Influence of calcium concentration on formation of tetravalent chromium doped Y3Al5O12 ceramics

Yttrium Aluminium Garnet (YAG) ceramics doped with chromium were prepared by solid-state reactive sintering in a vacuum. The influence of the charge compensator Ca²⁺ concentration on microstructure, optical properties and efficacy of Cr³⁺ oxidation to Cr⁴⁺ under air annealing was investigated. A non-monotonic dependence of these features on the amount of CaO as an additive was found. The changes in ceramic transparency and microstructure were explained considering the interaction between CaO and Cr₂O₃ at the ceramic grain boundaries, which leads to a different pore evolution in distinct samples during sintering. The efficacy of the oxidation of Cr³⁺ to Cr⁴⁺ strongly depends on the concentration of Ca dissolved in the YAG. The calcium solubility decreases due to the higher oxygen partial pressure of the extra phases on the grain boundaries that decreases the amount of generated Cr⁴⁺ ions. Such phenomenon explains the lower concentration of Cr⁴⁺ ions in the sample with 0.8% of Ca against the one with 0.5%. The experiment shows that the ceramic with 0.5% of Ca has a better in-line transmission and a higher concentration of Cr⁴⁺ ions in comparison with samples with a different Ca concentration.     

Influence of Cr doping on the phase composition of Cr,Ca:YAG ceramics by solid state reaction sintering

In the present work, the influence of Cr and Ca co-additives on the phase formation under conditions emulated the real sintering process of Cr⁴⁺:YAG ceramics is studied. The XRD analysis of the treated samples revealed the difference in formation rates of intermediate phases between the samples with and without the Cr₂O₃ additive. The formation of intermediate phases in the solid-state reaction between Y₂O₃ and Al₂O₃ is observed to shift toward higher temperatures (ie, toward the stage of fast shrinkage) if the mixture of Cr₂O₃ and CaO is added. The reason for such shift is the appearance of new intermediate, which contains Cr⁴⁺ ions in perovskite structure, as has been established by optical absorption and luminescent investigations. It is found that the Cr,Ca:YAG ceramics prepared by vacuum solid state reaction sintering at 1750°C, 10 hours possesses better optical transparency than Ca:YAG ceramics prepared under the same conditions.     

Effect of Ca2+ and Mg2+ ions on the sintering and spectroscopic properties of cr-doped yttrium aluminum garnet ceramics

In this work, we investigated the effects of Ca²⁺ and Mg²⁺ ions and annealing temperature on the spectroscopic parameters of chromium-doped yttrium aluminum garnet ceramics (Cr:YAG). Samples were obtained with either a separate or a simultaneous addition of calcium and magnesium oxides. To achieve this, aqueous suspensions were prepared using Y₂O₃, Al₂O₃, Cr₂O₃, MgO, and CaO high-purity powders as raw materials. The obtained suspensions were freeze-granulated, pressed into pellets, debinded, and subjected to reactive sintering in vacuum at 1715°C for 6 h. Each material was annealed in air with temperatures between 1300 and 1700°C. Samples were also compared to Cr:YAG ceramics with the addition of silica as a sintering aid. All the materials obtained were then exposed to 445 nm excitation, and emission spectra in the visible and infrared wavelengths were recorded. The results showed that the emission spectra of Cr:YAG ceramics varied according to the annealing conditions: as-sintered samples exhibited strong emissions of around 680 nm and, after air annealing, of around 1400 nm. This phenomenon is attributed to the Cr³⁺→Cr⁴⁺ transition. Samples doped solely with MgO exhibited the highest emission intensity in the infrared region. Thus, Mg²⁺ ions provided the best conversion efficiency of chromium ions.     

