Dense Iodoapatite Ceramics Consolidated by Low‐Temperature Spark Plasma Sintering

Pb_9.85(VO₄)₆I_1.7, a potential waste form for long‐lived I‐129 immobilization, experiences phase decomposition and thus iodine loss at an elevated temperature above 400°C, presenting a significant challenge for effective management of radioactive iodine. In this work, we report low‐temperature consolidation of dense iodoapatite pellets with above 95% theoretical density by spark plasma sintering (SPS) at temperatures as low as 350°C for 20 min without iodine loss. Microstructure analysis indicates a nanocrystalline ceramic with an average grain size less than 100 nm. Grain growth dominates the sintered microstructure at higher temperatures and longer durations. The dense nanoceramics have significantly‐improved fracture toughness as compared with bulk coarsened grain structures. The effects of sintering temperatures (350°C, 400°C, 500°C, and 700°C) and durations (0–20 min) on microstructure, density, fracture morphology, and mechanical properties including Young's modulus and hardness of bulk samples were investigated. Low temperature densified iodoapatites suggest immense potential of SPS as an advanced materials fabrication technology for the development of waste forms for immobilization of volatile radionuclides including radioactive iodine.     

Properties of Low‐Temperature Sintering PNN–PMW–PSN–PZT Piezoelectric Ceramics with Ba(Cu1/2W1/2)O3 Sintering Aids

Piezoelectric ceramics Pb(Ni_1/3Nb_2/3)O₃–Pb(Mg_1/2W_1/2)O₃–Pb(Sb_1/2Nb_1/2)O₃–Pb(Zr_0.39Ti_0.61)O₃ with Ba(Cu_1/2W_1/2)O₃ sintering aids were fabricated using economical industrial oxide powders and their piezoelectric, dielectric, and ferroelectric properties were investigated in order to develop low‐temperature sintering ceramics for multilayer piezoelectric actuators. A quadratic formula and the Curie–Weiss law reveal that the ceramics are typical displacive‐type ferroelectric relaxors. The ceramics sintered as low as 900°C have good piezoelectric properties of d₃₃ = 551 pC/N, k_p = 0.52, ε_r = 3583, tgδ = 0.02, and T_C = 161°C, which is much promising to manufacture multilayer piezoelectric transducers.     

Enhancing Electrical Properties in NBT–KBT Lead-Free Piezoelectric Ceramics by Optimizing Sintering Temperature

Conventional sintering of (Na_{1− x} K _x )_0.5Bi_0.5TiO₃ (abbreviated as NKBT x , x =18–22 mol%) lead-free piezoelectric ceramics was investigated to clarify the optimal sintering temperature for densification and electrical properties. Both sintered density and electrical properties were sensitive to sintering temperature; particularly, the piezoelectric properties deteriorated when the ceramics were sintered above the optimum temperature. The NKBT20 and NKBT22 ceramics synthesized at 1110°–1170°C showed a phase transition from tetragonal to rhombohedral symmetry, which was similar to the morphotropic phase boundary (MPB). Because of such MPB-like behavior, the highest piezoelectric constant ( d ₃₃) of about 192 pC/N with a high electromechanical coupling factor ( k _p) of about 32% were obtained in the NKBT22 ceramics sintered at 1150°C.     

Dielectric Properties and Low‐Temperature Sintering of the Ba0.6Sr0.4TiO3 Ceramics with B2O3/CuO Additions

The sintering behaviors and dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated as a function of B₂O₃ and CuO content. The addition of both B₂O₃ and CuO reduced the sintering temperature of Ba_0.6Sr_0.4TiO₃ about 500°C. It was suggested that a liquid phase BaCu(B₂O₅) was formed and assisted the densification of Ba_0.6Sr_0.4TiO₃ ceramics. Ba_0.6Sr_0.4TiO₃ ceramics co‐doped with 3.0 mol% B₂O₃, and 2.0 mol% CuO, sintered at 950°C for 5 h, had a dense microstructure and showed good microwave dielectric properties of a moderate dielectric constant (ε = 1048), low dielectric loss (0.0090) and high tunability (42.2%) at dc electric field of 30 kV/cm.     

