Synthesis of glass–ceramics in the CaO–MgO–SiO2 system with B2O3, P2O5, Na2O and CaF2 additives

Glass–ceramics based on the CaO–MgO–SiO₂ system with limited amount of additives (B₂O₃, P₂O₅, Na₂O and CaF₂) were prepared. All the investigated compositions were melted at 1400 °C for 1 h and quenched in air or water to obtain transparent bulk or frit glass, respectively. Raman spectroscopy revealed that the main constituents of the glass network are the silicates Q¹ and Q² units. Scanning electron microscopy (SEM) analysis confirmed liquid–liquid phase separation and that the glasses are prone to surface crystallization. Glass–ceramics were produced via sintering and crystallization of glass-powder compacts made of milled glass-frit (mean particle size 11–15 μm). Densification started at 620–625 °C and was almost complete at 700 °C. Crystallization occurred at temperatures >700 °C. Highly dense and crystalline materials, predominantly composed of diopisde and wollastonite together with small amounts of akermanite and residual glassy phase, were obtained after heat treatment at 750 °C and 800 °C. The glass–ceramics prepared at 800 °C exhibited bending strength of 116–141 MPa, Vickers microhardness of 4.53–4.65 GPa and thermal expansion coefficient (100–500 °C) of 9.4–10.8 × 10⁻⁶ K⁻¹.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Enhanced piezoelectric properties and temperature stability of Bi4Ti3O12-based Aurivillius ceramics via W/Nb substitution

Bi₄Ti₃O₁₂ (BIT), a typical Aurivillius ceramics with high Curie temperature (T_c ? 675 °C), has great potential for high temperature applications. This work provides an effective method of inducing structure distortion, relieving the tetragonal strain of the TiO₆ octahedron and decreasing the concentration of oxygen vacancies to improve the piezoelectricity and temperature stability of BIT ceramics. Bi₄Ti_2.98W_0.01Nb_0.01O₁₂ possesses an optimum piezoelectric coefficient (d₃₃) of 32 pC/N, a high T_c of 655 °C and a large resistivity of 3 × 10⁶ Ω·cm at 500 °C. The maximum d₃₃ reported here is approximately quadruple than that of pure BIT (?7 pC/N). Moreover, the d₃₃ of W/Nb co-doped BIT and the in-situ temperature stability of the compression-mode sensor present a highly stable characteristic in the range of 25–600 °C. These results imply that W/Nb-modified BIT ceramics is a promising candidate for application at high temperatures of up to 600 °C.     

Densification,flexural strength and dielectric properties of CaO-MgO-ZnO-SiO2/Al2O3 glass ceramics for LTCC applications

Novel glass ceramics for LTCC applications with high flexural strength can be achieved by CaO-MgO-ZnO-SiO₂(CMSZ) glass cofiring with Al₂O₃. The sintering shrinkage behavior, crystalline phases, mechanical and dielectric properties, and thermal expansion of the CMZS/Al₂O₃ glass ceramic were determined. The X-ray diffraction results revealed that multiphases (CaMgSi₂O₆, Al₂Ca(SiO₄)₂ and ZnAl₂O₄) formed in the sintering process of the CMZS/Al₂O₃ glass ceramic. The flexural strength of CMZS/Al₂O₃ glass ceramics first increases and then decreases with increasing Al₂O₃ content. The CMZS/Al₂O₃ glass ceramic with 50 wt % Al₂O₃ sintered at 890 °C for 2 h achieved the best performance, with a maximum flexural strength of 256 MPa, dielectric constant (ε_r) of 7.89, dielectric loss (tan δ) of 3.41 × 10⁻³ (12 GHz), temperature coefficient of resonance frequency (τ_f) of −29 ppm/°C, and the CTE value of 7.93 × 10⁻⁶/°C.     

Enhancing temperature stability in potassium-sodium niobate ceramics through phase boundary and composition design

Phase boundaries and composition design were explored to achieve both high piezoelectricity and favorable temperature stability in potassium-sodium niobate ceramics, using (1-x)(K,Na)(Nb,Sb)O₃-xBi(Na,K)(Zr,Sn,Hf)O₃ ceramics. A rhombohedral-tetragonal (R-T) phase boundary was constructed at x=0.035–0.04 by co-doping with Sb⁵⁺ and Bi(Na,K)(Zr,Sn,Hf)O₃. More importantly, a superior temperature stability was observed in the ceramics with x=0.035, accompanying with a stable unipolar strain at room temperature to 100 °C. The ceramics with x=0.035 also exhibited improved piezoelectric properties (e.g., piezoelectric coefficient d₃₃∼465 pC/N and electromechanical coupling factor k_p=0.47) and Curie temperature (T_c∼240 °C). The Rietveld refinement and in-situ temperature-dependent piezoresponse force microscopy (PFM) results indicated that the enhancement of the piezoelectric properties was caused by the easy domain switching, high tetragonal fraction, and tetragonality, while the improved temperature stability mainly originated from the stable domain structures.     

