Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Varistor properties and aging behavior of ZnO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> ceramics with sintering process

The microstructure, electrical properties, and DC-accelerated aging behavior of the ZnO-V₂O₅-Mn₃O₄ ceramics were investigated at different sintering temperatures of 850–925°C. The microstructure of the ZnO-V₂O₅-Mn₃O₄ ceramics consisted of ZnO grain as a primary phase, and Zn₃(VO₄)₂ which acts as a liquid-phase sintering aid, in addition to Mn-rich phase as secondary phases. The maximum value (3,172 V/cm) and minimum value (977 V/cm) of breakdown field were obtained at sintering temperature of 850 and 900°C, respectively. The nonlinear coefficient exhibited the highest value, reaching 30 at 925°C and the lowest value, reaching 4 at 850°C. The optimum sintering temperature was 900°C, which exhibited not only high nonlinearity with 24 in nonlinear coefficient, but also the high stability, with %ΔE_1mA = −0.9% and %∆α = −12.5% for DC-accelerated aging stress of 0.85 E_1mA/85°C/24 h.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Low-temperature sintering and microwave dielectric properties of Mg<Subscript>3</Subscript>B<Subscript>2</Subscript>O<Subscript>6</Subscript>-LMZBS composites

The Mg₃B₂O₆ ceramics with lithium magnesium zinc borosilicate (LMZBS) glass were prepared at a lower sintering temperature. The effects of the glass addition on the densification, phase development, microstructure and microwave dielectric properties of the Mg₃B₂O₆ ceramics were investigated. The addition of LMZBS glass improved the densification and lowered the sintering temperature of Mg₃B₂O₆ ceramics from 1,300 to 950 °C. X-ray diffraction patterns showed that Mg₃B₂O₆ transformed into Mg₂B₂O₅ and a new phase, Li₂ZnSiO₄, crystallized from the glass phase. Because of the high dielectric performance of these phases, Mg₃B₂O₆ mixed with 55 wt% LMZBS sintered at 950 °C for 3 h had ε_r = 6.8, Q × f = 50,000 GHz, and τ_f = ?64 ppm/°C at 7.28 GHz. The chemical compatibility of ceramic-glass composites with Ag was also investigated for LTCC.     

Microwave dielectric properties of Ba<Subscript>5</Subscript>Nb<Subscript>4</Subscript>O<Subscript>15</Subscript> ceramic by molten salt method

Ba₅Nb₄O₁₅ powders were synthesized by molten-salt method in NaCl–KCl flux at a low temperature of 650–900 °C for 2 h, which is lower than that of the conventional solid-state reaction. This simple process involved mixing of the raw materials and salts in a certain proportion. Subsequent calcination of the mixtures led to Ba₅Nb₄O₁₅ powders at 650–900 °C. XRD and SEM techniques were used to characterize the phase and morphology of the fabricated Ba₅Nb₄O₁₅ powders, respectively. After sintering at 1,300 °C for 2 h, the densified Ba₅Nb₄O₁₅ ceramics with good microwave dielectric properties of ε_r = 39.2, Q × f approximated as 27,200 GHz and τ _f  = 72 ppm/°C have been obtained.     

Effect of Ti-ion non-stoichiometry on microstructure and microwave dielectric characteristic of Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> ceramics

This paper studies the microwave dielectric properties, microstructure, vibration and densification of Li₂ZnTi_3+xO_8+2x (\(- 0.04 \le {\text{x}} \le +0.06\)) ceramics, manufactured via a conventional mixed oxide route. The X-ray diffraction and Raman spectroscopy revealed the unit cell parameter and cation ordering in LZT non-stoichiometry in their vibrational modes. The densification and phase composition were characterized by the EDX and SEM methods. It was found that a slight Ti vacancy can improve the relative density to the maximum value (96.2%). The XRD results showed that the second phase of TiO₂ in the Li₂ZnTi_3.06O_8.12 composition is formed. The sintered samples were detected in the microwave frequency range by using the resonance technique. The \({\text{~}}{\tau _f}\) values of the ceramics within Ti excess adjusted to near zero. The Li₂ZnTi_2.96O_7.92 ceramic showed the best relative density, single phase and best microwave dielectric \({\varepsilon _r}~={\text{ }}25.98\), Q?×?f?=?61,000 GHz, \({\tau _f}={\text{ }} - 17.4{\text{ ppm/}}^\circ {\text{C}}\) sintered at 1100 °C for 4 h.     

