Microwave dielectric properties of Na<Superscript>+</Superscript> and M<Superscript>3+</Superscript>-doped Ba(Mg<Subscript>0.5</Subscript>W<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> ceramics

In this study, phase evolution, microstructure, and microwave dielectric properties of (Ba_0.98Na_0.02)(Mg_0.48M³⁺_0.02W_0.5)O₃ (M³⁺?=?Al, Ga, Sc, In, Yb, Y, Dy, Gd, and Sm) ceramics sintered at 1700 °C for 1 h were investigated. All the compounds exhibited an ordered cubic perovskite structure. Regardless of the ionic radius of the doped M³⁺ ions, BaWO₄ was detected as the secondary phase in all the compounds. The field emission scanning electron microscopy (FE-SEM) images revealed a dense microstructure in all the compounds, except in the Al-doped compound, which exhibited an insufficient grain growth. The large and irregularly shaped grains indicated that the liquid phase sintering occurred. Splitting of the A_1g(O) mode was observed in the Raman spectra of large M³⁺ ion-doped compounds. Splitting of the F_2g modes did not occur and the bands were sharp, indicating that the cubic symmetry was retained. As the ionic radius of the doped M³⁺ ions increased, the dielectric constant (ε_r) increased slightly. The compounds doped with M³⁺?=?Sc, In, Yb, and Y exhibited a very high quality factor (Q?×?f₀) in the range of 250,000 ~ 280,000 GHz. In the case of the compounds doped with M³⁺?=?Al, Ga, Sc, In, Yb, Y, and Dy, the value of the temperature coefficient of resonant frequency (τ_f) was in the range of ?24 ~ ?19 ppm/°C, while the Gd and Sm-doped compounds exhibited positive values of 2.8 and 31.2 ppm/°C, respectively. The dielectric constant, quality factor, and temperature coefficient of resonant frequency of the In-doped compound, i.e., (Ba_0.98Na_0.02)(Mg_0.48In_0.02W_0.5)O₃, were 18.7, 286,557 GHz, and???24.4 ppm/°C, respectively.     

Effect of Ca substitution by Fe on the thermoelectric properties of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> ceramics

(Ca_1-xFe_x)₃Co₄O₉ polycrystalline samples (x?=?0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1 and 0.2) have been prepared by solid state reaction and sintered by spark plasma sintering. Their thermoelectric properties have been studied between 323 and 1000 K. The substitution limit is low (< 3%). For higher iron contents, formation of Co₃O₄, Ca₂FeCoO₅ and a calcium ferrite compound occurs. Concerning electrical conductivity and power factor, an optimum value exists for x?=?0.03 substitution. This optimum power factor is circa 10% higher than the one of the unsubstituted sample. The optimum thermal diffusivity is measured for the sample with x?=?0.02 and is circa 9% lower than the one of the unsubstituted sample. Therefore, the dimensionless figure of merit ZT is finally increased by 14% for the (Ca_0.98Fe_0.02)₃Co₄O₉ and (Ca_0.97Fe_0.03)₃Co₄O₉ compositions.     

Effect of transition metal substitution on elastoplastic properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel

LiMn₂O₄ (LMO) derivatives partially substituted with transition metals (e.g., Ni) have received attention for their higher energy density achieved at higher charge voltage than pure LMO, and may be attractive cathode candidates for emerging all solid state batteries. Accurate mechanical properties of these high voltage spinels are required for prediction of electrode and electrolyte fracture that may compromise battery lifetime and performance. Here, we quantified the Young’s elastic modulus E and hardness H for LMO, LiMn_1.5Ni_0.5O₄ (LMNO), and LiMn_1.5Ni_0.42Fe_0.08O₄ (LMNFO) spinel microparticles via instrumented grid nanoindentation. Elastic modulus E and hardness H increased by more than 40% (up to 145 and 11 GPa, respectively) as a result of Ni or Ni/Fe substitution; such substitution also reduces the lattice parameter and increases the oxidization state of Mn. These results demonstrate how changes in transition metal occupancy can significantly affect the mechanical properties of LMO spinel, and provide critical parameters for designing against fracture in all solid state batteries.     