Low‐Temperature Sintering of β‐Spodumene Ceramics Using Li2O–GeO2 as a Sintering Additive

Low‐temperature sintering of β‐spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li₂O–GeO₂ sintering additive. Single‐phase β‐spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α‐alumina, and lithium carbonate powders mixture via the solid‐state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li₂O–GeO₂ additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10^?6 K^?1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt‐quenching routes. As a result, β‐spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li₂O–GeO₂ sintering additive via the conventional solid‐state reaction route. These results suggest that β‐spodumene ceramics sintered with Li₂O–GeO₂ sintering additive has a potential use as LTCC for multichip modules.     

Localized Temperature Stability in Low‐Temperature Cofired Ceramics

Low‐temperature cofired ceramic (LTCC) is a multilayer 3D packaging, interconnection, and integration technology. For LTCC modules targeting radio and microwave frequency (RF and MW) applications, a low or near 0 ppm/°C temperature coefficient of resonant frequency (τ_f) ensures temperature stability of embedded resonator and filter functions. The base dielectrics of most commercial LTCC systems have a τ_f in the range ?50 to ?80 ppm/°C. This study explored a method to achieve a zero τ_f on stripline (SL) resonators by locally cofiring, in a multilayer LTCC structure, compensating dielectrics (CD) with an opposite τ_f to that of the host dielectric. The formulation, synthesis, dielectric properties, and microstructure of SrTiO₃ (STO)‐based low‐fire τ_f CD are presented. Chemical interactions and physical compatibility between the compensating and the host LTCC dielectrics are investigated for cofireability. The dependence of τ_f compensation on the wt% of STO, the printed thickness, and the location of the CD in multilayer LTCC are discussed. The most effective τ_f compensation is achieved by integrating CD next to the resonator lines, and can be explained by the concentration of electromagnetic energy via total internal reflection of electromagnetic waves inside the CD layer.     

Low‐Temperature Sintering and Microwave Dielectric Properties of CaMoO4‐Based Temperature Stable LTCC Material

The CaMoO₄–xY₂O₃–xLi₂O ceramics were prepared by the solid‐state reaction method. The sintering behavior, phase evolution, microstructure, and microwave dielectric properties were investigated. CaMoO₄ solid solution was obtained when x = 0.030, and two‐phase system including tetragonal CaMoO₄ phase and cubic Y₂O₃ phase formed when 0.066 ≤ x ≤ 1.417. A temperature stable CaMoO₄‐based microwave dielectric ceramic with ultralow sintering temperature (775°C) was obtained in the CaMoO₄–xY₂O₃–xLi₂O system when x = 0.306, which showed good microwave dielectric properties with a low permittivity of 9.5, a high Q_f value of 63 240 GHz, and a near‐zero temperature coefficient of resonant frequency of +7.2 ppm/°C.     

Grain Size Effects on Piezoelectric Properties and Domain Structure of BaTiO3 Ceramics Prepared by Two‐Step Sintering

A series of highly dense barium titanate (BaTiO₃) ceramics with the average grain size (GS) from 0.29 to 8.61 μm are successfully prepared by two‐step sintering, and the GS effect on piezoelectric coefficient (d₃₃) is systematically discussed in this work. It is found that when GS above 1 μm, d₃₃ can be enhanced with decreasing GS, reaching a maximum value of 519 pC/N around 1 μm due to the high activity of domain wall mobility. Subsequently, d₃₃ rapidly drops with a further decrease in GS owing to the reduced domain density. The results suggest that it is possible to prepare high‐performance BaTiO₃ ceramics by controlling the GS and domain configuration properly, which brings great revitalization to the BaTiO₃‐based piezoceramics.     