Influence of CuO and B<Subscript>2</Subscript>O<Subscript>3</Subscript> on sintering and dielectric properties of tungsten bronze type microwave ceramics: a case study in Ba<Subscript>4</Subscript>Nd<Subscript>9.3</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript>

The effect of CuO and B₂O₃ co-doping on the sintering behavior, microstructure and microwave dielectric properties of tungsten bronze type Ba₄Nd_9.3Ti₁₈O₅₄ (BNT) ceramics has been investigated by means of a traditional solid-state mixed oxide route. On the one hand, it was indicated that the mixture of CuO and B₂O₃ is an effective sintering aid for BNT matrix compositions owing to the existence of a low-temperature eutectic reaction. On the other hand, it was found that the addition of CuO and B₂O₃ has an obvious effect on microwave dielectric properties of BNT ceramics, depending on the amount of sintering aids, the sample density and microstructure. The liquid phases from sintering aids can promote densification, but simultaneously induce grain growth which tends to decrease the sintering driving force. BNT ceramics doped with 3 wt% CuO–B₂O₃ mixture can be well sintered at 950°C for 4 h and still exhibit relatively good microwave dielectric properties.     

Microwave synthesis and sintering characteristics of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

CaCu₃Ti₄O₁₂ (CCTO) was synthesized and sintered by microwave processing at 2·45 GHz, 1·1 kW. The optimum calcination temperature using microwave heating was determined to be 950°C for 20 min to obtain cubic CCTO powders. The microwave processed powders were sintered to 94% density at 1000°C/60 min. The microstructural studies carried out on these ceramics revealed the grain size to be in the range 1–7 μm. The dielectric constants for the microwave sintered (1000°C/60 min) ceramics were found to vary from 11000–7700 in the 100 Hz–00 kHz frequency range. Interestingly the dielectric loss had lower values than those sintered by conventional sintering routes and decreases with increase in frequency.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Effect of B2O3 and CuO additions on the sintering temperature and microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics

The effects of B₂O₃–CuO (BCu, the weight ratio of B₂O₃ to CuO is 1:1) addition on the sintering behavior, microstructure, and the microwave dielectric properties of 3Li₂O–Nb₂O₅–3TiO₂ (LNT) ceramics have been investigated. The low-amount addition of BCu can effectively lower the sintering temperature of LNT ceramics from 1125 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 2 wt% BCu-added ceramic sintered at 900 °C has better microwave dielectric properties of ε _r  = 50.1, Q × f = 8300 GHz, τ _f  = 35 ppm/°C. Silver powders were cofired with the dielectric under air atmosphere at 900 °C. The SEM and EDS analysis showed no reaction between the dielectric ceramic and silver powders. This result shows that the LNT dielectric materials are good candidates for LTCC applications with silver electrode.     

Low temperature preparation of the Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript> ceramics with the addition of BaO and B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Zn₂SiO₄ ceramics with the addition of BaO and B₂O₃ are fabricated by traditional solid-state preparation process at a sintering temperature of 900 °C. The introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is achieved by adding 10 and 20 wt. % flux BB to the mixed ZnO-SiO₂ ceramic powders pre-sintered at 1,100 °C, respectively. The chemical composition of the flux BB (50 wt.%BaO-50 wt.% B₂O₃) is located at a liquid phase zone with a temperature range of about 869–900 °C in the binary diagram BaO-B₂O₃. In addition, the introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is also achieved by the means of a chemical combination of H₂SiO₃, H₃BO₃, ZnO and Ba(OH)₂·8H₂O, which can result in the formation of the hydrated barium borates with low melting characteristics. In turn, by the liquid sintering aid of the barium borate melts, the preparation process of the Zn₂SiO₄ ceramics can be further simplified. In the two preparation methods, the Zn₂SiO₄ ceramics with the 1.5–2.0 ZnO/SiO₂ molar ratios and the addition of a 10 wt. % flux BB can show good dielectric properties whereas the bending strength mainly depends on the microstructure of the Zn₂SiO₄ ceramics and SiO₂ content in the composition of the specimen.     

Influence of Sm substitution on the phase,microstructure and microwave dielectric properties of SrLa<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript>

New dielectric ceramics in the SrLa_4−xSm_xTi₅O₁₇ (0 ≤ x ≤ 4) composition series were prepared through a solid state mixed oxide route to investigate the effect of Sm⁺³ substitution for La⁺³ on the phase, microstructure and microwave dielectric properties. At x = 0–3, all the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1500–1580 °C. At x = 4, a mixture of Sm₂Ti₂O₇ and SrTiO₃ formed. The maximum Sm⁺³-containing single phase ceramics, SrLaSm₃Ti₅O₁₇, exhibited relative permittivity (ε_r) = 42.6, temperature coefficient of resonant frequency (τ _f ) = −96 ppm/^oC and quality factor (Q _u f _o ) = 7332 GHz. An analysis of results presented here indicates that SrLa_4−xSm_xTi₅O₁₇ ceramics, exhibiting τ _f  ~ 0 and ε_r ~ 53 could be achieved at x ~ 1.4 but at the cost of decrease in Q _u f _o .     