Assessment of conversion efficiency of Cr4+ ions by aliovalent cation additives in Cr:YAG ceramic for edge cladding

0.25at.% Cr:YAG ceramics were successfully fabricated as the edge cladding of Yb:YAG transparent ceramic slabs through vacuum sintering of co‐precipitated powders, using oxide additives to introduce different cations. The effects of various cation additives (Si⁴⁺, Ca²⁺, and Si⁴⁺ + Ca²⁺) on the conversion efficiency of Cr⁴⁺ ions and optical characteristics of the Cr:YAG edge cladding were investigated. Measurements of the absorption spectra of the Cr:YAG ceramics without any additives revealed 2 absorption bands centered at 430 nm and 600 nm, which imparted the sample with a green color. The introduction of only Si⁴⁺‐bearing additive did not promote the transition of Cr ions from the 3+ to 4+ state. Theoretical analysis and experimentation revealed that the addition of CaO not only enhanced the microstructure and improved the transmittance of the Cr:YAG ceramic, but also introduced vacancies that assisted in the formation of Cr⁴⁺ ions. It was determined that CaO has the same effect on the conversion efficiency of Cr⁴⁺ ions whether it is added as a single additive or in combination with SiO₂. The underlying mechanisms by which these aliovalent cation additives influence the formation of Cr⁴⁺ ions and affect optical properties are discussed in detail. High quality composite ceramics with Yb:YAG transparent ceramic slabs and dark brown‐colored Cr⁴⁺: YAG ceramic edge cladding were achieved through the addition of 0.05 wt.% CaO to the edge cladding, with no interfacial effects between the 2 regions being observed.     

Sintering additives regulated Cr ion charge state in Cr doped YAG transparent ceramics

Cr: YAG and Cr, Nd: YAG transparent ceramics have significant application prospects in solid state lasers, therefore a controllable charge state of Cr ion in Cr doped YAG transparent ceramics is necessary. In this study, a successful regulation of Cr charge state in both Cr, Nd: YAG and Cr: YAG transparent ceramics was achieved, by a simple optimizing the sintering additives. Both ceramics with the Cr doping concentration of 0.3?at% reached to the theoretical transmittance, after the vacuum sintering and the subsequent annealing process. It was found that by adopting silica additive, divalent charged Cr²⁺ ions could be detected from the vacuum sintered samples, and they were transferred into trivalent state after further annealing in air. Meanwhile, by vacuum sintering ceramics with divalent additives (CaO and MgO), a stable trivalent charged Cr ion could be obtained, and the subsequent air annealing process indicated a significant conversion from Cr³⁺ to Cr⁴⁺. Further increasing the Cr concentration was not benefit to the optical quality as well as the conversion of Cr³⁺ ion in Cr, Nd: YAG transparent ceramics.     

Effects of Sintering Aids on the Transparency and Conversion Efficiency of Cr4+ Ions in Cr: YAG Transparent Ceramics

Tetravalent chromium‐doped Y₃Al₅O₁₂ ceramics were fabricated by solid‐state reactive sintering method using high‐purity Y₂O₃, α‐ Al₂O₃, and Cr₂O₃ powders as the starting materials. CaO and MgO were co‐doped as the sintering aids. The effects of TEOS and divalent dopants (CaO and MgO) on the optical qualities, the conversion efficiency of Cr⁴⁺ ions, and the microstructure evolutions of 0.1 at.% Cr⁴⁺: YAG ceramics were investigated. Fully dense, dark brown colored Cr⁴⁺: YAG ceramics with an average grain size of 3.1 μm were achieved. The in‐line transmittance of the as‐prepared ceramic at 2000 nm was 85.3% (4 mm thick), and the absorption coefficient at 1030 nm (the characteristic absorption peak of Cr⁴⁺ ions) was as high as 3.7 cm^?1, which was higher than that of corresponding single crystals fabricated by Czochralski method.     