Temperature dependence photo-luminescence of Nd<Superscript>3+</Superscript> doped PLZT ceramic

Temperature dependence of photo-luminescence for Nd³⁺ doped PLZT(9/65/35) was measured across its structural phase transition temperature. The absorption corresponding to ⁴ I _9/2 → ⁴ F _5/2, ² H _9/2 energy level near 808 nm was used for exciting the sample. The major emission bands at 0.9, 1.06, and 1.34 μm were observed. No shift in the peak position of these emission bands was observed across the diffused structural transition with increase in temperature. However, a 10% increase in FWHM was observed. The absence of any discernible peak shift is attributed to the shielding of the intra-configurational 4f-4f transitions, in trivalent Nd³⁺ ions, by external 5 s and 5d orbitals. The red shifted phonon side bands appeared with increase in temperature.     

Structure and properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-0.38PbTiO<Subscript>3</Subscript> ceramics with MPB composition

0.62Bi(Mg_1/2Ti_1/2)O₃-0.38PbTiO₃-xwt%Bi₂O₃ (BMT-0.38PT-xBi₂O₃) ceramics were prepared by conventional powder-processing method. It indicated that the morphotropic phase boundary (MPB) region located in 0.0?≤?x?≤?0.3. For x?=?0.3, it exhibited good piezoelectric properties, d₃₃ ~245pC/N and k_p ~40 %. With the increase of Bi₂O₃ content, the Curie temperature (T_c) was found to increase, and the dielectric loss was found to decrease above 200 °C compared with BMT-0.38PT sample. Finally, it can be found that depolarization temperature was around 350 °C by thermal depoling method.     

Effects of Processing Conditions on the Dielectric Properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

There have been a number of recent reports of anomalously large permittivities (ε _r ≈ 10⁴) in the material CaCu₃Ti₄O₁₂. The dielectric spectra is characterized by a large, relatively temperature independent permittivity near room temperature which exhibits a dielectric relaxation above 100 K. The crystal structure of CaCu₃Ti₄O₁₂ can be described as pseudo-perovskite with a cubic unit cell with a lattice constant of 7.391 Å. The ubiquitous occurrence of this dielectric behavior in ceramics, single crystals, and thin films suggests that the polarization is not related to a simple conducting grain/insulating grain boundary-type system. While the precise origin of the dielectric response is not entirely clear, in this work it is shown that processing conditions have a significant influence on the room temperature dielectric properties. Specifically, the permittivity and loss exhibit a strong dependence on the oxygen partial pressure and sintering time. In fact, studies of the effects of sintering time and supporting evidence from capacitance-voltage measurements conclusively show that there is no direct relationship between the permittivity and grain size, as is the case in classical boundary layer systems. Lastly, with aliovalent doping the room temperature dielectric properties can be optimized to provide a high permittivity (ε _r ～ 8,000) dielectric with relatively low loss (tan δ < 0.05 at 1 kHz).     

Influence of the processing rates and sintering temperatures on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

The stoichiometric CaCu₃Ti₄O₁₂ pellets were prepared by the solid state synthesis. X-ray diffraction data revealed the tenorite CuO and cuprite Cu₂O secondary phases on the unpolished CaCu₃Ti₄O₁₂ samples regardless of the heating rates. Also, the dielectric constant marked the highest for the CaCu₃Ti₄O₁₂ sample sintered at the lowest heating rate (1°C/min), which was explained by the increased grain conductivity due to the cation reactions. On the other hand, Cu₂O phase was found only on the unpolished CaCu₃Ti₄O₁₂ sample sintered over 1100°C and those are considered as the remains reduced from the CuO phase. The higher sintering temperature showed the increased dielectric constant and the loss tangent of the CaCu₃Ti₄O₁₂ samples, and this result could be interpreted by the impedance measurement data. The relationship between the processing condition and the dielectric properties was discussed in terms of the cation non-stoichiometry and the defect chemistry in CaCu₃Ti₄O₁₂.     