Synthesis,microstructure and microwave dielectric properties of Ca<Subscript>4-x</Subscript>Mg<Subscript>x</Subscript>La<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript> ceramics

Ca_4-xMg_xLa₂Ti₅O₁₇ ceramics were prepared by a solid state ceramic route for x = 0, 0.5, 1, 2, 3 and 4. The structure and microstructure of the ceramics were investigated using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. X-ray diffraction results show that the Ca_4-x Mg _x La₂Ti₅O₁₇ adopts an orthorhombic crystal structure with no secondary phase observed for x from 0 to 0.5. Secondary phase, MgTiO₃ occurs with further increasing doping level (1 ≤ x ≤ 3). When x = 4, mixture phases La_0.66TiO_2.993, MgTiO₃ and a trace of unknown phase coexist. Ca₄La₂Ti₅O₁₇ ceramic exhibits a relative permittivity (ε_r) ~ 65, quality factor (Q × f) ~13,338 GHz (at ~4.75 GHz), and temperature coefficient of resonant frequency (τ _f ) ~ 165 ppm/°C. The sintering temperature was distinctly reduced from 1,580 °C for x = 0 to 1,350 °C for x = 4. With increasing Mg content, ε_r and τ_f obviously decrease, while Q × f value initially decreases and then increases. The ceramic for x = 2 shows ε_r ~ 50, Q × f ~ 9,451 and τ _f  ~ 62.5 ppm/°C. By the complete replacement of Ca with Mg, Mg₄La₂Ti₅O₁₇ ceramic sintered at 1,350 °C for 4 h combines a high dielectric permittivity (ε _r  = 31), high quality factor (Q × f ~ 15,021) and near-zero temperature coefficient of resonant frequency (τ _f  ~ 4.0 ppm/°C). The materials are suitable for microwave applications.     

Electrical and thermal properties of PTFE-Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> composites

A new polymer-ceramic composite was prepared using PTFE and low loss Sr₂ZnSi₂O₇. The dielectric properties of the composite were studied in the microwave and radiofrequency ranges. The relative permittivity (ε_r) and dielectric loss (tan δ) increased with the filler loading from 0.10 to 0.50 volume fractions (v_f). The observed values of ε_r, thermal conductivity and coefficient of thermal expansion (CTE) were compared with the corresponding theoretical predictions. The ability of the composite towards moisture absorption resistance was studied as a function of filler loading. It was also found that the variation of ε_r was less than 2% in the temperature range 25–90 °C, at 1 MHz. For a filler content of 0.50 v_f, the PTFE/Sr₂ZnSi₂O₇ composite exhibited ε_r = 4.4_, tan δ = 0.003 (at 4–6 GHz), CTE = 38.3 ppm/°C, thermal conductivity = 2.1 W/mK and moisture absorption = 0.09 wt%.     

Dielectric and piezoelectric properties of MnO<Subscript>2</Subscript>-doped K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>Nb<Subscript>0.92</Subscript>Sb<Subscript>0.08</Subscript>O<Subscript>3</Subscript> lead-free ceramics

Lead-free MnO₂-doped K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramics have been fabricated by a conventional ceramic technique and their dielectric and piezoelectric properties have been studied. Our results show that a small amount of MnO₂ (0.5–1.0 mol%) is enough to improve the densification of the ceramics and decrease the sintering temperature of the ceramics. The co-effects of MnO₂ doping and Sb-substitution lead to significant improvements in the ferroelectric and piezoelectric properties. The K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramic with 0.5 mol%MnO₂ doping possesses optimum propeties: d ₃₃ = 187 pC/N, k _P = 47.2%, ε _r = 980, tanδ = 2.71% and T _c = 287 °C. Due to high tetragonal-orthorhombic phase transition temperature (T _O-T ~ 150 °C), the K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramic with 0.5 mol%MnO₂ doping exhibits a good thermal stability of piezoelectric properties.     

The optimization of microwave dielectric properties of the Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> ceramic by the phase purity control

In recent reports, the microwave dielectric properties of Li₂ZnTi₃O₈ ceramic deviate largely from the optimal value. In this paper by the Rietveld refinement method, the co-existence of the secondary phases is confirmed which is due to the zinc volatilization. Thus, the excessive ZnO addition is introduced to obtain a high purity Li₂ZnTi₃O₈ phase. Microwave dielectric properties are theoretically calculated to prove the above statement, based on the property indices of these phases. The calculated result is consistent to the measured data, with relative deviation around 5%. The optimized properties make the ceramic a promising ceramic candidate for the microwave applications.     

