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    Titanate Nanosheets/Cellulose Composite Showing Improved Crystallinity and Decreased Water Wettability by Gamma-Irradiation
    (2025-11-25)
    Tariwong, Yaowaluk
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    Pulphol, Phieraya
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    Sangtawesin, Tanagorn
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    Seriwattanachai, Chaowaphat
    ;
    Kanjanaboos, Pongsakorn
    While molecularly thin nanosheets have been increasingly studied as functional coatings, their use as a hydrophobic and γ-irradiation-tolerant component in biologically derived matrices is to be demonstrated. Herein, simple dip-coating was employed to fabricate titanate nanosheets/cellulose composites, which were subjected to γ-irradiation up to 50 kGy. Their surface chemistry was evaluated by water contact angle (WCA) measurements and X-ray photoelectron spectroscopy (XPS). Upon irradiation, the WCA of all samples nonmonotonically increased in three stages from ∼29 to 50° (noncoated) and ∼46 to 80° (composite, optimized at ∼1.2 wt %Ti loading, or 0.2 mg·cm<sup>–2</sup>). The titanium content and the 4+ valence did not change with the dose, suggesting the radiolytic stability. The dual surface modification occurs while cellulose fiber morphology and nanoscale mechanical properties are preserved. The increased WCA at the cellulose-part is explained by the γ-irradiation-induced crystallization according to the increased crystallinity index and improved thermal stability. At the other component, nanosheet coating results in increased surface roughness and diminished water–surface interactions. The latter is deduced from DSC measurements of water evaporation from pristine and 50 kGy-irradiated Cs<inf>0.7</inf>Ti<inf>1.825</inf>O<inf>4</inf>layered crystal-a nanosheet precursor. Our work suggests further exploration of nanosheets with diverse structures and compositions as coatings or fillers, which could find applications in γ-irradiation-sterilized barrier films.
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    Phase Evolution, Microstructure and Electrical Behavior of (Ba0.97Ca0.03)(Ti0.94-x/2Sn0.06-x/2Wx)O3 Ceramics Synthesized via the Solid-State Combustion Technique
    (2022-01-01)
    Udeye, Thanya
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    Onsri, Thanakrit
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    Yotthuan, Surirat
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    Pulphol, Phieraya
    ;
    This research studied the effect of W<sup>4+</sup> substitution on the phase formation, microstructure and electrical properties of (Ba<inf>0.97</inf>Ca<inf>0.03</inf>)(Ti<inf>0.94-x/2</inf>Sn<inf>0.06-x/2</inf>W<inf>x</inf>)O<inf>3</inf> (BCTSW) ceramics with x = 0, 0.005, 0.010, 0.015 and 0.020 mol%. The BCTSW ceramics were synthesized by the solid-state combustion technique, using glycine as fuel. The powders and green pellets of BCTWS were calcined and sintered at 1100 °C for 4 h and 1400 °C for 2 h, respectively. A pure perovskite phase with coexisting orthorhombic and tetragonal phases were observed for all samples. The content of the tetragonal phase increased when x rose, as verified by the Rietveld refinement procedure. The average grain size and the measured density of the samples tended to decrease from 35 ± 0.56 to 1.9 ± 0.12 µm and 5.59 to 4.88 g/cm<sup>3</sup>, respectively, when x increased. The dielectric behavior of the ceramics strongly degenerated upon W<sup>4+</sup> substitution. The undoped BCTS ceramic showed a well-saturated P-E hysteresis loop. With W<sup>4+</sup> substitution, the samples’ P-E loops became unsaturated and a leakage current was created.
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    Tailoring charge affinity, dielectric property, and band gap of bacterial cellulose paper by multifunctional Ti2NbO7 nanosheets for improving triboelectric nanogenerator performance
    (2023-02-01)
    Sriphan, Saichon
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    Pharino, Utchawadee
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    Charoonsuk, Thitirat
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    Pulphol, Phieraya
    ;
    Pakawanit, Phakkhananan
    Transparent, flexible, and high-performance triboelectric nanogenerator (TENG) from nature-derived materials are required for sustainable society development. However, low triboelectricity from natural material is generally observed. Tunable electronic band diagram (EBD) through facile manipulation is one of the efficient methods to promote the TENG output, requiring fundamental, in depth understanding. Herein, we employed the high quality, single crystal-like Ti<inf>2</inf>NbO<inf>7</inf> nanosheets (NSs) with dual dielectric and semiconducting properties as filler for bacterial cellulose (BC)-based TENG. Several techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), ultraviolet—visible (UV—vis) absorption, energy dispersive X-ray spectroscopy (EDS), and synchrotron radiation X-ray tomographic microscopy (SRXTM) were applied to characterize the long-range structure, microstructure, optical properties, elemental composition, and three-dimensional (3D) distribution of components in the composites. The semi-transparent and flexible 5 vol.% Ti<inf>2</inf>NbO<inf>7</inf> NSs/BC preserved the integrity of cellulose, contained well-dispersed nanosheets, reduced optical band gap (4.20 vs. 5.75 eV for BC), and increased surface roughness. The dielectric permittivity and conductivity increased with nanosheets content. Adding negatively-charged Ti<inf>2</inf>NbO<inf>7</inf> NSs could regulate the charge affinity of BC composite via shifting of Fermi energy over that of Al. It is found that adding 5 vol.% NSs into the BC film improved electrical outputs (~ 36 V and ~ 8.8 µA), which are 2–4 times higher than that of pure BC, even when paired with Al which lies adjacent in triboelectric series. Our work demonstrated the method to enhance BC-based TENG performance through EBD regulation using multifunctional Ti<inf>2</inf>NbO<inf>7</inf> NSs. [Figure not available: see fulltext.]