Synergetic effect of site-controlled two-step Ca doping on magnetic and electrical properties of M-type strontium hexaferrites

M-type strontium (SrM) hexaferrites exhibiting large magnetocrystalline anisotropy, high saturation magnetization and coercivity, and narrow ferrimagnetic resonance (FMR) linewidth have a great potential for applications in high-performance motors and self-biased circulators. Ca doping in SrM hexaferrites is an effective method for tailoring the intrinsic electromagnetic parameters and modifying polycrystalline microstructure to meet the application requirements. However, the regulation mechanism of Ca doping is still obscure, and its regulation effect is not optimized. Here, the magnetic and electrical properties of SrM hexaferrites with site-controlled two-step Ca doping are reported. The spatial concentration distribution and diffusion dynamics of Ca²⁺ ions are investigated when introduced by CaCO₃ as the reactant and sintering additive, respectively. The existence of the Ca²⁺ ions in the crystallites added as the reactant reduces the diffusion of the Ca²⁺ ions in the grain boundaries added as the additive, which synergistically tailors the magnetocrystalline anisotropy field, crystallite orientation, and polycrystalline morphology, and further optimizes the coercivity, remanence, and maximum energy product. Moreover, the impact of the Ca²⁺ ions on the resistivities of the grain and grain boundary is also investigated, revealing the synergetic effect of Ca²⁺ ions at different sites on lowering the loss. These results prove the effectiveness of the site-controlled two-step Ca doping in synergistically enhancing the magnetic and electrical properties of SrM hexaferrites.     

Annealing induced discoloration of transparent YAG ceramics using divalent additives in solid-state reaction sintering

Tetraethyl orthosilicate (TEOS) was commonly served as a sintering additive to promote the densification of transparent Y₃Al₅O₁₂ (YAG) ceramics. However, Si⁴⁺ that decomposed from TEOS would restrain the conversion of dopants into a higher valence state (e.g., Cr³⁺ → Cr⁴⁺). In this study, by using divalent sintering additives (CaO and MgO), the colorless and highly transparent YAG ceramics (T = 84.6%, at 1064 nm) were obtained after vacuum sintering at 1840 °C for 8 h and without subsequent annealing in air. An absorption peak centered at ∼320 nm was observed before annealing, and it extended to ∼550 nm after annealing at 1450 °C for 10 h in air. A discoloration phenomenon occurred and more scattering centers were observed with the formation of new [Mg/Ca²⁺F⁺] color centers. Air annealing did not improve the optical quality of the as-fabricated YAG ceramics with divalent dopants as sintering additives, owing to the formation of scattering centers.     

Influence of calcium doping concentration on the performance of Ce,Ca:LuAG scintillation ceramics

Ce,Ca:LuAG scintillation ceramics with different Ca²⁺ co-doping concentrations were prepared by the solid-state reaction method. The concentration of Ce³⁺ was fixed at 0.3 at% and the concentration of Ca²⁺ ranged from 0 to 1.2 at%. We systematically studied how the Ca²⁺ concentration affects the optical quality of Ce,Ca:LuAG ceramics by influencing the microstructure in the vacuum sintering and HIP post-treatment. Good optical transmittance could be obtained with Ca²⁺ concentrations between 0.05 and 0.8 at%, which reached 76.0–81.9 % at 520 nm. The PL and scintillation decay times decrease with increasing Ca²⁺ concentration up to 0.6 at% with no clear trend above this value. The light yield (LY) values at different shaping times decrease with increasing Ca²⁺ concentration but the fast scintillation component (LY_0.5 μs/ LY_3.0 μs) increases significantly from 79 % to 97 %. The co-doping of Ca²⁺ also reduces the afterglow level by more than one order of magnitude.     

Fabrication and properties of transparent Tb:YAG fluorescent ceramics with different doping concentrations

Terbium doped yttrium aluminum garnet (Tb:YAG) transparent ceramics with different doping concentrations were fabricated by the solid-state reaction method using commercial Y₂O₃, α-Al₂O₃ and Tb₄O₇ powders as raw materials. Samples sintered at 1750 °C for 20 h were utilized to observe the optical transmittance, microstructure and fluorescence characteristics. It is found that all the Tb: YAG ceramics with different doping concentrations exhibit homogeneous structures with grain size distributions around 22–29 µm. For the 5 at% Tb:YAG transparent ceramics, the grain boundaries are clean with no secondary phases. The photoluminescence spectra show that Tb:YAG ceramics emit predominantly at 544 nm originated from the energy levels transition of ⁵D₄→⁷F₅ of Tb³⁺ ions, and the intensity of the emission peak reaches a maximum value when the Tb³⁺ concentration is 5 at%. The in-line transmittance of the 5 at% Tb:YAG ceramics is 73.4% at the wavelength of 544 nm, which needs to be further enhanced by optimizing the fabrication process. We think that Tb:YAG transparent ceramics may have potential applications in the high-power white LEDs.     

