无机材料学报 ›› 2023, Vol. 38 ›› Issue (2): 125-136.DOI: 10.15541/jim20220338
冯静静1(), 章游然1,2, 马名生1, 陆毅青1, 刘志甫1,2()
收稿日期:
2022-06-17
修回日期:
2022-07-29
出版日期:
2023-02-20
网络出版日期:
2022-09-15
通讯作者:
刘志甫, 研究员. E-mail: liuzf@mail.sic.ac.cn作者简介:
冯静静(1989-), 女, 博士. E-mail: fengjingjing@mail.sic.ac.cn
基金资助:
FENG Jingjing1(), ZHANG Youran1,2, MA Mingsheng1, LU Yiqing1, LIU Zhifu1,2()
Received:
2022-06-17
Revised:
2022-07-29
Published:
2023-02-20
Online:
2022-09-15
Contact:
LIU Zhifu, professor. E-mail: liuzf@mail.sic.ac.cnAbout author:
FENG Jingjing (1989-), female, PhD. E-mail: fengjingjing@mail.sic.ac.cn
Supported by:
摘要:
采用常规热烧结实现陶瓷粉体的致密化, 烧结温度通常超过1000 ℃, 这不仅需要消耗大量能源, 还会使一些陶瓷材料在物相稳定性、晶界控制以及与金属电极共烧等方面面临挑战。近年来提出的冷烧结技术(Cold Sintering Process, CSP)可将烧结温度降低至400 ℃以下, 利用液相形式的瞬态溶剂和单轴压力, 通过陶瓷颗粒的溶解-沉淀过程实现陶瓷材料的快速致密化。冷烧结技术具有烧结温度低和时间短等特点, 自开发以来受到广泛关注, 目前已应用于近百种陶瓷及陶瓷基复合材料, 涉及电介质材料、半导体材料、压敏材料和固态电解质材料等。本文介绍了冷烧结技术的发展历程、工艺技术及其致密化机理, 对其在陶瓷材料及陶瓷-聚合物复合材料领域的研究现状进行了综述, 其中根据溶解性的差异主要介绍了Li2MoO4陶瓷、ZnO陶瓷和BaTiO3陶瓷的冷烧结现状。针对冷烧结技术工艺压力高的问题及可能的解决途径进行了探讨, 并对冷烧结技术未来的发展趋势进行了展望。
中图分类号:
冯静静, 章游然, 马名生, 陆毅青, 刘志甫. 冷烧结技术的研究现状及发展趋势[J]. 无机材料学报, 2023, 38(2): 125-136.
FENG Jingjing, ZHANG Youran, MA Mingsheng, LU Yiqing, LIU Zhifu. Current Status and Development Trend of Cold Sintering Process[J]. Journal of Inorganic Materials, 2023, 38(2): 125-136.
Technique | Name (Abbreviation) | Definition |
---|---|---|
Traditional sintering | Conventional sintering (ConvS) | Thermal sintering at heating rate of 1-10 ℃/min |
Two step sintering (TSS) | Thermal sintering divided in two steps (heating; cooling and densification) | |
Fast firing (FF) | Rapid sintering with short soaking times and high heating rates | |
Sinter forging (SF) | Sintering in presence of uniaxial pressure in die-less configuration | |
Hot pressing (HP) | Sintering at high temperature and in presence of uniaxial pressure | |
Hydrothermal hot pressing (HIP) | Sintering at high temperature and in presence of hydrostatic pressure | |
Liquid phase sintering | Cold sintering process (CSP) | Sintering at T<400 ℃ in presence of solvent and uniaxial pressure |
Cold hydrostatic consolidation (CHC) | Sintering at room temperature in presence of solvent and hydrostatic pressure | |
Hydrothermal hot pressing (HHP) | Pressure-assisted sintering in hydrothermal conditions | |
Hydrothermal reaction sintering (HRS) | Sintering of oxide ceramics in presence of supercritical water | |
Water vapor-assisted sintering (WVAS) | Conventional sintering in a humid atmosphere | |
Reactive hydrothermal liquid-phase densification (rHLPD) | Sintering at low temperature assisted by hydrothermal reaction | |
Flash-like | Flash sintering (FS) | Rapid sintering at low furnace temperature in presence of electric field |
Thermally insulated flash sintering (TIFS) | Flash sintering where the sample is thermally insulated from the environment | |
Flash sinterforging (FSF) | Flash sintering in presence of uniaxial pressure in die-less configuration | |
Sliding electrodes flash sintering (SEFS) | Flash sintering where the electrodes are in relative motion with respect to the sample | |
Water-assisted flash sintering (WAFS) | Flash sintering in humid atmosphere | |
Contactless flash sintering (CLFS) | Flash sintering with electrodes in non-contact mode | |
SPS-like | Spark plasma sintering (SPS) | Sintering in presence of a DC electric potential and uniaxial pressure |
Deformable punch spark plasma sintering (DPSPS) | Spark plasma sintering at very high pressure (1000-2000 MPa) | |
Flash spark plasma sintering (FSPS) | Hybrid technique of flash sintering and spark plasma sintering | |
Cool spark plasma sintering (CSPS) | Spark plasma sintering at T<400 ℃ and high pressure (300-600 MPa) | |
High pressure spark plasma sintering (HPSPS) | Spark plasma sintering at high pressure (102-103 MPa) | |
Sacrificial material spark plasma sintering (SMPS) | Spark plasma sintering with a sacrificial die to form samples with complex shapes | |
Others | Ultrafast high-temperature sintering (UHS) | Rapid sintering at heating rate of 103-104 ℃/min |
