The Effects of Calcium‐to‐Phosphorus Ratio on the Densification and Mechanical Properties of Hydroxyapatite Ceramic

In this work, hydroxyapatite (HA) powders were synthesized using calcium hydroxide Ca(OH)₂ and orthophosphoric acid H₃PO₄ via wet chemical precipitation method in aqueous medium. Calcium‐to‐phosphorus (Ca/P) ratio was set to 1.57, 1.67, 1.87 that yield calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA, respectively. These synthesized HA powders (having different Ca/P ratio) were characterized in terms of particle size and microstructural examination. Then, the densification and mechanical properties of the calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA were evaluated from 1000 to 1350°C. Experimental results have shown that no decomposition of hydroxyapatite phase was observed for stoichiometric HA (Ca/P = 1.67) and calcium‐deficient HA (Ca/P = 1.57) despite sintered at high temperature of 1300°C. However, calcium oxide (CaO) was detected for calcium‐rich HA (Ca/P = 1.87) when samples sintered at the same temperature. The study revealed that the highest mechanical properties were found in stoichiometric HA samples sintered at 1100–1150°C, having relative density of ~99.8%, Young's modulus of ~120 GPa, Vickers hardness of ~7.23 GPa, and fracture toughness of ~1.22 MPam^1/2.     

Novel Series of Low‐Firing Microwave Dielectric Ceramics: Ca5A4(VO4)6 (A2+ = Mg,Zn)

Using a conventional solid‐state reaction Ca₅A₄(VO₄)₆ (A²⁺ = Mg, Zn) ceramics were prepared and their microwave dielectric properties were investigated for the first time. X‐ray diffraction revealed the formation of pure‐phase ceramics with a cubic garnet structure for both samples. Two promising ceramics Ca₅Zn₄(VO₄)₆ and Ca₅Mg₄(VO₄)₆ sintered at 725°C and 800°C were found to possess good microwave dielectric properties: ε_r = 11.7 and 9.2, Q × f = 49 400 GHz (at 9.7 GHz) and 53 300 GHz (at 10.6 GHz), and τ_f = ?83 and ?50 ppm/°C, respectively.     

Dielectric Properties of Ba0.8Ca0.2TiO3–Bi(Mg0.5,Ti0.5)O3–NaNbO3 Ceramics

Ceramics in the system 0.45Ba_0.8Ca_0.2TiO₃–(0.55?x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃, x = 0–0.02 were fabricated by a conventional solid‐state reaction route. X‐ray powder diffraction indicated cubic or pseudocubic symmetry for all samples. The parent 0.45Ba_0.8Ca_0.2TiO₃–0.55Bi(Mg_0.5Ti_0.5)O₃ composition is a relaxor dielectric with a near‐stable temperature coefficient of relative permittivity, ε_r = 950 ± 10% across the temperature range 80°C–600°C. Incorporation of NaNbO₃ at x = 0.2 extends the lower working temperature to ≤25°C, with ε_r = 575% ± 15% from temperatures ≤25°C to >400°C, and tan δ < 0.025 from 25°C to 400°C. Values of dc resistivity ranged from ~10⁹ Ω·m at 250°C to ~10⁶ Ω·m at 500°C. The properties suggest that this material may be of interest for high‐temperature capacitor applications.     

Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

Interfacial Reactions Between Anorthite (CaAl2Si2O8) and Al 7075 Alloy at 850°C and 1150°C