Influence of the calcination procedure on the thermoelectric properties of calcium cobaltite Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript>

Calcium cobaltite is one of the most promising oxide p-type thermoelectric materials. The solid-state reaction (or calcination, respectively), which is well known for large-scale powder synthesis of functional materials, can also be used for the synthesis of thermoelectric oxides. There are various calcination routines in literature for Ca₃Co₄O₉ powder synthesis, but no systematic study has been done on the influence of calcination procedure on thermoelectric properties. Therefore, the influence of calcination conditions on the Seebeck coefficient and the electrical conductivity was studied by modifying calcination temperature, dwell time, particle size of raw materials and number of calcination cycles. This study shows that elevated temperatures, longer dwell times, or repeated calcinations during powder synthesis do not improve but deteriorate the thermoelectric properties of calcium cobaltite. Diffusion during calcination leads to idiomorphic grain growth, which lowers the driving force for sintering of the calcined powder. A lower driving force for sintering reduces the densification. The electrical conductivity increases linearly with densification. The calcination procedure barely influences the Seebeck coefficient. The calcination procedure has no influence on the phase formation of the sintered specimens.     

Effects of MnO<Subscript>2</Subscript> addition on microstructure and electrical properties of (Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>) <Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>TiO<Subscript>3</Subscript> ceramics

In this letter, MnO₂-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT-6) lead-free piezoelectric ceramics were synthesized by solid state reaction, and the microstructure and electrical properties of the ceramics were investigated. X-ray diffraction (XRD) reveals that all specimens take on single perovskite type structure, and the diffraction peaks shift to a large angle as the MnO₂ addition increases. Scanning electron microscopy shows that the grain sizes increases, and then decreases with increasing the MnO₂ content. The experiment results indicate that the electrical properties of ceramics are significantly influenced by the MnO₂ content, and the ceramics with homogeneous microstructure and excellent electrical properties are obtained with addition of 0.3 wt% MnO₂ and sintered at 1160°C. The piezoelectric constant (d₃₃), the electromechanical coupling factor (k _p ), the dissipation factor (tan δ) and the dielectric constant (ɛ _r ) reach 160 pC/N, 0.29, 0.026 and 879, respectively. These excellent properties indicate that the MnO₂-doped BNBT-6 ceramics can be used for actuators.     

Ionic conduction and crystal structure of aluminum doped NASICON-type LiGe<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> glass-ceramic crystallized at different times and temperatures

In this communication, NASICON-type glass-ceramic (lithium germanium phosphate, LiGe₂(PO₄)₃) was prepared as lithium super ionic conductor using aluminum as dopant for ionic conduction improvement. The solid solution was Li_1?+?xAl_xGe_2-x(PO₄)₃ (x?=?0.5) that Ge⁴⁺ ions were partially substituted by Al³⁺ ions in crystal structure. Initial glasses were converted to glass-ceramics at different times and temperatures for maximum ionic conduction achievement. The crystals were characterized by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy-Dispersive X-ray spectroscopy (EDX), Differential Scanning Calorimetry (DSC) and Complex Impedance Spectroscopy (CIS) methods. The maximum lithium ion conductivity for glass-ceramic, 5.32?×?10^?3 S/cm at 26 °C was obtained for specimen crystallized at 850 °C for 8 h with minimum activation energy of 0.286 eV. Increasing the crystallization temperature results in secondary phase formation in grain boundary and increasing in crystallization time results in microcracks formation in specimen. Both phenomena decreased the ionic conductivity.     