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    Electrical conductivity, magnetism, and optical properties of reduced BaCeO 3
    (2019-03-01)
    Pulphol, Phieraya
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    ; ;
    Kolodiazhnyi, Taras
    BaCeO <inf>3</inf> -based perovskites are well-known proton and oxygen ion conductors. For practical applications as electrolytes in solid oxide fuel cells, these compounds must be robust towards reduction of cerium ion. In this work, we explore the effect of reducing atmosphere on the physical properties of undoped and Nb-doped BaCeO <inf>3</inf> . The BaCeO <inf>3</inf> perovskite structure is thermodynamically stable at least up to 1450 <sup>∘</sup> C upon annealing in H <inf>2</inf> -containing atmosphere. Annealing at 1550 <sup>∘</sup> C causes a decomposition of the BaCeO <inf>3</inf> . The higher annealing temperature leads to higher concentration of Ce <sup>3 +</sup> ions and a higher electrical conductivity. With increasing the annealing temperature from 1300 to 1450 <sup>∘</sup> C , the activation energy of conductivity decreases from E <inf>a</inf> = 0.31–0.263 eV. We attribute the electrical conductivity in reduced BaCeO <inf>3</inf> to the activation of the small polaron hopping in agreement with the recent first-principles calculations. However, in contrast to the theoretical predictions, we find no evidence of the Ce <sup>3 +</sup> –Ce <sup>3 +</sup> spin-singlet small bipolarons.
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    AC Conductivity and dielectric properties of lepidocrocite-type alkali titanate tunable by interlayer cation and intralayer metal
    (2020-11-02)
    Charoonsuk, Thitirat
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    Sriphan, Saichon
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    Pulphol, Phieraya
    ;
    ;
    The lepidocrocite-type layered alkali titanate AxMyTi2-yO4 has diverse chemical compositions with variation in charge per formula unit x, the interlayer cation A+, and the intralayer metal M. Despite this multivariable nature, the composition dependence of physical properties is not well explored. We report herein the AC conductivity and the complementary dielectric properties of Cs0.7M0.35Ti1.65O4, K0.8M0.4Ti1.6O4 (M = Zn, Ni), and the mixed-interlayer ion Cs0.6K0.1Zn0.35Ti1.65O4. For Cs0.7Zn0.35Ti1.65O4, the total AC conductivity is ~7 × 10-8 to 2 × 10-6 S·cm-1 at 200-350 °C, associating with an activation energy Ea ∼865 meV. Meanwhile, the conductivity of K0.8Zn0.4Ti1.6O4 is higher by 1 order of magnitude at much lower temperature (25-150 °C) and a smaller Ea ∼250 meV. This difference originates from the compositional robustness of the cesium-containing samples, contrasting with the sintering-induced changes in the potassium analogues. For the latter, the loss of the interlayer K+ ion results in (i) generation of carriers due to charge compensation, (ii) reduction of sheet charge density and weakening of electrostatic attraction, and (iii) widening of the interlayer distance, all contributing to a lower Ea in K0.8M0.4Ti1.6O4. The angular frequency dependence of conductivity, dielectric permittivity (up to a colossal value of 109), and dielectric loss follows the universal power law. Our work demonstrates the potential of simple compositional variation for electrical properties tuning, prompting a more in-depth investigation covering a wider range of possible candidates of x, A+, and M in lepidocrocite titanate.