The present work reports an investigation of the interactions of Al 7075 alloy and anorthite at 850°C (150 h) and 1150°C (24 h). Transmission electron microscopy, electron probe microanalysis, X‐ray diffraction, and scanning electron microscopy coupled with energy‐dispersive spectroscopy were used to identify the mineralogical and microstructural changes at the metal–ceramic interface. At 850°C, the phase formation mechanisms were (a) Si⁴⁺–Al³⁺ interdiffusion between the Al alloy and anorthite to form calcium dialuminate (CA₂) and Ca²⁺–Mg²⁺ interdiffusion between the Al alloy and calcium dialuminate to form spinel. At 1150°C, spinel + Al₂O₃ and calcium hexaluminate (CA₆) + CA₂ were the major and minor phase mixtures, respectively in the corroded area. A thin layer of calcium monoaluminate (CA), gehlenite, and Si was present in the immediate vicinity of anorthite. The early stages of corrosion at 1150°C and 850°C were identical. However, due to thickening of the corroded region (viz., spinel formation) and enhanced evaporation of Mg at the higher temperature, the interdiffusion path evolves from Si⁴⁺–Al³⁺ + Ca²⁺–Mg²⁺ to Si⁴⁺–Al³⁺ + Ca²⁺–Al³⁺, thus establishing the following phase evolution path at the interface:      

Structural and Crystal Chemical Investigation of Intermediate Phases in the System Ca2SiO4–Ca3(PO4)2–CaNaPO4

Two intermediate compounds of the system Ca₂SiO₄–Ca₃(PO₄)₂–CaNaPO₄ were synthesized by reaction sintering at 1600°C and analyzed structurally, chemically, and optically. The structure of Ca₇(PO₄)₂(SiO₄)₂ nagelschmidtite (space group P6₁, a = 10.7754(1) Å, c = 21.4166(3) Å) was determined by single crystal X‐ray analysis. Its unit cell can be interpreted as a supercell (≈ 2 × a, 3 × c) of the high‐temperature polymorph α‐Ca₂SiO₄. Evidence for pseudo‐hexagonal symmetry is shown. Using electron microprobe, the solid solution Ca_7?xNa_x(PO₄)_2+x(SiO₄)_2?x, (x ≤ 2), of nagelschmidtite was confirmed. Volume thermal expansion coefficients of Ca_6.8Na_0.2(PO₄)_2.2(SiO₄)_1.8 and Ca_5.4Na_1.5(PO₄)_3.7(SiO₄)_0.3 were determined using high‐temperature X‐ray powder diffraction, yielding mean α_V = 3.95 and 5.21 [×10^?5/°C], respectively. Ca₁₅(PO₄)₂(SiO₄)₆ is a distinct phase in the binary section Ca₂SiO₄–Ca₃(PO₄)₂ and was found to extend into the ternary space according to Ca_15?xNa_x(PO₄)_2+x(SiO₄)_6?x, (x ≤ 0.1). Quenching experiments of the latter allowed for structural analysis of a strongly disordered, defective high‐temperature polymorph of the α‐Ca₂SiO₄–α‐Ca₃(PO₄)₂ solid solution. Structural relations between nagelschmidtite, Ca₁₅(PO₄)₂(SiO₄)₆ and the end‐member compounds of the system are discussed.     

Stability of High‐Temperature Dielectric Properties for (1 − x)Ba0.8Ca0.2TiO3–xBi(Mg0.5Ti0.5)O3 Ceramics

Ceramics in the solid solution system, (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃, were prepared by a conventional mixed oxide route. Single‐phase perovskite‐type X‐ray diffraction patterns were observed for compositions x < 0.6. A change from tetragonal to single‐phase cubic X‐ray patterns occurred at x ≥ 0.1. Dielectric measurements indicated relaxor behavior for x ≥ 0.1. Increasing the Bi(Mg_0.5Ti_0.5)O₃ content improved the temperature sensitivity of relative permittivity ?_r at high temperatures. At x = 0.5, a near‐plateau relative permittivity, 835 ± 40, extended across the temperature range, 65°C–550°C; the permittivity increased at x = 0.6 to 2170 ± 100 for temperatures 160°C–400°C (1 kHz). The corresponding loss tangent, tanδ, was ≤0.025 for temperatures between 100°C and 430°C for composition x = 0.5; at x = 0.6, losses increased sharply at >300°C. Comparisons of dielectric properties with other materials proposed for high‐temperature capacitor applications suggest that (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃ ceramics are a promising base material for further development.     