Microwave dielectric properties and compatibility with silver of low-fired Ba2Ti3Nb4O18 ceramics with BaCu(B2O5) addition

The effects of BaCu(B₂O₅) (BCB) additions on the sintering temperature and microwave dielectric properties of Ba₂Ti₃Nb₄O₁₈ ceramic have been investigated. The addition of BCB can lower the sintering temperature of Ba₂Ti₃Nb₄O₁₈ ceramic from 1,250 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 5 wt% BCB added Ba₂Ti₃Nb₄O₁₈ ceramic sintered at 900 °C for 2 h exhibited good microwave dielectric properties of Q × f = 17,600 GHz, ε _r = 38.2 and τ _f  = 7 ppm/°C. The dielectric ceramic demonstrated stability against the reaction with the Ag electrode, which suggests that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>6</Subscript>Mg<Subscript>7</Subscript>Ti<Subscript>3</Subscript>O<Subscript>16</Subscript> ceramics with LiF additive for LTCC applications

Li₆Mg₇Ti₃O₁₆ ceramics were prepared by the conventional solid-state method with 1–5 wt% LiF as the sintering aid. Effects of LiF additions on the phase compositions, sintering characteristics, micro-structures and microwave dielectric properties of Li₆Mg₇Ti₃O₁₆ ceramics were investigated. The LiF addition could effectively lower the sintering temperature of Li₆Mg₇Ti₃O₁₆ ceramics from 1550 to 900 °C. For different LiF-doped compositions, the optimum dielectric permittivity (ε _r ) and quality factor (Q·f) values first increased and then decreased with the increase of LiF contents, whereas the temperature coefficient of resonant frequency (τ _f ) fluctuated between ??14.39 and ??8.21 ppm/°C. Typically, Li₆Mg₇Ti₃O₁₆ ceramics with 4 wt% LiF sintered at 900 °C exhibited excellent microwave dielectric properties of ε _r ?=?16.17, Q·f?=?80,921 GHz and τ _f ?=???8.21 ppm/°C, which are promising materials for the low temperature co-fired ceramics applications.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>3</Subscript>Mg<Subscript>2</Subscript>NbO<Subscript>6</Subscript> ceramics for LTCC application

The Li₃Mg₂NbO₆ ceramics doped with ZnO-B₂O₃-SiO₂ (ZBS) additives were synthesized via the conventional solid-state reaction process. The influence of ZBS additives on phase composition, sintering behavior, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated in detail. The XRD patterns showed that the sintered specimen presented a single phase and no secondary phase appeared. We found that proper amount of ZBS additives could significantly reduce the sintering temperature from 1250 to 925?°C and promote the densification of Li₃Mg₂NbO₆ ceramics. The ε_r and Q?×?f value were strongly affected by bulk density and grain size, respectively. As ZBS content increased, the τ_f value shifted toward negative direction. In summary, excellent microwave dielectric properties of ε_r?~?14.84, Q?×?f?~?73,987 GHz, τ_f?~??16.05 ppm/°C could be obtained in 0.5 wt.% ZBS modified sample when sintered at 925?°C for 4 h. Furthermore, the material was compatible with Ag electrode, demonstrating that it would be a promising candidate material for LTCC application.     

Microstructures and microwave dielectric properties of Li2ZnTi3O8 ceramics prepared by reaction-sintering process

The Li₂ZnTi₃O₈ ceramic was prepared by reaction-sintering process and its microwave dielectric properties were investigated. With increasing sintering temperature or dwell time, the relative densities, ε_r values and Q × f values of Li₂ZnTi₃O₈ ceramic increased initially and then decreased. The smaller τ_f value of Li₂ZnTi₃O₈ ceramic sintered at 975 °C was due to the low degree of oxygen octahedral distortion. When the sintering temperature exceeded 975 °C, the τ_f values of Li₂ZnTi₃O₈ ceramics were independent of sintering temperature. The tetragonal-shaped grains tend to appear in Li₂ZnTi₃O₈ ceramics sintered at higher temperature and longer dwell time, which was dominated by phase boundary reaction mechanism. Typically, The Li₂ZnTi₃O₈ ceramic sintered at 1,025 °C for 6 h had a maximum relative density of 97.4 % and good microwave dielectric properties of ε_r = 25.8, Q × f = 77,100 GHz, τ_f = ?12.4 ppm/°C. The results show that the reaction-sintering process is a simple and effective method to produce dense Li₂ZnTi₃O₈ ceramics with excellent dielectric properties.