Effect of oxygen treatment on structure and electrical properties of Mn-doped Ca0.6Sr0.4TiO3 ceramics

Different oxygen treatment methods, including O₂ and N₂ annealing, were conducted on Ca_0.6Sr_0.4TiO₃ (CST) ceramics with varying Mn content (0?mol%, 0.5?mol% and 2.0?mol%). Structure characterization, including XRD and SEM, indicated the minimal effect of annealing on the microstructure. Grain boundaries were found to be sensitive to oxygen treatments, and annealing in O₂ resulted in increased grain boundary resistance, while in N₂ led to the opposite result. The insulating properties of bulk ceramics were found to be dominated by grain boundaries. Both the concentration and mobility of oxygen vacancies were confirmed to affect the energy storage properties to some extent in this work.     

Grain-size effect on Cr3+ and F-centres photoluminescence in nanophase MgAl2O4 ceramics

Photoluminescence (PL) spectroscopy of transparent MgAl₂O₄ spinel ceramics with grain size between 100 and 300 nm was studied at 7 K temperature in the near-IR-VUV range of spectrum with synchrotron radiation excitation. The PL spectra were composed of optical transitions from spatially different regions of the ceramics, which analysis evidenced grain size effect on the emission line-shapes and intensities. In particular, emission of impurity Cr³⁺ ions, being structured in the crystalline bulk, became broad-band in the grain boundary regions, which was associated with respectively strong and weak local crystalline fields. It was observed that (i) excitons and F centres transfer energy to Cr³⁺ and (ii) Cr(²E_g)/Cr(⁴T_2g) and F-centres/Cr³⁺ PL intensity ratios underwent a linear dependence on the grain size.     

Improved non-ohmic and dielectric properties of Cr3+ doped CaCu3Ti4O12 ceramics prepared by a polymer pyrolysis solution route

CaCu_3-xCr_xTi₄O₁₂ (x?=?0.00–0.20) ceramics were prepared via a polymer pyrolysis solution route. Their dielectric properties were improved by Cr³⁺ doping resulting in an optimal dielectric constant value of 7156 and a low tanδ?value of 0.092 in a sample with x?=?0.08. This might have resulted from a decrease in oxygen vacancies at grain boundaries. XANES spectra confirmed the presence of Cu⁺ ions in all ceramic samples with a decreasing Cu⁺/Cu²⁺ ratio due to an increased content of Cr³⁺ ions. All CaCu_3-xCr_xTi₄O₁₂ ceramics showed nonlinear characteristic with improvement in both the breakdown field (E_b) and its nonlinear coefficient (α). Interestingly, the highest values of α, ～ 114.4, and that of E_b, ～8455.0?±?123.6?V?cm^?1, were obtained in a CaCu_3-xCr_xTi₄O₁₂ sample with x?=?0.08. The improvement of dielectric and nonlinear properties suggests that they originate from a reduction of oxygen vacancies at grain boundaries.     

Processing and properties of luminescent Cr3+ doped transparent alumina ceramics

Transparent Cr₂O₃-doped alumina ceramics were prepared by slip casting, followed by pre-sintering in ambient atmosphere and hot isostatic pressing. The effect of dopant concentration on material properties, including microstructure and optical properties was evaluated. Real in-line transmittance in the range of 20–44 % was measured for the ceramics with the mean grain size <520 nm: the transmittance decreased with increasing grain size and Cr content. The excitation spectra consisted of two broad bands with maxima at 404 nm and 558 nm, corresponding to ⁴A_2g → ⁴T_1g and ⁴A_2g → ⁴T_2g transitions of Cr³⁺ ions in octahedral sites of α-Al₂O₃. The intensive deep red narrow emissions under violet/green light excitation, R-lines (²E_g → ⁴A_2g transition), were observed at 692.5 nm and 693.8 nm, that are very close to ruby single crystal. The highest emission was achieved at the Cr³⁺ concentration of 0.4 at.%. The luminescence decay curves exhibited single-exponential behaviour with decay times of ∼3.6 ms.     