Structure,Mechanisms of Reaction,and Strength of an Alkali‐Activated Blast‐Furnace Slag

This research examines the chemical activation of blast‐furnace slag pastes with alkaline solutions by means of various characterization techniques. Pastes were activated using sodium silicate solutions with modulus (Ms) of 0, 1, 1.5, 2, and Na₂O at 5%, 10%, and 15%. Compressive strengths of up to 108 MPa were achieved for Ms = 1–1.5 after 720 d of curing at 20°C. The addition of Na₂O > 10% resulted in the formation of hydrotalcite and carbonated pastes with low compressive strength. X‐ray diffraction, microanalysis of outer products (OP), and nuclear magnetic resonance (NMR) results showed that the main reaction products in the activated cements with Ms = 1 and 5%Na₂O had an average ratio Ca/Si = 0.71–0.9 and consisted of a mixture of two kinds of C–S–H; one similar to a 9 Å tobermorite‐type calcium silicate hydrate (Ca₅Si₆O₁₆(OH)₂ and other amorphous related to a cross‐linked structure of C–N–(A)–S–H gel. Both were intermixed with hydrotalcite and cross‐linked structures of silica gel.     

Hydroxyapatite,tricalcium phosphate and biphasic materials prepared by a liquid mix technique

The Pechini based liquid-mix technique has been applied to prepare either single phases of hydroxyapatite –Ca₁₀(PO₄)₆OH₂– (OHAp), α and β-tricalcium phosphate –Ca₃(PO₄)₂–, (α-TCP, β-TCP) or biphasic calcium phosphates (BCP). Compositions with a Ca/P molar ratio between 1.5 and 1.667 were synthesized and subjected to a thermal treatment up to 1400 °C. α and β-TCP were both prepared from a Ca/P ratio of 1.5, but while β-TCP is isolated at 900 °C and remains stable up to 1100 °C, it is necessary to anneal at 1400 °C for 72 h to obtain pure α-TCP. OHAp is obtained as a single phase from a 1.667 Ca/P ratio after annealing at 1000 °C for 24 h and starts to decompose at 1400 °C. Between these two extremes a whole range of biphasic calcium phosphates can be prepared by using this technique with an accurate control of the starting reactants. These materials have been characterized by FTIR, XRF, BET, XRD and, based on this technique, a phase quantification determination (QXRD). The solubility of these products was tested in a buffered solution at 37 °C and pH=7.4.     

Calcium Cl/OH-apatite,Cl/OH-apatite/Al2O3 and Ca3(PO4)2 fibre nonwovens: Potential ceramic components for osteosynthesis

Polycrystalline calcium phosphate ((Cl/OH)Ap = Ca₅(PO₄)₃(OH/Cl); TCP = Ca₃(PO₄)₂) fibres were prepared from aqueous solutions of calcium chloride and phosphoric acid using poly(ethylene oxide) (PEO) as spinning aid. Generation of nonwoven materials was accomplished via rotary jet spinning. Polycrystalline (Cl/OH)Ap fibres 10–25 μm in diameter were obtained with 37% ceramic yield by pyrolysis of the green fibres followed by sintering at 1150 °C in air. X-ray diffraction (XRD) analysis provided evidence for apatite formation starting at 650 °C while (Cl/OH)Ap ceramic fibres were obtained at 1100 °C via transformation through intermediate dicalcium dichloride hydrogen phosphate (Ca₂Cl₂(HPO₄)) and calcium pyrophosphate (Ca₂P₂O₇) phases. A glass-forming Al-based additive was applied to enhance the mechanical properties of the Cl/OH)Ap ceramic fibres and indeed resulted in the formation of (Cl/OH)Ap/Al₂O₃ fibres with improved mechanical stability. Finally, TCP, (Cl/OH)Ap and (Cl/OH)Ap/Al₂O₃ fibres were subjected to seeding with mesenchymal stem cells. Negligible cytotoxicity is observed.     