Low‐Temperature Sintering Microwave Characteristics of B2O3‐doped CaLa4Ti4O15 Dielectric Ceramics

Preparation and microwave dielectric properties of B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics have been investigated. X‐ray diffraction data show that CaLa₄Ti₄O₁₅ ceramic has a trigonal structure coupled with a second phase of CaLa₄Ti₅O₁₇. The CaLa₄Ti₄O₁₅ ceramic with addition of 0.5 wt% B₂O₃, sintered at 1220°C for 4 h, exhibits microwave dielectric properties with a dielectric constant of 45.8, Q × f value of 24,000 GHz, and temperature coefficient of resonant frequency (τ_f) of ?19 ppm/^°C. B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics, which have better sintering behavior (decrease in sintering temperature ~ 330°C) and dielectric properties than pure CaLa₄Ti₄O₁₅ ceramics, are candidates for applications in microwave devices.     

Low‐Temperature Magnetic and Dielectric Anomalies in Rare‐Earth‐Substituted BiFeO3 Ceramics

In this work, we report on the magnetic and dielectric anomalies observed in dense Bi_1–xRE_xFeO₃ ceramics (RE = Dy, Tb; 0 ≤ x ≤ 0.3) at cryogenic temperatures. For compositions with a high content of rare‐earth ions, thermomagnetic experiments revealed a distinct anomaly in the magnetization curves at temperatures below 200 K. The temperature of the magnetic anomaly along with a thermal hysteresis was found to be dependent on the rare‐earth concentration and magnetic field strength. Low‐temperature dielectric measurements showed an anomalous relaxor‐like behavior of the relative permittivity and dielectric loss in highly doped ceramic samples. The anomalies in low‐temperature magnetization and dielectric response are suggested to result from the presence of GdFeO₃‐like orthoferrite phase and/or bismuth rare‐earth‐mixed iron garnet impurities.     

Low‐Temperature Sintering and Electric Properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 Ferroelectric Ceramics with CuO Additive

The low‐temperature sintering and electric properties of Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ (PZTN 95/5) ferroelectric ceramics with CuO addition was investigated. The CuO addition significantly promoted the densification and reduced the sintering temperature of PZTN 95/5 ceramics by more than 200°C. The 0.2 wt% CuO‐added sample sintered at 1150°C exhibited the optimum relative density of 96.7% and excellent electric properties with values of P_r = 37.80 μC/cm², T_C = 223°C, ε_r = 329, and tan δ = 0.016, which were superior to that of PZTN 95/5 ceramics sintered at 1350°C.     

Sintering Behavior and Dielectric Properties of Ultra‐Low Temperature Fired Silver Molybdate Ceramics

Ag₂MoO₄ ceramic was prepared by using the solid‐state reaction method, which could be sintered at 450°C for 2 h, having a relative permittivity of 8.08, a Qf value of 17 000 GHz, and a temperature coefficient of resonance frequency about ?133 ppm/°C. Ag₂MoO₄ ceramic was chemically compatible with silver but reacted seriously with aluminum to form (Ag_0.5Al_0.5)MoO₄ during the sintering. The fitting of infrared spectra and the Shannon's additive rule were employed to study intrinsic dielectric behaviors of the ceramics at microwave region. Ionic displacive polarization and the electronic polarization contributed almost equally to the dielectric permittivity of the ceramic at microwave region. The Ag₂MoO₄ ceramics could be a good candidate for ultra‐low temperature co‐fired microwave devices.     

Low‐Cost Silicon Nitride from β‐Silicon Nitride Powder and by Low‐Temperature Sintering

Aiming to manufacture low‐cost silicon nitride components, a low‐cost β powder was chosen as a raw powder and low‐temperature sintering at 1550–1600°C under atmospheric pressure nitrogen was carried out. The silicon nitride from β powder with 5 wt% Y₂O₃ and 5 wt% MgAl₂O₄ additives and sintered at 1600°C for 8 h was successfully densified, and it exhibited moderate strength and toughness of 553 MPa ± 22 and 3.5 MPa m^1/2, respectively. The results indicate that the low‐temperature sintering of the low‐cost β powder has a potential to reduce cost of components.     