Effect of divalent cation addition on structure,conductivity and grain boundary properties in La doped ceria oxygen ion conductors

The aim of this work is to investigate the effect of divalent cations on the structure and electrical properties of Ce_0.85La_0.1D_0.05O_2-δ (D = Ca, Sr and Ba) oxygen ion conductors. The X-Ray structural analysis confirms the presence of CeDO₃ minor phase in addition to cubic fluorite phase of ceria in Sr²⁺ and Ba²⁺ added compositions. The lattice parameter of the compositions significantly depends on the ionic radius of dopants and the presence of D²⁺ ions in ceria lattice. The Ca²⁺ added composition shows the highest free oxygen vacancy concentration due to its lowest association energy and complete dissolution of Ca²⁺ ions into ceria lattice. The dopant-vacancy association energy and grain interior conductivity changes with the ionic radii of the divalent dopants. The grain boundary capacitance depends on dielectric constant, grain size and grain boundary thickness. The grain boundary conductivity shows 46% over total conductivity for Sr²⁺ added composition. The presence of CeDO₃ phase and space charge layer promotes the grain boundary resistances and affects the ion dynamics. Schematic models are proposed to understand the ion migration in grain boundaries. The scavenging effect is found to be highest in Sr²⁺ ions added composition. The defect structures, the presence of CeDO3 phase and electrical properties are correlated with each other.     

Gd3+ doping induced microstructural evolution and enhanced visible luminescence of Pr3+ activated calcium fluoride transparent ceramics

Transparent Pr³⁺ doped Ca_1-xGd_xF_2+x (x = 0, 0.01, 0.03, 0.06, 0.10, 0.15) polycrystalline ceramics with fine-grained microstructures were prepared by the hot-pressing method. The dependence of microstructure, optical transmittance, luminescence performances and mechanical properties on the Gd³⁺ concentrations for Pr³⁺:Ca_1-xGd_xF_2+x transparent ceramics were investigated. The Gd³⁺ ions show positive effects on the microhardness of Pr³⁺:Ca_1-xGd_xF_2+x transparent ceramics as a result of the decrease in the grain sizes. Excited by the Xenon lamp of 444 nm, typical visible emissions located at 484 nm, 598 nm and 642 nm were observed. Furthermore, the incorporation of Gd³⁺ ions can greatly enhance the photoluminescence performance owing to the improvement in the concentration quenching effect. The quenching concentration of Pr³⁺ ions in CaF₂ transparent ceramics increased to 1 at.% as a result of the positive effect of Gd³⁺ codoping. The energy transfer mechanism of Pr³⁺ in the Pr³⁺:Ca_1-xGd_xF_2+x transparent ceramics has been investigated and discussed.     

Structural,electrical, and magnetic transport properties of La0.72Ca0.28Mn1−xCrxO3 (0 ≤ x ≤ 0.06) ceramics

To obtain comprehensive materials with both high temperature coefficient of resistivity (TCR) and magnetoresistance (MR) at low magnetic fields, polycrystalline La_0.72Ca_0.28Mn_1?xCr_xO₃ (x = 0, 0.02, 0.04, 0.06) ceramics were prepared herein by sol–gel method. Electronic configuration of Cr³⁺ ions is similar to that of Mn⁴⁺ ions, therefore, successive substitution of Mn with Cr increases electrical resistivity and decreases metal–insulator transition temperature of ceramics, even yielding hump-like feature for Cr-rich (x = 0.06) samples. The best TCR (28.50%·K^?1) and MR (72.37%) values were obtained simultaneously at Cr dopant content of 0.02 (La_0.72Ca_0.28Mn_0.98Cr_0.02O₃). Strong response of the material to temperature and magnetic field was caused by minimal symmetry of orthorhombic structure and the most robust Jahn–Teller distortion. With increasing Cr content, Mn³⁺/Mn⁴⁺ or Mn³⁺/Cr³⁺ double exchange was diluted, and Cr³⁺/Cr³⁺ or Cr³⁺/Mn⁴⁺ superexchange was promoted. However, the internal competition effect was not conducive to the improvement of material properties.     