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    The apparent PTCR effect in layered alkali titanates - A correlation between temperature dependent electrical properties and thermal analyses
    (2024-12-01)
    Pulphol, Phieraya
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    Chaithaweep, Kanokwan
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    ;
    Adsorbed water promotes proton conduction in ceramics at ambient conditions prior to its evaporation, apparently leading to the positive temperature coefficient of resistivity (PTCR) effect. Using surface water-containing Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> (1.8 mol water/mol titanate) as an example, the static conductivity (at 50 °C) of ∼10<sup>−5</sup> S cm<sup>−1</sup> is one thousand times that at 200 °C due to the enhanced proton conduction. At 50–150 °C, the conductivity decreases by 4 orders of magnitude because water evaporation decreases the number of charge carriers. At 150–400 °C, the conduction in water-free Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> is thermal-activated with the apparent activation energy E<inf>a</inf> ∼58–72 kJ mol<sup>−1</sup>, depending on the formalisms. We show clearly that an endothermic DSC peak (water evaporation) in Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> coincides with all eight presentations of AC properties examined. Similar correlations are obtained from the TG/DTG curves in Cs<inf>2</inf>Ti<inf>5</inf>O<inf>11</inf>·H<inf>2</inf>O containing mostly intercalated water. The correlation between thermal analyses and AC properties points out that water molecules essentially contribute to the charge transport at ambient conditions of layered alkali titanates. This scenario might be potentially extended to other humidity-sensitive ceramics.
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    Structural, optical, and electrical properties of cellulose/titanate nanosheets composite with enhanced protection against gamma irradiation
    (2023-10-01) ;
    Kwamman, Tanagorn
    ;
    Pulphol, Phieraya
    ;
    ;
    Charoonsuk, Thitirat
    Two-dimensional (2D) materials have emerged as a promising functional filler in nanocomposites due to their unique anisotropy and resilience to harsh conditions. We report herein the use of Ti<inf>0.91</inf>O<inf>2</inf> nanosheets as a protective component against γ-irradiation to cellulose paper. The titanate nanosheets were prepared via a sequence of solid-state synthesis of lepidocrocite-type Cs<inf>0.7</inf>Ti<inf>1.825</inf>O<inf>4</inf>, proton exchange to H<inf>0.7</inf>Ti<inf>1.825</inf>O<inf>4</inf>·H<inf>2</inf>O, and exfoliation with tetrabutylammonium hydroxide. The nanosheets were incorporated into the commercial cellulose filter paper by a simple dip coating up to 0.6 mg cm<sup>−2</sup>, equivalent to 10 wt% TiO<inf>2</inf>. The nanosheets distribution was demonstrated by energy dispersive X-ray (EDX) mapping, synchrotron radiation X-ray tomographic microscopy (SRXTM), and atomic force microscopy (AFM). It is found that γ-irradiation (up to 50 kGy) destroyed the cellulose Iβ crystallinity of uncoated paper, but this is less pronounced in the cellulose/titanate nanosheets composite. This was also confirmed by the lack of a 235 nm-absorption characteristics of irradiation-induced decomposition product(s) in nanosheets-containing papers, which also exhibit UVA shielding property. The coated samples remained white while the uncoated ones were darkened with γ-irradiation. In addition, the nanosheets-coated papers showed dielectric permittivity, loss tangent, and AC conductivity which were invariant of the γ-dose, unlike those from the uncoated ones. Our work demonstrates the use of lead-free Ti<inf>0.91</inf>O<inf>2</inf> nanosheets as a γ-shielding component to slow down/prevent structural, optical, and electrical properties damages in cellulose paper, which could extend to other nature-derived materials.
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    Phase evolution, microstructure and electrical response of KNNT ceramics with Li+ substitution and doping
    (2022-01-01)
    Yotthuan, Surirat
    ;
    Udeye, Thanya
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    Prasertpalichat, Sasiphon
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    Pulphol, Phieraya
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    Lead-free (K<inf>0.5</inf>Na<inf>0.5</inf>)(Nb<inf>0.7</inf>Ta<inf>0.3</inf>)O<inf>3</inf> (KNNT) ceramics with Li<sup>+</sup> substitution (KN<inf>0.5-x</inf>Li<inf>x</inf>NT) and direct (KNNT-xLi) doping at x = 0, 0.01, 0.02, 0.03 and 0.04 mol% were synthesized by the solid-state combustion route. The phase, microstructure, dielectric and ferroelectric properties of the ceramics were examined. The XRD pattern of the ceramics revealed orthorhombic and tetragonal phases in all specimens. The Rietveld refinement procedure showed that increasing either the Li<sup>+</sup> substitution or doping levels enhanced the amount of the tetragonal phase. It was found that Li<sup>+</sup> doping, either substitutional or additional, enhanced the Curie temperature (T <inf>C</inf>) by increasing the tetragonal distortion, while the dielectric constant (ε <inf>C</inf>) decreased. The good remanent P-E loops of the KN<inf>0.5-x</inf>Li<inf>x</inf>NT ceramics were found with x = 0.01 (P <inf>r</inf>∼10.89 µC/cm<sup>2</sup> and E <inf>C</inf>∼13.09 kV/cm), while for KNNT-xLi ceramics, it was obtained with x = 0.02 (P <inf>r</inf>∼15.65 µC/cm<sup>2</sup> and E <inf>C</inf>∼11.46 kV/cm), which were confirmed by remanent P-E hysteresis measurements.