Structure,Microwave Dielectric Properties,and Novel Low‐Temperature Sintering of xSrTiO3–(1−x)LaAlO3 Ceramics with LTCC Application

xSrTiO₃–(1?x)LaAlO₃ ceramics with ZnO–B₂O₃ sintering aid were prepared by solid‐state reaction method leading to a significant decrease in sintering temperature from 1550°C to 1050°C. The structure, microwave dielectric properties, and low‐temperature sintering behavior were systematically investigated. The results revealed the relationships among ionic size, ionic polarizability and cell volume. With increasing additive, chemical ordering of B‐site cations was indicated with selected area electron diffraction (SAED) patterns, HRTEM images and Raman spectrum, which contributed to the greatly enhanced microwave dielectric properties. Particularly, the 0.7Sr_0.85 Mg_0.15TiO₃–0.3LaAlO₃ ceramics modified with 10 wt % ZnO‐B₂O₃ can further decrease the sintering temperature down to 950°C without deteriorating its performance. Thermal tests implied ceramics featured good chemical compatibility with Cu/Ag electrode. Thus, they can be cofired with internal Cu/Ag electrodes in special patterns to fulfill different electrical functions for LTCC (low‐temperature cofired ceramic) application.     

Low‐Temperature Sintered NTC Thermistor Ceramics for Thick‐Film Temperature Sensors

Negative temperature coefficient (NTC) thermistor thick films were fabricated by screen printing on alumina substrates and firing at 900°C. Spinel‐type NiMn₂O₄ exhibits limited stability in air between 730 and 970°C only and interacts with the Bi₂O₃ additive. The Zn–Co‐substituted spinel Zn_0.75Ni_0.5Co_0.5Mn_1.25O₄ with 3 wt% additive shows complete densification at 900°C; no interaction between spinel and additive was observed. Alternatively, a Cu–Zn–Co‐substituted Cu_0.37Zn_0.52Ni_0.44Co_0.44Mn_1.23O₄ spinel with excellent sintering characteristics even without sintering additive was investigated. The thermistor films display a sheet resistance of about 300 kΩ/□ and B = 3300 K. The firing behavior, microstructure formation, and electrical properties of NTC thick films are reported.     

Piezoelectric Properties of Lead‐free Piezoelectric Ceramics and Their Energy Harvester Characteristics

The energy convergence efficiency (η) and dimensionless figure of merit (DFOM) of CuO‐added (Na_0.5K_0.5)NbO₃ (CNKN) ceramics are larger than those of NKN ceramics because of their large Q_m values and small dielectric losses. Moreover, the η and DFOM values of CNKN ceramics are comparable to those of P‐5C ceramics, which exhibit the highest η and DFOM. Furthermore, the CNKN harvester exhibits a high power density of 12 mW/cm³ at 93 Hz with a load resistance of 250 kΩ; this is similar to the PZT‐based energy harvester, indicating that the CNKN ceramic is a good candidate material for energy harvesters.     

Sintering Behavior,Properties, and Applications of Co‐Fired Piezoelectric/Low Temperature Co‐Fired Ceramic (PZT‐SKN/LTCC) Multilayer Ceramics

Materials and processing conditions have been developed allowing co‐firing of fluxed PZT‐SKN materials with commercial low temperature co‐fired ceramic (LTCC) tapes. Previously, Pb(Zr_0.53, Ti_0.47)O₃–Sr(K_0.25, Nb_0.75)O₃ (PZT‐SKN) ceramics fluxed with 1 wt% LiBiO₂ and 1 wt% CuO addition were shown to sinter to high density at 900°C for 1 h, with a large d₃₃ piezoelectric coefficient of ~415 pm/V. Currently, the master sintering curve (MSC) approach has been used to study the densification behaviors of fluxed PZT‐SKN and LTCC tapes. Different sintering mechanisms for fluxed PZT‐SKN ceramics and LTCC materials are confirmed by analyzing the apparent activation energy (Q_a). Using knowledge gained from MSC results, an optimized sintering profile was developed. Multilayer PZT‐SKN/HL2000 (HeraLock^? Tape, Heraeus) stacks co‐fired at 900°C for 0.5 h maintain large piezoelectric coefficient (high field d₃₃ > 340 pm/V). EDS analysis reveal limited interdiffusion of Pb from PZT‐SKN layers in LTCC and the appearance of Al, Ca, and Si in the PZT‐SKN near the PZT‐SKN/LTCC interface. Further, elemental interdiffusion was not detected at the center of piezoelectric layer in PZT‐SKN/LTCC multilayer ceramics and no subsequent reduction in piezoelectric coefficient d₃₃ was observed. Finally, a piezoelectric microbalance with mass sensitivity of 150 kHz/mg was fabricated using the materials and methods developed.     