Effects of Li2O-B2O3-SiO2 glass on the low-temperature sintering of Zn0.15Nb0.3Ti0.55O2 ceramics

The influences of Li₂O-B₂O₃-SiO₂ glass (LBS) on the activation energy, phase composition, the stability of the structure and microwave dielectric properties of Zn_0.15Nb_0.3Ti_0.55O₂ ceramics have been systematically investigated. LBS glass acted as flux former and contributed to the reactive liquid-phase sintering mechanism, which remarkably lowed the sintering temperature from 1150?°C to 900?°C and enhanced the shrinkage and densification of ceramic at the low sintering temperatures. The ceramics with 1.5?wt% LBS glass sintered at 900?°C for 3?h show great properties: ε_r = 73.59, Q × f = 8024?GHz, τ_f = 270.54?ppm/°C.     

Fabrication and dielectric properties of barium titanate-based glass ceramics for tunable microwave LTCC application

Low-fired ferroelectric glass ceramics were fabricated from glass powders with a basic composition of 0.65BaTiO₃·0.27SiO₂·0.08Al₂O₃. The combined addition of SnO₂ (or ZrO₂) and SrCO₃ was conducted to modify the dielectric properties of the glass ceramics. The Sr-component could be incorporated preferentially in the perovskite structure after heating at 1000 °C. The bulk and thick film samples obtained by sintering glass powder with a starting composition of 0.65(Ba_0.7Sr_0.3)(Ti_0.85Sn_0.15)O₃·0.27SiO₂·0.08Al₂O₃ at 1000 °C for 24 h showed a broadened ɛ_r–T relation with T_c ≈ 10 °C and ɛ_r(max) ≈ 280 and microwave tunability of 32% at 3 GHz, respectively.     

Influence of sintering conditions on piezoelectric properties of KNbO3 ceramics

A homogeneous KNbO₃ (KN) phase was formed in specimens that were sintered at 1020 °C and 1040 °C, without formation of the K₂O-deficient secondary phase, indicating that the amount of evaporation of K₂O during sintering was very small. However, the KN liquid phase was formed during sintering and assisted the densification of the KN ceramics. A dense microstructure was developed in the specimen sintered at 1020 °C for 6 h and abnormal grain growth occurred in this specimen. A similar microstructure was observed in the specimens sintered at 1040 °C for 1.0 h. The dielectric and piezoelectric properties of the KN ceramics were considerably influenced by the relative density. The KN ceramics sintered at 1020 °C for 6 h, which showed a large relative density that was 95% of the theoretical density, exhibited promising electrical properties: ɛ^T₃₃/ɛ_o of 540, d₃₃ of 109 pC/N, k_p of 0.29, and Q_m of 197.     

Low temperature fabrication of lead-free KNN-LS-BS ceramics via the combustion method

Lead-free piezoelectric 0.992(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–0.008BiScO₃; KNN-LS-BS ceramics were successfully prepared using the combustion method. The highest % perovskite phase was found in the sample calcined at 700 °C for 1 h. The structural phase of orthorhombic structure was also detected in this sample. For the sintered ceramics, a pure tetragonal perovskite phase was observed in the samples sintered between 1025 and 1100 °C. The microstructure of ceramics showed a square or rectangular shape and the average grain size increased with increasing of sintering temperature. The density of the ceramics increased with increasing of sintered temperature up to 1075 °C, were it reached 97.5% of theoretical density and then dropped in value when the sintered temperature further increased. The excellent electrical properties of ε_r at T_c=6600, tanδ at T_c=0.04, P_r (at 40 kV/cm)=19.4 μC/cm² and E_c (at 40 kV/cm)=24.1 kV/cm were obtained in the most dense ceramic. The results indicate that the KNN-LS-BS ceramics are promising lead-free piezoelectric materials.     