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    Effect of Adsorbed Water and Temperature on the Universal Power Law Behavior of Lepidocrocite-Type Alkali Titanate Ceramics
    (2021-06-17)
    Sriphan, Saichon
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    Pulphol, Phieraya
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    Charoonsuk, Thitirat
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    ;
    The ubiquitous (re)adsorption of atmospheric water by functional ceramics leads to some applications such as humidity sensing; at the same time, this phenomenon complicates the understanding of the nature of original conducting species. We presented herein the effects of adsorbed water on the electrical properties and charge transport of K0.8Zn0.4Ti1.6O4, Cs0.7Zn0.35Ti1.65O4, and Cs0.6K0.1Zn0.35Ti1.65O4 lepidocrocite-type alkali titanate ceramics. A small amount of atmospheric water (0.02-0.33 mol/mol) is merely adsorbed on the external surface but not intercalated into the interlayer space. In temperature scan experiments, water sorption leads to the dielectric permittivity/loss hysteresis loops, where the values upon cooling are unusually larger than those upon heating. In frequency scan experiments, multiple frequency- and temperature-dependent anomalies are detected. The AC conductivity was fitted to the Jonscher universal power law response (σ′AC = σDC + Aωs) from 101 to 106 Hz and 400-25 °C. We observed an uncommon U-shaped A(T) but an inverted U-shaped s(T), regardless of the interlayer ion, charge per formula unit, or pellet density. These plots allow a qualitative description of (i) the apparent activation energy, (ii) the effective dimension of the conduction pathway, and (iii) the charge carrier concentration, all as a function of the temperature under the influence of atmospheric water. Our physical interpretation is potentially applicable to other systems, providing insights into the (unintentional) water-induced conductions and complementing rigorous but time-consuming investigations by controlled humidity experiments.
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    Alternating current properties of bulk- and nanosheet-graphitic carbon nitride compacts at elevated temperatures
    (2023-08-23) ;
    Pulphol, Phieraya
    ;
    Chaithaweep, Kanokwan
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    Dabsamut, Klichchupong
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    Kobkeatthawin, Thawanrat
    The investigations of temperature-dependent electrical properties in graphitic carbon nitride (g-C<inf>3</inf>N<inf>4</inf>) have been largely performed at/below room temperature on devices commonly fabricated by vacuum techniques, leaving the gap to further explore its behaviors at high-temperature. We reported herein the temperature dependence (400 → 35 °C) of alternating current (AC) electrical properties in bulk- and nanosheet-g-C<inf>3</inf>N<inf>4</inf> compacts simply prepared by pelletizing the powder. The bulk sample was synthesized via the direct heating of urea, and the subsequent HNO<inf>3</inf>-assisted thermal exfoliation yielded the nanosheet counterpart. Their thermal stability was confirmed by variable-temperature X-ray diffraction, demonstrating reversible interlayer expansion/contraction upon heating/cooling with the thermal expansion coefficient of 2.2 × 10<sup>−5</sup>-3.1 × 10<sup>−5</sup> K<sup>−1</sup>. It is found that bulk- and nanosheet-g-C<inf>3</inf>N<inf>4</inf> were highly insulating (resistivity ρ ∼ 10<sup>8</sup> Ω cm unchanged with temperature), resembling layered van der Waals materials such as graphite fluoride but unlike electronically insulating oxides. Likewise, the dielectric permittivity ϵ′, loss tangent tan δ, refractive index n, dielectric heating coefficient J, and attenuation coefficient α, were weakly temperature- and frequency-dependent (10<sup>3</sup>-10<sup>5</sup> Hz). The experimentally determined ϵ′ of bulk-g-C<inf>3</inf>N<inf>4</inf> was reasonably close to the in-plane static dielectric permittivity (8 vs. 5.1) deduced from first-principles calculation, consistent with the anisotropic structure. The nanosheet-g-C<inf>3</inf>N<inf>4</inf> exhibited a higher ϵ′ ∼ 15 while keeping similar tan δ (∼0.09) compared to the bulk counterpart, demonstrating its potential as a highly insulating, stable dielectrics at elevated temperatures.