Low-Temperature Sintering of Lead-Based Piezoelectric Ceramics

The low-temperature sintering of lead-based piezoelectric ceramics has been studied. The sintering temperature of lead zirconate titanate (PZT) ceramics could be reduced from ∼ 1250° to ∼960°C by the addition of a small amount of the lower-melting frit, B₂O₃–Bi₂O₃—CdO. It exhibited the following dielectric and piezoelectric properties: K_p= 0.52 to 0.58, Q_m= 1000, ε^T₃₃/ε₀= 800 to 1000, tan δ= 50 × 10⁻⁴, ρ= 7.56 to 7.64 g/cm³. Ceramics with the aid of suitable dopants (CdO, SiO₂, and excess PbO) in the Pb-(Ni_1/3Nb_2/3)O₃—PZT family could be sintered at 860° to 900°C. For these materials, K_p= 0.56 to 0.61, Q_m= 1000, ε^T₃₃/ε₀= 1500 to 2000, tan δ≤ 50 × 10⁻⁴, ρ= 7.80 to 8.03 g/cm³. The microstructure, sintering mechanism, and the effects of various impure additions have been analyzed by means of scanning electron microscopy, scanning transmission electron microscopy, electron probe microanalysis, and X-ray photoelectron spectroscopy.     

CuO‐added KNbO3‐BaZrO3 lead‐free piezoelectric ceramics with low loss and large electric field‐induced strain

CuO‐added (1‐x)KNbO₃‐x mol%BaZrO₃ ceramics with 0.0≤x≤7.0 were sintered at 960°C. Large double polarization vs electric field (P‐E) and sprout‐shaped strain vs electric field (S‐E) hysteresis curves were obtained from the specimens with x≤2.0. They exhibited large polarizing electric fields (E_P) owing to the presence of a large number of defect dipoles (P_Ds) that formed between Cu²⁺ ions and oxygen vacancies. Small double P‐E hysteresis curves were observed for the specimens with x≥3.0 with reduced E_P because of the decreased number of P_Ds and the presence of a polymorphic phase structure containing both orthorhombic and pseudocubic structures. In particular, the specimen with x=5.0 exhibited a large strain of 0.16% at 8.0 kV/mm with a small E_P of 1.2 kV/mm and good fatigue property: this specimen maintained a strain of 0.13% at 6.0 kV/mm after 10⁶ cycles of 3.0 kV/mm.     

Fabrication,Microstructure, and Luminescent Properties of Ce3+ ‐Doped Lu3Al5O12 (Ce:LuAG) Transparent Ceramics by Low‐Temperature Vacuum Sintering

The fabrication of 0.5 mol% Ce:LuAG transparent ceramics starting from synthetic nanosized Ce:LuAG powders was investigated by low temperature vacuum sintering. It was found that high quality optical Ce:LuAG ceramics could be densified successfully by vacuum sintering (<10^–3 pa) at 1750°C for 10 h. The in‐line optical transmittance of as‐sintered Ce:LuAG ceramics with thickness of 0.7 mm could reach 73.48% at the wavelength of 550 nm. The microstructure observations revealed that transparent Ce:LuAG ceramics were composed of uniform LuAG grains with average size of 9 μm and HRTEM morphology indicated that no impurity segregation existed at grain boundaries or within Ce:LuAG grains. It was also demonstrated that the annealing treatment (at 1450°C for 20 h in air) could greatly enhance the luminescent intensity of as‐sintered Ce:LuAG ceramics under excitation of X‐ray radiation (75 kV, 25 mA), which makes it a potential candidate to be applied in radiation detector.