Low-Temperature Sintering of (K0.5Na0.5)NbO3 Piezoelectric Ceramics

(K_0.5Na_0.5)NbO₃ piezoelectric ceramics can be sintered at a temperature as low as 750 °C for 5 h by incorporating Li₂CO₃ + Bi₂O₃ + ZnO as the sintering aid, whereas the conventional sintering temperature is around 1,100 °C. The optimal “soft” piezoelectric properties are obtained for ceramics sintered at 850 °C for 5 h. The dielectric permittivity (ε), piezoelectric coefficient (d ₃₃), electromechanical coupling (k _p) and mechanical quality factors (Q _m) of (K, Na)NbO₃ modified with 5.5 wt% sintering aids are 1,436, 90 pC/N, 0.3 and 10, respectively. These values are similar to the values obtained for (K_0.5Na_0.5)NbO₃ ceramics sintered above 1,100 °C. The underlying mechanism for abrupt change of dielectric permittivity is explained.     

Bio-based thermosetting bismaleimide resins using eugenol,bieugenol and eugenol novolac

5,5′-Bieugenol (BEG) and eugenol novolac (EGN) were synthesized by the oxidative coupling reaction of eugenol (EG) and the addition–condensation reaction of EG with formaldehyde, respectively. The EG, BEG and EGN were prepolymerized with 4,4′-bismaleimidediphenylmethane (BMI) at 180 °C and then compression-molded at finally 250 °C for 6 h to produce cured EG/BMI (EB), BEG/BMI (BB) and EGN/BMI (NB) resins with eugenol/maleimide unit ratios of 1/1, 1/2 and 1/3. The FT-IR analysis of EBs and ¹³C NMR analysis of the model reaction product of EG/N-phenylmaleimide (PMI) 1/3 at 200 °C for 12 h suggested that the ene reaction and subsequent Diels-Alder/ene reactions mainly occurred for EBs. The FT-IR analyses of BBs and NBs supported the occurrence of ene reaction and subsequent thermal addition copolymerization in a similar manner to the well-known curing reaction of 2,2′-diallylbisphenol A and BMI. The glass transition temperature (T_g) and 5% weight loss temperature (T₅) of the cured resin increased with increasing BMI content, and EB 1/3 showed the highest T_g 377 °C and T₅ 475 °C. The flexural strengths and moduli of EBs and NBs were higher than those of BBs, and EB 1/2 showed the most balanced flexural strength and modulus (84.5 MPa and 2.75 GPa). The FE-SEM analysis revealed that there is no phase separation for all the cured resins.     

Preparation and properties of in-situ mullite whiskers reinforced aluminum chromium phosphate wave-transparent ceramics

In-situ mullite whisker reinforced aluminum chromium phosphate wave-transparent ceramics were designed and prepared. The phase transformation, microstructure, mechanical and electrical properties of the ceramics were investigated, and the mechanisms of in-situ growth and toughening were discussed. Results indicated that the in-situ growth of mullite whisker significantly improved the mechanical properties of the matrix, especially the high temperature flexural strength. The room temperature flexural strength, 1000 °C flexural strength and fracture toughness of the ceramics were 135.60 MPa, 121.71 MPa and 4.52 MPa m^1/2. After sintering at 1500 °C, the optimum properties of ε^'_r, tanδ and microwave transmittance at region 8–12 GHz were <3.6, <0.03 and>80%, respectively. The sinterability of ACP matrix was improved by the in-situ process of high mullization above 1450 °C. Using ACP binder as the raw material can avoid the phase transformation from B-AlPO₄ to T-AlPO₄. The synthesized mullite whiskers played a role in toughening by whiskers fracture, crack deflection and whisker pulling out.     

Enhanced piezoelectric properties and electrical resistivity in W/Cr co-doped CaBi2Nb2O9 high-temperature piezoelectric ceramics

W/Cr co-doped Aurivillius-type CaBi₂Nb_2-x(W_2/3Cr_1/3)_xO₉ (CBN) (x?=?0.025, 0.050, 0.075, 0.100, and 0.150) piezoelectric ceramics were prepared by the conventional solid-state reaction method. The crystal structure, microstructure, dielectric properties, piezoelectric properties, and electrical conductivity of these ceramics were systematically investigated. After optimum W/Cr modification, the CBN ceramics showed both high d₃₃ and T_C. The ceramic with x?=?0.1 showed a remarkably high d₃₃ value of ~15 pC/N along with a high T_C of ~931?°C. Moreover, the ceramic also showed excellent thermal stability evident from the increase in its planar electromechanical coupling factor k_p from 8.14% at room temperature to 11.04% at 600?°C. After annealing at 900?°C for 2?h, the ceramic showed a d₃₃ value of 14?pC/N. Furthermore, at 600?°C, the ceramic also showed a relatively high resistivity of 4.9?×?10⁵ Ω?cm and a low tanδ of 9%. The results demonstrated the potential of the W/Cr co-doped CBN ceramics for high-temperature applications. We also elucidated the mechanism for the enhanced electrical properties of the ceramics.     

