) 30 minutes and 800 W; (D) 30 minutes and 1000 W.

By means of the conventional hydrothermal synthesis using the Pluronic P123 copolymer (EO20PO70EO20, BASF, USA), Shi et al [26] obtained orthorhombic NaNbO3 with a fiber shape. The copolymer assists the particles crystallization during the reaction between Nb2O5 and NaOH at 200°C for 24 hours. Replacing the P123 with PEG-1000 (polyethylene glycol), cubic-like particles with a narrow size distribution is obtained. Ke et al [27] report the change of NaNbO3 morphology in line with the NaOH concentration used in the synthesis. The materials obtained from NaNbO3 with 1D morphology including fibers and wires can present good piezoelectric property [4]. A process used to obtain this morphology is the thermal treatment of Na2Nb2O5.H2O at temperatures around 300–550° C. The thermal treatment changes the crystalline structure of the material maintaining the 1D shape. Although piezo‐ electricity is an anisotropic property, the NaNbO3 with cubic morphology hardly presents good piezoelectricity due to the high symmetry of the cubes.

In this work, the thermal treatment of the product was carried out for a period of 4 hours at 550°C by microwave hydrothermal synthesis with 300 W at 180°C for 30 minutes; the meta‐ stable phase of Na2Nb2O5.nH2O is transformed into the orthorhombic structure of NaNbO3 maintaining the fiber-like morphology as shown in Figure 5. The thermal treatment promotes the dehydration of Na2Nb2O6.nH2O, forming NaNbO3 perovskite phase, which is found to be energetically more stable than Na2Nb2O6.nH2O.

In a previous work, we reported about the PL properties at room temperature of NaNbO3 particles and film as a function of anisotropic morphology; the NaNbO3 particles in question are fiber and cubic-like morphologically structured, being that the fibers are originated from the thermal treatment of Na2Nb2O6.nH2O fibers. The particles which presented major PL intensity are Na2Nb2O6.nH2O fibers prior to thermal treatment, and the smaller PL emission is found to be presented by NaNbO3 fiber-like particles [22].

The order–disorder of the materials including surface defects, cation or anion vacancies, lattice distortions and the recombination process in semiconductors can be evaluated based on the Perovskite-Based Mesostructures and Related Composites — Influence Exerted by Morphology and Interface http://dx.doi.org/10.5772/60654 67

**Figure 5.** XRD patterns and FE–SEM of Na2Nb2O5.nH2O prior to following thermal treatment at 500°C for 4 hours to form NaNbO3 particles.

**Figure 4.** FE–SEM of particles obtained by microwave hydrothermal synthesis using different powers.(A) 30 minutes

By means of the conventional hydrothermal synthesis using the Pluronic P123 copolymer (EO20PO70EO20, BASF, USA), Shi et al [26] obtained orthorhombic NaNbO3 with a fiber shape. The copolymer assists the particles crystallization during the reaction between Nb2O5 and NaOH at 200°C for 24 hours. Replacing the P123 with PEG-1000 (polyethylene glycol), cubic-like particles with a narrow size distribution is obtained. Ke et al [27] report the change of NaNbO3 morphology in line with the NaOH concentration used in the synthesis. The materials obtained from NaNbO3 with 1D morphology including fibers and wires can present good piezoelectric property [4]. A process used to obtain this morphology is the thermal treatment of Na2Nb2O5.H2O at temperatures around 300–550° C. The thermal treatment changes the crystalline structure of the material maintaining the 1D shape. Although piezo‐ electricity is an anisotropic property, the NaNbO3 with cubic morphology hardly presents

In this work, the thermal treatment of the product was carried out for a period of 4 hours at 550°C by microwave hydrothermal synthesis with 300 W at 180°C for 30 minutes; the meta‐ stable phase of Na2Nb2O5.nH2O is transformed into the orthorhombic structure of NaNbO3 maintaining the fiber-like morphology as shown in Figure 5. The thermal treatment promotes the dehydration of Na2Nb2O6.nH2O, forming NaNbO3 perovskite phase, which is found to be