Effect of Ca substitution on microwave dielectric properties of BaV<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics

Effects of Ca substitution for Ba on the phase composition, microstructure, sintering behavior and microwave dielectric properties of nominal ceramics Ba_1-xCa_xV₂O₆ (0.2?≤?x?≤?0.5) were investigated. The XRD, Raman and SEM results revealed that BaV₂O₆ and CaV₂O₆ composite ceramics were formed. Nominal ceramics Ba_1-xCa_xV₂O₆ could be well densified at about 550 °C via a solid-state reaction method. The microwave dielectric properties exhibited strong dependence on the composition and microstructure. Typically, the Ba_0.7Ca_0.3V₂O₆ ceramics sintered at 550 °C exhibited excellent microwave dielectric properties: ε_r?=?10.9, Qxf?=?17,100 GHz (at 9.9 GHz), and τ_f?=?4 ppm/°C. Meanwhile, Ba_0.7Ca_0.3V₂O₆ ceramics also showed good chemical compatibility with Al electrode. These results indicated that the Ba_0.7Ca_0.3V₂O₆ ceramics could be a promising candidate for the ULTCC technology.     

Excellent dielectric constants observed in heterogeneous conduction Ba(Zr<Subscript>0.25</Subscript>Ti<Subscript>0.75</Subscript>)O<Subscript>3</Subscript> ceramics doped with Sr(Fe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>)O<Subscript>3</Subscript>

The (1-x)Ba(Zr_0.25Ti_0.75)O₃-xSr(Fe_0.5Nb_0.5)O₃ or (1-x)BZT-xSFN ceramics have been fabricated via a solid-state reaction technique. All ceramics exhibit a pure phase perovskite with cubic symmetry. The addition of a small amount of SFN (x?=?0.1) produces an obvious change in dielectric behavior. Very high dielectric constants (ε_r?>?164,000 at 1 kHz and temperature?>?150°C) are observed and the value is obviously higher than dielectric constants for Ba(Zr_0.25Ti_0.75)O₃ and Sr(Fe_0.5Nb_0.5)O₃ ceramics. The ferroelectric measurement data suggests that the unmodified sample exhibited a ferroelectric behavior. However, a transformation from a ferroelectric to a relaxor-like behavior is noted with increasing x concentration. Impedance Spectroscopy (IS) analysis indicates that the presence of excellent dielectric constants is due to the heterogeneous conduction in the ceramics after adding SFN, which can be explained in terms of the Maxwell-Wagner polarization mechanism.     

Dielectric properties of pure and Mn-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics over a wide temperature range

The effect of manganese doping on the dielectric properties of CaCu₃Ti_4-xMn_xO₁₂ (x?=?0, 0.02, 0.04) were investigated over a broad temperature range (93–723 K) in the frequency range from 100 Hz to 10 MHz. Two dielectric relaxations and two dielectric anomalies were observed. The low-temperature relaxation appearing in the temperature range below 200 K is the characteristic relaxation for CaCu₃Ti₄O₁₂. This relaxation was attributed to the polaron relaxation due to electron hopping between Ti³⁺ and Ti⁴⁺ states. Due to the negative factors of notable decreases in the Ti³⁺/Ti⁴⁺ and Cu³⁺/Cu²⁺ ratios and the concentration of oxygen vacancies as revealed by X-ray photoemission spectroscopy, Mn-doping was found to gradually destroy rather than move this relaxation to a higher temperature. The high-temperature relaxation occurring around room temperature was found to be a Maxwell-Wagner relaxation caused by grain boundaries. Our results confirm that the colossal dielectric behavior in the tested samples results from both polaron and Maxwell-Wagner relaxations, but is predominated by the latter relaxation. The low-temperature anomaly behaves as a phase-transition-like behavior. It was argued to be created by oxygen vacancies transition from static disorder to dynamic disorder. The high-temperature anomaly is an artificial effect caused by negative capacitance.     