Excellent high-temperature piezoelectric performances of ternary BiScO3-PbTiO3-(Sr0.7Bi0.2)TiO3 ceramics achieved via multiple optimization strategy

In harsh environments, the piezoelectric devices with critical component of high-temperature piezoelectric materials are in great demand. BiScO₃-PbTiO₃ ceramics with large piezoelectric coefficient (d₃₃) and high Curie temperature (T_c), shows a high-level dissipation factor (tanδ), causing serious self-heating. Here, a multiple-level approach, that is, regulation of phase and domain structures, domain pinning by isolated defects, and enlargement of the activation energy, is proposed to achieve a well-balanced piezoelectric performance. Based on this strategy, novel BiScO₃-PbTiO₃-(Sr_0.7Bi_0.2)TiO₃ +MnO₂ ceramics (Mn:BS-PT-SBT) were fabricated. Among them Mn:BS-0.62PT-0.03SBT displays an ultralow tanδ of 1.62% at 200 °C, a large d₃₃ of 358 pC N⁻¹, and a high T_c of 425 °C. Moreover, the fabricated acoustic emission sensor maintains a high amplitude of 99 dB within 25–200 °C, and the emission transducer has a large residual power ratio twice that of commercial P-5 G at 200 °C. This study provides an effective route for designing piezoelectric ceramics that operate competitively at high temperatures.     

Active Filler (Aluminum–Aluminum Nitride) Controlled Polycarbosilane Pyrolysis

The processing and reaction mechanism of metallic aluminum (Al) powder as an active filler that controls polycarbosilane (PCS) precursor pyrolysis are investigated. Since Al can react with N₂ to produce aluminum nitride (AlN), the linear shrinkage upon pyrolysis decreases and the ceramic yield of PCS increases. The linear shrinkage is zero when the volume ratio between Al and PCS, νAl/PCS, is about 56%. Aluminum also enhances the three-point bending strength of the ceramics with a flexural strength of 212 MPa when νAl/PCS is 60%. The relationship among pyrolysis temperature, T _p, linear shrinkage and flexural strength of the derived ceramics has been investigated. The results showed that, for the Al-containing PCS-derived ceramics, a linear expansion occurred as the flexural strength was enhanced when T _p increased from 400 to 1000°C. The reaction mechanism of Al-controlled PCS pyrolysis was investigated by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and elemental line-scanning electron microscopy (ELSEM). The results showed that the SiC powder took on the role of a catalyst, which decreased the nitridation temperature of aluminum and increased the conversion yield from Al to AlN. An erratum to this article can be found at     

Effect of MgO addition on the properties of PbO –TiO2–B2O3 glass and glass–ceramics

Glass samples with composition of (50?X) PbO–X MgO–25 TiO₂–25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The amorphous nature of glass samples were confirmed by XRD. The glass transition temperature, T_g and crystallization temperature T_c were determined from the DTA. It has been observed that the addition of MgO enhances the T_g. The rise in T_g with MgO content may be attributed to the greater field strength of Mg²⁺ cation (as compared to Pb²⁺) which leads to the formation of stronger bonds. These glass samples were converted to glass–ceramics by following a two-stage heat treatment schedule. It was observed that there was good correlation between the density and CTE results of the glass–ceramics. The XRD results revealed the formation of tetragonal lead titanate as a major crystalline phase in the glass–ceramics. The addition of MgO to the glass contributes to the formation of MgB₄O₇. The dielectric constant for all the glass–ceramic samples was observed to be higher than that of corresponding glass samples. Further, with addition of MgO the room temperature dielectric constant for glass–ceramic samples increases up to 10 mol% of MgO and then decreases for 15 mol%. It has been further observed that the variation of dielectric constant of glass–ceramic samples with MgO content is exactly opposite to the variation of crystallite size of PbTiO₃ embedded in the glass ceramic-samples.     