In a previous work, we reported about the PL properties at room temperature of NaNbO3 particles and film as a function of anisotropic morphology; the NaNbO3 particles in question are fiber and cubic-like morphologically structured, being that the fibers are originated from the thermal treatment of Na2Nb2O6.nH2O fibers. The particles which presented major PL intensity are Na2Nb2O6.nH2O fibers prior to thermal treatment, and the smaller PL emission is

The order–disorder of the materials including surface defects, cation or anion vacancies, lattice distortions and the recombination process in semiconductors can be evaluated based on the

and 600 W; (B) 60 minutes and 600 W; (C) 30 minutes and 800 W; (D) 30 minutes and 1000 W.

good piezoelectricity due to the high symmetry of the cubes.

energetically more stable than Na2Nb2O6.nH2O.

66 Ferroelectric Materials – Synthesis and Characterization

found to be presented by NaNbO3 fiber-like particles [22].

PL process. PL is an efficient method for investigating the electronic structure and optical properties of materials. PL properties are a great probe for investigating changes around the site environment at short-range (2−5 Å) and medium-range order (5−20 Å) of clusters where the degree of local order is pronounced [28]. The PL emission region is associated to the defects of the materials. When the material presents deep-level defects, it generates intermediary energy levels near the conduction band which are represented by the PL emission at low energy (yellow/green region of electromagnetic spectrum). Shallow levels generate states next to the valence band where they exhibit PL emission at a higher energy (violet/blue region) [28].

Prior to thermal treatment, the fibers show PL emission around 550 nm, which is then found to decrease following thermal treatment. Furthermore, the band is seen to shift toward a higher energy region. Like the NaNbO3 fiber, the cubic particles also emit higher energy (450 nm) (cf. Figure 4 Ref 22), and this displacement indicates that NaNbO3 crystalline structure is more stable compared to Na2Nb2O6.nH2O [22].

At low temperature, Almeida et al [29] obtained two PL bands centered at approximately 430 nm and 540 nm in glass-ceramic-containing NaNbO3 crystal. The emission at 430 nm was attributed to the direct exciton recombination, and the low quantum efficiency is likely to indicate that the emission at 540 nm emanates from trap states. At room temperature, the PL band is centered only in the region around 430 nm, next to NaNbO3 PL emission region as we have reported in a previous work [22].

In a previously published paper [22], we proposed that the PL bands can be attributed to the bulk energy levels consistent with their attribution to the transitions between O2– and Nb5+, based on the local structure of NbO6 octahedra. By similar structure analyses, NbO6 assumes the form of a regular octahedron, which comes from the strong covalent bonding as a result of the orbital hybridization between Nb **d** and O **2p**. Without the presence of structural defects capable of changing the clusters organization, this crystalline structure is characterized by a high symmetry. However, the order–disordered NaNbO3 presents a symmetry rupture along the O–Nb–O bonds that result in complex clusters with different coordination numbers ([NbO6]–[NbO5]) or distortions in the [NbO6]–[NbO6] octahedral clusters. The wide-band visible emission observed is a characteristic property of practically all self-activated ABO3 perovskites [22,30].

Some materials present a change in the PL emission according to the morphology [31]. However, as far as our investigation is concerned, the PL results are seen not to be related to the morphology of the NaNbO3 but rather to the organization of the crystalline structure. This observation is backed by the results observed in [22] where the orthorhombic NaNbO3 presents fiber-like and cubic-like particles, where both have PL emission in the same region. The PL emission region observed here is not the same for Na2Nb2O6.nH2O which presents fiber-like particles to boot [22].

The microwave hydrothermal process is capable of producing NaNbO3 with a more disor‐ ganized structure when compared to NaNbO3 obtained by thermal treatment of Na2Nb2O6.nH2O. This can be associated to the heating of Na2Nb2O6.nH2O so as to yield NaNbO3 with fiber-like morphology which tends to promote a better self-assembly of the crystalline structure than in cubic-like particles. This assembly decreases the structural defects as well as the intermediary levels within the band gap, resulting in a lower PL emission [22].