Dielectric and Piezoelectric Properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-K<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-NaNbO<Subscript>3</Subscript>Lead-Free Ceramics

The ternary lead-free piezoelectric ceramics system of (1 – x) [0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃] – xNaNbO₃(x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) were synthesized by conventional solid state reaction method. The crystal structure, dielectric, piezoelectric properties and P-E hysteresis loops were investigated. The crystalline structure of all compositions is mono-perovskite phase ascertained by XRD, and the lattice constant was calculated from the XRD data. Temperature dependence of dielectric constant _r and dissipation factor tan measurement revealed that all compositions experienced two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric, and these two phase transitions have relaxor characteristics. Both transition temperatures T_d and T_m are lowered due to introduction of NaNbO₃. P-E hysteresis loops show that 0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃ ceramics has the maximum P_r and E_c corresponding to the maximum values of electromechanical coupling factor K_p and piezoelectric constant d_33. The piezoelectric constant d₃₃ and electromechanical coupling factor K_p decrease a little, while the dielectric constant ₃₃^T/₀ improves much more when the concentration of NaNbO₃ is 8 mol%.     

Multiferroic,magnetoelectric and magneto-impedance properties of NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/(Pb,Sr) TiO<Subscript>3</Subscript> bilayer films

We prepared NiFe₂O₄/(Pb, Sr)TiO₃ (NFO/PST) bilayer films by the chemical solution method and investigated their multiferroic, magnetoelectric and magneto-impedance properties. Multiferroic properties have been observed at room temperature. The bilayer films exhibit saturation polarization P _s ? 26.6 μC/cm² and saturation magnetization M _s ? 134 emu/cm³. With increasing Sr content, M _s. and P _s values of the NFO/PST bilayer films decrease. The variation may be ascribed to the influence of interfacial strain and decrease in tetragonality. High magnetoelectric coupling effect has been observed in the NFO/PST bilayer films with maximum value of α _E  = 6.35 Vcm^?1 Oe^?1 measured at H _DC  ~ 1 kOe and f ~ 10 kHz for Sr ~ 10% (NFO/PST10). The magneto-impedance measurements establish a strong dependence on magnetic field, further confirming magnetoelectric response in NFO/PST bilayer films. An alternative approach for impedance analysis of NFO/PST10 bilayer film provides direct evidence of strain mediated magnetoelectric coupling at room temperature. The results indicate that NFO/PST bilayer films can be considered as a potential multiferroic magnetoelectric material.     

Influence of substitution on dielectric diffuseness in Ba<Subscript>(1-x)</Subscript>Bi<Subscript>(2+2x/3)</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics prepared by chemical precursor decomposition method

Barium bismuth niobate, Ba_(1-x)Bi_(2+2x/3)Nb₂O₉ (BBN with x = 0.0, 0.1, 0.2, 0.3, 0.4) ceramic powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). The single phase layered perovskite was prepared throughout the composition range studied. No intermediate phase was found during heat treatment at and above 600°C. The crystallite size and the particle size, obtained from XRD and TEM respectively, were in the range of 15–30 nm. The addition of Bi₂O₃ substantially improved the sinterability associated with high density (96%) which was otherwise difficult in the case of pure BaBi₂Nb₂O₉ (BBN x = 0.0). The sintering was done at 900°C for 4 h. The relative permittivity of BBN ceramics at both room temperature and in the vicinity of the temperature of maximum permittivity (T_m) has increased significantly with increase in bismuth content and loss is also decreased to a certain level of bismuth doping. T_m increased with increase in Bi₂O₃. The diffuseness (γ) in the phase transition was found to increase from 1.54 to 1.98 with the increase in Ba²⁺ substitution level from x = 0.0 to x = 0.3.     