Temperature‐Stable Relative Permittivity from −70°C to 500°C in (Ba0.8Ca0.2)TiO3–Bi(Mg0.5Ti0.5)O3–NaNbO3 Ceramics

Temperature‐stable relaxor dielectrics have been developed in the solid solution system: 0.45Ba_0.8Ca_0.2TiO₃–(0.55 ? x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃. Ceramics of composition x = 0 have a relative permittivity ?_r = 950 ± 15% over a wide temperature range from +70°C to 600°C. Modification with NaNbO₃ at x = 0.2 decreases the lower limiting temperature to ?70°C, but also decreases relative permittivity such that ?_r ~ 600 ± 15% over the temperature range ?70°C to 500°C. For composition x = 0.3, the low‐temperature dispersion in loss tangent, tan δ, (at 1 kHz) shifts to lower temperature, giving tan δ values ≤0.02 across the temperature range ?60°C to 300°C in combination with ?_r ~ 550 ± 15%. Values of dc resistivity for all samples are of the order of 10¹⁰ Ω m at 250°C and 10⁷ Ω m at 400°C.     

Bond characteristics,sintering behavior and microwave dielectric properties of Ce2[Zr1−x(Ca1/3Sb2/3)x]3(MoO4)9 ceramics

Ce₂[Zr_1?x(Ca_1/3Sb_2/3)_x]₃(MoO₄)₉ (CZ_1?x(CS)_xM) (x = 0.02–0.10) ceramics were prepared by the conventional solid-state reaction method. The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by using the Phillips–Van Vechten–Levine (P–V–L) theory. Phase composition and microstructures were evaluated by scanning electron microscopy and X-ray diffraction patterns. Lattice parameters were obtained by Rietveld refinements based on XRD data. Excellent properties for Ce₂[Zr_0.96(Ca_1/3Sb_2/3)_0.04]₃(MoO₄)₉ ceramic sintered at 775 °C: ε_r = 10.68, Q×f = 85,336 GHz and τ_f = ?7.58 ppm/°C were achieved.     

Preparation and Luminescence Properties of Blue‐emitting Phosphor Ba2Ca(PO4)2:Eu2+

Using the conventional high temperature solid‐state reaction method Ba₂Ca(PO₄)₂:Eu²⁺ phosphors were prepared. The phase structure, photoluminescence (PL) properties, and the PL thermal stability of the samples were investigated, respectively. Under the excitation at 365 nm, the phosphor exhibited an asymmetric broad‐band blue emission with peak at 454 nm, which is ascribed to the 4f–5d transition of Eu²⁺. It was further proved that the dipole–dipole interactions results in the concentration quenching of Eu²⁺ in Ba₂Ca_1?x (PO₄)₂:xEu²⁺ phosphors. When the temperature turned up to 150°C, the emission intensity of Ba₂Ca_0.99(PO₄)₂:0.01Eu²⁺ phosphor was 59.07% of the initial value at room temperature. The activation energy ΔE was calculated to be 0.30 eV, which proved the good thermal stability of the sample. All the properties indicated that the blue‐emitting Ba₂Ca(PO₄)₂:Eu²⁺ phosphor has potential application in white LEDs.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Evolution of Mineralogical Phases by 27Al and 29Si NMR in MK‐Ca(OH)2 System Cured at 60°C

The evolution of the metastable phases in metakaolin/Ca(OH)₂ systems cured at high temperatures, remains mostly unknown, newer techniques may now help to establish both the kinetic mechanism of the pozzolanic reaction and the thermodynamic stability of the main hydrated hexagonal phases: Stratlingite (C₂ASH₈) and tetra calcium aluminate hydrate (C₄AH₁₃). For this reason this work examines the kinetics of the pozzolanic reaction in the MK/Ca(OH)₂ system over 123 d at 60°C using nuclear magnetic resonance spectroscopy (²⁷Al and ²⁹Si NMR). The results obtained by ²⁷Al and ²⁹Si NMR show that during the first 30 h, the metastable phases C₂ASH₈ and C₄AH₁₃, coexist with the cubic phase (C₃ASH₆) obtained directly from the pozzolanic reaction. The gel C–S–H is clearly identified after 21 h of reaction, whereas at shorter times the C–S–H bands overlap those with the unreacted metakaolin ones. After 123 d of pozzolanic reaction, the first signs of the cubic phase are detected, a consequence of the conversion reaction of the metastable phases, and a phenomenon not previously identified.     