Low‐Temperature Sintering and Piezoelectric Properties of CuO‐Added KNbO3 Ceramics

Dielectric and piezoelectric properties of CuO‐added KNbO₃ (KN) ceramics were investigated. The CuO reacted with the Nb₂O₅, formed a CuO–Nb₂O₅‐related liquid phase during the sintering, and assisted the densification of the KN ceramics at low temperatures. Moreover, some of the Cu²⁺ ions replaced the Nb⁵⁺ ions in the matrix and behaved as a hardener. The dielectric and piezoelectric properties of the KN ceramics were considerably influenced by the relative density. The 1.0 mol% CuO‐added KN ceramic sintered at 960°C for 1.0 h, which showed a maximum relative density, exhibited a high phase angle of 86.9°, P_r of 14.8 μC/cm², and E_c of 1.8 kV/mm. This specimen also exhibited good dielectric and piezoelectric properties: ε^T₃₃/ε_o of 364, d₃₃ of 122 pC/N, k_p of 0.29, and Q_m of 611.     

Influence of polymer type on adhesion performance of a blended cement mortar

The purpose of this study was to examine the influence of various polymeric materials on the adhesion characteristics of a rapid setting, minimum defect mortar based upon a blend of calcium sulfoaluminate (CSA) cement and ordinary Portland cement (OPC). Four different polymer powders were added to the base mortar at a polymer/cement ratio (p/c) of 0.15. The water/cement (w/c) ratio remained constant for all mortars at 0.42. The polymeric materials consisted of an acrylic polymer powder with T_g=−10 °C, a styrene butadiene rubber (SBR) polymer powder with T_g=15 °C and two vinyl acetate/ethylene (VAE) polymer powders, one with T_g=−7 °C and the other with T_g=20 °C. Mortars were tested for direct tensile strength following ASTM C307 and pull-off strength following a variant of ASTM C1583 after curing for either 24 h or 13 days at ambient laboratory temperature of 23 °C. Mortars were cast over concrete, wood, metal and glass substrates. Pull-off tests over concrete substrate resulted in substrate failure for all polymer modified mortars. Pull-off tests cast over wood, glass and metal substrate materials highlighted the SBR polymer for demonstrating the poorest adhesion performance. Statistical analysis was performed with Minitab software.     

Optimizing the piezoelectric properties of Ba0·85Ca0·15Zr0·10Ti0·90O3·lead-free ceramics via two-step sintering

The two-step sintering of lead-free Ba₀·₈₅Ca₀·₁₅Zr₀·₁Ti_0·9O₃·(BCZT) ceramics was investigated as a way to enhance its piezoelectric properties. The variations in grain size as a function of the calcination and sintering conditions and its effect on performance is discussed. Results indicate that as the calcination and first-step sintering temperatures increased, grain size became large and was independent of the second sintering step. Large grains were responsible for the enhanced piezoelectric properties by causing lattice distortion, larger domains, and easy motion of domain walls. The BCZT ceramic calcined at 1200 °C and sintered at 1540 °C without holding and then cooled to 1400 °C and held at 1400 °C for 4 h exhibited optimal performance with the highest remnant polarization P_r ∼13.5 μC/cm², the largest piezoelectric constant d₃₃ ∼ 529 pC/N at room temperature, and the highest Curie temperature T_c ∼125 °C. Two-step sintering has been turned out to be an effective method to realize high-performance BCZT ceramics by microstructure optimization.     

Low-temperature synthesis of K0.5Na0.5NbO3 ceramics in a wide temperature window via cold-sintering assisted sintering method and enhanced electrical properties

High temperatures (≥ 1100 °C) and narrow temperature window (～ 20 °C) for sintering dense K_0.5Na_0.5NbO₃ ceramics always deteriorate their electrical properties. Here, via cold-sintering assisted sintering method, dense K_0.5Na_0.5NbO₃ ceramics were obtained in a wide temperature span between 800 °C and 1000 °C. An aqueous solution of NaOH and KOH mixture was used as transient liquid. Effects of liquid content (LC), molar concentration (MC) of liquid, cold-sintering temperature (T_CS), and post-annealing temperature (T_AN) on densification and electrical properties of the ceramics were investigated in detail. The ceramics prepared using LC = 10 wt%, MC = 10 mol/L, T_CS = 350 °C, and T_AN = 900 °C exhibit excellent electrical properties with d₃₃ = 123 pC/N, ε_r = 609, tanδ = 0.021, P_r = 28.0 μC/cm², P_m = 39.2 μC/cm², and E_c = 20.3 kV/cm. Compared to the ceramics with same or similar compositions via conventional solid-state sintering, the present K_0.5Na_0.5NbO₃ ceramics exhibit excellent electrical properties. The study endows the cold-sintering assisted sintering the successful method to prepare K_0.5Na_0.5NbO₃ ceramics at low temperatures and in a wide temperature window.