Studies of structural,dielectric and impedance properties of Bi<Subscript>9</Subscript>Fe<Subscript>5</Subscript>Ti<Subscript>3</Subscript>O<Subscript>27</Subscript> ceramics

Bi₉Fe₅Ti₃O₂₇ is an eight-layered material belonging to the family of bismuth layered structured ferroelectromagnets. The polycrystalline sample of this compound was prepared by a standard solid-state reaction technique. The formation of the compound in an orthorhombic crystal structure was confirmed by an X-ray diffraction (XRD) technique (lattice parameters: a?=?5.5045[27] Å, b?=?5.6104[27] Å, c?=?76.3727[27] Å). Detailed studies of surface morphology of the compound using scanning electron microscopy (SEM) exhibit that the compound has domains of plate shaped grains. Studies of dielectric and electric properties in a wide temperature range (30–500 °C) at different frequencies (100 Hz–1 MHz) exhibit an anomaly at 291?±?2 °C, which is related to ferroelectric to paraelectric phase transition as suggested by hysteresis loop at room temperature. The values and nature of temperature variation of dc conductivity exhibit the NTCR behavior of the compound.     

Raman and infrared spectroscopy of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> - BaTiO<Subscript>3</Subscript> ceramics

Lead-free Na_0.5Bi_0.5TiO₃ -BaTiO₃ ceramics have been prepared in the whole range of concentrations and studied at room-temperature by means of X-ray, Raman scattering and infrared techniques. X-ray measurements revealed rhombohedral, rhombohedral-tetragonal boundaries and tetragonal modifacations depending on the contents of BaTiO₃. The distinct changes of the Raman and infrared spectra with increasing of BaTiO₃ content, which were correlated with X-ray results, were observed. The broad phonon spectra indicated the disorder in the A site of Na_0.5Bi_0.5TiO₃ -BaTiO₃ system.     

Structural,dielectric and magnetic properties of particulate composites of relaxor (BaTi<Subscript>0.85</Subscript>Sn<Subscript>0.15</Subscript>O<Subscript>3</Subscript>) and ferrite (NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>) synthesized by gel-combustion method

Particulate composites of (1-x) BaTi_0.85Sn_0.15O₃ – x NiFe₂O₄ (with x?=?5, 10,15 and 20 wt%) were synthesized using the solid-state reaction method by sintering at 1350 °C for 4 h. Formation of the diphase composites was confirmed by X-ray diffraction (XRD) and Fourier Transform Infra-red (FTIR) techniques. Temperature (RT-200 °C) and frequency (20 Hz- 1 MHz) dependent of AC conductivity, dielectric constant and dissipation have been studied. The dielectric constant exhibits strong frequency dispersion in the range 20 Hz-1 kHz which is attributed to Maxwell-Wagner interfacial polarization occurring at grain-grain-boundaries interface/interface of grains of BTS-NF. The M-H curve of all the composites exhibited a hysteresis loops typical charcateistic of a ferromagnetic material. The ferromagnetic ordering in the composites on account of NiFe₂O₄ as a constituent is explained using bound magnetic polarons (BMPs) model. The experimental magnetic data have been fitted to BMP model. Value of M_s is smaller, whereas of H_c and M_r are higher of the composites compared to value for NiFe₂O₄. The temperature at which divergence in the M vs. T plot in ZFC and FC starts is higher for the composites than for NiFe₂O₄.     

Preparation of superconductive P3 cobalt oxyhydrates Na<Subscript>x</Subscript>(H<Subscript>2</Subscript>O)<Subscript>y</Subscript>CoO<Subscript>2</Subscript> with three-layered CoO<Subscript>2</Subscript> using NaMnO<Subscript>4</Subscript> solution

We report the synthesis of the superconductive P3 cobalt oxyhydrates by immersing α-NaCoO₂ in aqueous NaMnO₄ solution for the first time. It is a novel route to form the superconductive phase of cobalt oxyhydrates without resort to the commonly used Br₂/CH₃CN solution. Topotactic transformation of the parent compound α-NaCoO₂ results in water intercalation and hence a significant expansion of the c-axis in the unit cell. The P3 cobalt oxyhydrates exhibits an onset superconducting transition at about 4.2 K.