Effect of Ca2+ Substitution on the Structure,Microstructure, and Microwave Dielectric Properties of Sr2Al2SiO7 Ceramic

The effect of Ca²⁺ substitution on the structure, microstructure, and microwave dielectric properties of Sr–gehlenite (Sr₂Al₂SiO₇) ceramic has been investigated. The structure and microstructure of Sr_2?xCa_xAl₂SiO₇ ceramics were analyzed via X‐ray diffraction (XRD) as well as scanning and transmission electron microscopic techniques. While the end‐members (x = 0 and 2) form isostructural compounds, a highly defective, nonstoichiometric, Ca‐rich secondary phase was observed via bright‐field transmission electron microscopy and energy dispersive X‐ray spectroscopy in compositions corresponding to x = 0.75 and 1.5. The concentration of secondary phase in x = 0.75 is too low to be detected via XRD or scanning electron microscopy. Identical selected‐area electron‐diffraction patterns of the compounds (x = 0, 1, and 2) confirmed that they belong to the space group P2₁m (no. 113) with tetragonal crystal symmetry. The porosity‐corrected relative permittivity at microwave frequencies showed a gradual increase with Ca²⁺ content; however, Ca²⁺ substitution made only marginal changes to the microwave dielectric properties except in the case of x = 1.5, in which the secondary phase reduced the quality factor considerably. Thermal conductivity decreased with increasing Ca²⁺ content, and the compounds with defective structures showed the lowest thermal conductivity. All the compounds exhibited low coefficients of linear thermal expansion, with values varying in the range 2.3–3.6 ppm/°C.     

Hydration of Ca7ZrAl6O18 phase

The hydraulic properties of the Ca₇ZrAl₆O₁₈ (C₇A₃Z) phase as well as the hydration products and thermal decomposition mechanism of this hydrated phase were studied. Microcalorimetric analysis has shown that the C₇A₃Z phase reacts with water very quickly, especially in the first 2 h after the start of the experiment. Hydration of calcium zirconium aluminate proceeds with the formation of high refractory calcium zirconate (with melting point 2345 °C), apart from the hydrated, nearly amorphous material. According to the DTA–TG–EGA, FT-IR and SEM/EDS examinations it has been found that not only the hydrates CAH₁₀, C₂AH₈ and C₄AH₁₉ are present, but also C₃AH₆ (C = CaO, A = Al₂O₃, H = H₂O), the only hydrated calcium aluminate which is a thermodynamically stable phase above 40 °C. Unhydrated Ca₇ZrAl₆O₁₈ and CaZrO₃ phases have been found by XRD, but crystalline hydrates have not been detected.     

The relationship between crystal structure and modified microwave dielectric properties of Ca3SnSi2-xGexO9 ceramics

Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.8) and (1–y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.4 and 0.5) microwave dielectric ceramics were prepared by traditional solid-state reaction through sintering at 1250°C–1425°C for 5 h and at 875°C for 2 h, respectively. Ge⁴⁺ replaced Si⁴⁺, and Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.4) solid solutions were obtained. At 0.1 ≤ x ≤ 0.4, the Ge⁴⁺ substitution for Si⁴⁺ decreased the sintering temperature of Ca₃SnSi_2-xGe_xO₉ from 1425 to 1300°C, the SnO₆ octahedral distortions, and the average CaO₇ decahedral distortions, which affected the τ_f value. The large average decahedral distortions corresponded with nearer-zero τ_f values at Ca₃SnSi_2-xGe_xO₉ (0.1 ≤ x ≤ 0.4) ceramics. The τ_f value and sintering temperature of Ca₃SnSi_2-xGe_xO₉ (x = 0.4) ceramic were adjusted to near-zero by CaSnSiO₅ and decreased to 875°C upon the addition of 2 wt% LiF. The (1 – y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.5) ceramic sintered at 875°C for 2 h exhibited good microwave dielectric properties: ε_r = 10.3, Q × f = 14 300 GHz (at 12.2 GHz), and τ_f = ‒5.8 ppm/°C.     

