Cold sintering process: A new era for ceramic packaging and microwave device development

Cold sintering process (CSP) is an extremely low‐temperature sintering process (room temperature to ~200°C) that uses aqueous‐based solutions as transient solvents to aid densification by a nonequilibrium dissolution‐precipitation process. In this work, CSP is introduced to fabricate microwave and packaging dielectric substrates, including ceramics (bulk monolithic substrates and multilayers) and ceramic‐polymer composites. Some dielectric materials, namely Li₂MoO₄, Na₂Mo₂O₇, K₂Mo₂O₇, and (LiBi)_0.5MoO₄ ceramics, and also (1?x)Li₂MoO₄?xPTFE and (1?x)(LiBi)_0.5MoO₄?xPTFE composites, are selected to demonstrate the feasibility of CSP in microwave and packaging substrate applications. Selected dielectric ceramics and composites with high densities (88%‐95%) and good microwave dielectric properties (permittivity, 5.6‐37.1; Q × f, 1700‐30 500 GHz) were obtained by CSP at 120°C. CSP can be also used to potentially develop a new co‐fired ceramic technology, namely CSCC. Li₂MoO₄?Ag multilayer co‐fired ceramic structures were successfully fabricated without obvious delamination, warping, or interdiffusion. Numerous materials with different dielectric properties can be densified by CSP, indicating that CSP provides a simple, effective, and energy‐saving strategy for the ceramic packaging and microwave device development.     

Recent Progress in Applications of the Cold Sintering Process for Ceramic–Polymer Composites

Ceramic–polymer composites are of interest for designing enhanced and unique properties. However, the processing temperature windows of sintering ceramics are much higher than that of compaction, extrusion, or sintering of polymers, and thus traditionally there has been an inability to cosinter ceramic–polymer composites in a single step with high amounts of ceramics. The cold sintering process is a low‐temperature sintering technology recently developed for ceramics and ceramic‐based composites. A wide variety of ceramic materials have now been demonstrated to be densified under the cold sintering process and therefore can be all cosintered with polymers from room temperature to 300 °C. Here, the status, understanding, and application of cold cosintering, with different examples of ceramics and polymers, are discussed. One has to note that these types of cold sintering processes are yet new, and a full understanding will only emerge after more ceramic–polymer examples emerge and different research groups build upon these early observations. The general processing, property designs, and an outlook on cold sintering composites are outlined. Ultimately, the cold sintering process could open up a new multimaterial design space and impact the field of ceramic–polymer composites.     

石榴石固态电解质的冷烧结工艺制备及性能

以LiNO3、Al(NO3)3·9H2O、La(NO3)3·6H2O、ZrO(NO3)2·5H2O为原料，采用溶胶-凝胶法制备Li5.95Al0.35La3Zr2O12粉体，随后加入聚乙烯醇（PVA）水溶液作为液相介质，通过冷烧结工艺制备Li5.95Al0.35La3Zr2O12石榴石固态电解质。冷烧结工艺后采用后续热处理改善离子传导性能。采用质量体积法和电化学阻抗谱对Li5.95Al0.35La3Zr2O12石榴石固态电解质的体积密度和离子电导率进行了测试，采用XRD与SEM进行晶体结构与形貌表征。结果表明，冷烧结时间和压力对样品的晶体结构几乎没有影响。冷烧结时间过长会导致样品开裂，在15~30 min时，冷烧结时间对样品的致密性和电导率影响不大，在烧结时间较短的样品中发现了杂相。提高冷烧结压力可明显提高样品的致密性和电导率，在200℃、510 MPa、30 min的冷烧结条件下可以获得具有较高离子电导率（2.66×10-6 S/cm）的Li5.95Al0.35La3Zr2O12石榴石固态电解质，此时材料的晶界电阻较小。但继续增加冷烧结压力，由于热处理过程中第二相的分解和晶粒生长受到抑制，样品的致密性和电导率反而下降。     

Direct Integration of Cold Sintered,Temperature-Stable Bi2Mo2O9-K2MoO4 Ceramics on Printed Circuit Boards for Satellite Navigation Antennas

Bi₂Mo₂O₉-K₂MoO₄ (BMO-KMO) composite ceramics with >95% theoretical density were densified by cold sintering at 150 °C. XRD, Raman, back-scattered SEM and EDX spectroscopy indicated that the BMO and KMO phases coexisted in all composites without inter-diffusion and secondary phases. Temperature coefficient of resonant frequency with near-zero value ∼ -1 ppm/°C was acheived for BMO-10%KMO with pemittivity ∼ 31 and quality factor ∼ 3,000 GHz. Cold-sintered composite ceramics were directly pressed/integrated onto a printed circuit board (PCB) using the Cu metallisation as a ground plane for the design and fabrication of a circularly polarized microstrip patch antenna suitable for satellite navigation systems which achieved efficiencies 87% at 1561 MHz (BeiDou) and 88% at 1575 MHz (GPS/Galileo). The low cost, low energy integration of temperature stable, cold sintered ceramics directly onto a PCB represents a step change in substrate fabrication technology for RF devices.     

Influence of the cold sintering process and post annealing on the microstructure and Li-ion conductivity of LiTa2PO8 solid electrolyte

Recently, LiTa₂PO₈ (LTPO) has attracted interest as a potential Li-ion solid electrolyte material because of its high bulk ionic conductivity and low grain boundary ionic conductivity. However, most ceramic-based solid electrolytes are fabricated via the high-temperature sintering process (typically above 1000 °C); such temperatures can cause the evaporation of Li from the compound. To replace high-temperature sintering of ceramics, the cold sintering process (CSP) was introduced; this process enables the densification of ceramics and composites at extremely low temperatures (below 300 °C). In this work, we investigate the effect of using the CSP and post annealing on the microstructure and Li-ion conductivity of LTPO pellets. It is found that the CSP pellets have an amorphous phase between particles. This intermediate amorphous phase creates a better contact between particles and is hypothesized to lead to more Li-ion migration paths. The CSP pellet is found to have a high density and high ionic conductivity of (1.19 × 10^?5 S/cm). The pellet obtained via the CSP has Li-ion conductivity similar to that of the pellet obtained via dry pressing after it has been annealed. The CSP pellet after post annealing shows good connections between particles and a high Li-ion conductivity of 1.05 × 10^?4 S/cm, which is comparable to the conductivity of a pellet obtained via high-temperature sintering. This work provides new evidence that the CSP is a promising alternative to high-temperature sintering for fabricating ceramic solid electrolytes.