Highly-doped YAG:Sm3+ transparent ceramics: Effect of Sm3+ ions concentration

YAG:Sm³⁺ (3–15 at.%) transparent ceramics, a promising cladding material for suppressors of parasitic oscillations at 1064 nm of YAG:Nd³⁺ lasers, have been prepared by solid-state reactive sintering at 1725 °C. The effect of samarium ions concentration on the microstructure and optical properties of YAG:Sm³⁺ sintered ceramics was studied for the first time. The solubility limit of samarium ions in the garnet matrix was found to lie within the range of 9–11 at.%. The spectroscopic characterization of YAG:Sm³⁺ (3–15 at.%) ceramic samples showed that the absorption coefficients corresponding to Sm³⁺ ions transitions increased linearly with increasing Sm³⁺ doping. Also, the increase in the concentration of Sm³⁺ ions contributes to the increase in the intensities of the satellites, leading to the broadening of the main spectral lines and implicitly to the increase of the absorption coefficient around 1064 nm. It was shown that YAG:Sm³⁺ ceramics doped with 9 at.% Sm³⁺ ions possess optical losses of 0.07 cm^?1 at 808 nm and an optical absorption coefficient of 4.45 cm^?1 at 1064 nm. The concentration dependence of the ⁴G_5/2 level decay confirmed that the luminescence extinction is due to the energy transfer between the Sm³⁺ ions through cross-relaxation processes. All these results show that highly-doped YAG:Sm³⁺ (9 at.%) ceramics could be the best candidate for parasitic oscillation suppression in high-power YAG:Nd³⁺ lasers at 1064 nm.     

Effect of complex Si4++Mg2+ additive on sintering and properties of undoped YAG ceramics

The paper is devoted to studying of Si⁴⁺+Mg²⁺ complex additive for obtaining transparent YAG ceramics for laser applications. Ceramics were fabricated by reactive vacuum sintering of commercial Y₂O₃, Al₂O₃ powders taken in a stoichiometric mixture with TEOS and MgO as sintering aids. Microstructure and optical properties of YAG:Si⁴⁺,Mg²⁺ ceramics were investigated as a function of the Si⁴⁺/Mg²⁺ ratio. It was found that the influence of complex additive does not correspond to the direct superposition of known Si⁴⁺- and Mg²⁺-induced sintering mechanisms and involves interaction between Si⁴⁺ and Mg²⁺ ions during sintering. It was shown that C_Si/C_Mg> 1 provides more effective pore elimination and uniform microstructure when C_Si/C_Mg< 1 gives more intense inhibition of grain grown which may be important for scaling the size of ceramics.     

Enhancement of giant dielectric response in Ga-doped CaCu3Ti4O12 ceramics

The influences of Ga³⁺ doping ions on the microstructure, dielectric and electrical properties of CaCu₃Ti₄O₁₂ ceramics were investigated systematically. Addition of Ga³⁺ ions can cause a great increase in the mean grain size of CaCu₃Ti₄O₁₂ ceramics. This is ascribed to the ability of Ga³⁺ doping to enhance grain boundary mobility. Doping CaCu₃Ti₄O₁₂ with 0.25 mol% of Ga³⁺ caused a large increase in its dielectric constant from 5439 to 31,331. The loss tangent decreased from 0.153 to 0.044. The giant dielectric response and dielectric relaxation behavior can be well described by the internal barrier layer capacitor model based on Maxwell?Wagner polarization at grain boundaries. The nonlinear coefficient, breakdown field, and electrostatic potential barrier at grain boundaries decreased with increasing Ga³⁺ content. Our results demonstrated the importance of ceramic microstructure and electrical responses of grain and grain boundaries in controlling the giant dielectric response and dielectric relaxation behavior of CaCu₃Ti₄O₁₂ ceramics.