Preparation of a Novel Cementitious Material from Hydrothermally Synthesized C–S–H Phases

New cementitious materials based on calcium hydrosilicate hydrates were recently developed as potential substitutes for ordinary portland cement, but with a reduced CO₂ footprint. The materials are produced by hydrothermal processing of SiO₂ and Ca(OH)₂, giving rise to calcium silicate hydrates, followed by mechanical activation of the latter via cogrinding with various siliceous materials. Thus, the chemical composition in terms of C/S ratio could be adjusted over a broad range (1–3). In this study the synthesis of a previously unknown cementitious material produced via the combination of mechanical activation in a laboratory mill and thermal treatment of a mixture of quartz and hydrothermally synthesized calcium silicate hydrates: α‐Ca₂[HSiO₄](OH) (α‐C₂SH) and Ca₆[Si₂O₇](OH)₆ (jaffeite) are reported. It forms independently of the type of mill used (eccentric vibrating mill, vibration grinding mill) after thermal treatment of the ground materials at 360°C–420°C. The new material is X‐ray amorphous and possesses a CaO/SiO₂ ratio of 2. A characteristic feature in regards to the silicate anionic structure is the increased silicate polymerization (up to 27% Si₂O₇ dimers) as revealed by the trimethylsilylation method. Infrared (IR) spectra show a very broad absorption band centered at about 935 cm^?1. Another characteristic feature is the presence of ~2.5 wt% H₂O as shown by thermogravimetry (TG) coupled with IR spectroscopy. As this water is bound mostly as hydroxyl to Ca, we refer to this new cementitious material as calcium‐oxide–hydroxide–silicate (C–CH–S). Calorimetric measurements point to a very high hydraulic reactivity which is beyond that for typical C₂S materials. The influence of the type of grinding on the thermal behavior of α‐C₂SH upon its transformation into water‐free Ca₂SiO₄ modifications is discussed.     

Mechanistic study of the effect of Ca–Sn co-doping on the microwave dielectric properties and magnetic properties of YIG

To investigate the crystal structure, electrical properties, and magnetic properties of Ca–Sn co-doped Y_3-xCa_xFe_5-xSn_xO₁₂ (x = 0.00–0.25 in steps of 0.05), solid-state reaction experiments, first principles calculations, and complex crystal bonding theoretical calculations were performed. The relative permittivity (ε_r) is strongly correlated with the average bond ionicity when Ca²⁺ is added. Furthermore, appropriate Sn⁴⁺ substitution significantly lowers the dielectric loss (tanδ_ε) associated with the lattice energy. The right amount of Ca–Sn co-doping can change the saturation magnetization (4πM_S) and improve the microscopic morphology of YIG, lowering the ferromagnetic resonance linewidth (ΔH) of YIG. The optimized microwave dielectric and magnetic properties are as follows: ε_r = 14.7, tanδ_ε = 4.15 × 10^?4, 4πM_S = 1680 G, and ΔH = 53 Oe for Y_2.8Ca_0.2Fe_4.8Sn_0.2O₁₂ sintered for 6 h at 1425 °C. Based on this material, a simple 3D model of a strip-line circulator with an insertion loss of less than 0.3 dB at each port and isolation greater than 20 dB in the 10–12 GHz range was developed, indicating the potential of the material for microwave high-frequency components such as circulators.