Cold sintering (CS) | Sintering of ductile materials at high pressure and low temperature | |
Microwave sintering (MWS) | Densification assisted by heating with an electromagnetic radiation | |
Induction sintering (IS) | Densification assisted by heating with an induction system | |
Capacitor discharge sintering (CDS) | Rapid sintering with electric energy supplied by capacitor discharge |
表1 烧结技术定义表[13-14]
Table 1 Definition table of sintering techniques[13-14]
Technique | Name (Abbreviation) | Definition |
---|---|---|
Traditional sintering | Conventional sintering (ConvS) | Thermal sintering at heating rate of 1-10 ℃/min |
Two step sintering (TSS) | Thermal sintering divided in two steps (heating; cooling and densification) | |
Fast firing (FF) | Rapid sintering with short soaking times and high heating rates | |
Sinter forging (SF) | Sintering in presence of uniaxial pressure in die-less configuration | |
Hot pressing (HP) | Sintering at high temperature and in presence of uniaxial pressure | |
Hydrothermal hot pressing (HIP) | Sintering at high temperature and in presence of hydrostatic pressure | |
Liquid phase sintering | Cold sintering process (CSP) | Sintering at T<400 ℃ in presence of solvent and uniaxial pressure |
Cold hydrostatic consolidation (CHC) | Sintering at room temperature in presence of solvent and hydrostatic pressure | |
Hydrothermal hot pressing (HHP) | Pressure-assisted sintering in hydrothermal conditions | |
Hydrothermal reaction sintering (HRS) | Sintering of oxide ceramics in presence of supercritical water | |
Water vapor-assisted sintering (WVAS) | Conventional sintering in a humid atmosphere | |
Reactive hydrothermal liquid-phase densification (rHLPD) | Sintering at low temperature assisted by hydrothermal reaction | |
Flash-like | Flash sintering (FS) | Rapid sintering at low furnace temperature in presence of electric field |
Thermally insulated flash sintering (TIFS) | Flash sintering where the sample is thermally insulated from the environment | |
Flash sinterforging (FSF) | Flash sintering in presence of uniaxial pressure in die-less configuration | |
Sliding electrodes flash sintering (SEFS) | Flash sintering where the electrodes are in relative motion with respect to the sample | |
Water-assisted flash sintering (WAFS) | Flash sintering in humid atmosphere | |
Contactless flash sintering (CLFS) | Flash sintering with electrodes in non-contact mode | |
SPS-like | Spark plasma sintering (SPS) | Sintering in presence of a DC electric potential and uniaxial pressure |
Deformable punch spark plasma sintering (DPSPS) | Spark plasma sintering at very high pressure (1000-2000 MPa) | |
Flash spark plasma sintering (FSPS) | Hybrid technique of flash sintering and spark plasma sintering | |
Cool spark plasma sintering (CSPS) | Spark plasma sintering at T<400 ℃ and high pressure (300-600 MPa) | |
High pressure spark plasma sintering (HPSPS) | Spark plasma sintering at high pressure (102-103 MPa) | |
Sacrificial material spark plasma sintering (SMPS) | Spark plasma sintering with a sacrificial die to form samples with complex shapes | |
Others | Ultrafast high-temperature sintering (UHS) | Rapid sintering at heating rate of 103-104 ℃/min |
Cold sintering (CS) | Sintering of ductile materials at high pressure and low temperature | |
Microwave sintering (MWS) | Densification assisted by heating with an electromagnetic radiation | |
Induction sintering (IS) | Densification assisted by heating with an induction system | |
Capacitor discharge sintering (CDS) | Rapid sintering with electric energy supplied by capacitor discharge |
Binary compound | Ternary compound | Quaternary compound | Quinary compound |
---|---|---|---|
MoO3 | Li2CO3 | LiFePO4 | LiAl0.5Ge1.5(PO4)3 |
WO3 | CsSO4 | LiCoPO4 | Li0.5xBi1-0.5xMoxV1-xO4 |
V2O3 | Li2MoO4 | KH2PO4 | (Bi0.95Li0.05)(V0.9Mo0.1)O4 |
V2O5 | Na2Mo2O7 | Ca5(PO4)3(OH) | Li1.5Al0.5Ge1.5(PO4)3 |
ZnO | K2Mo2O7 | (LiBi)0.5MoO4 | - |
Bi2O3 | ZnMoO4 | CsH2PO4 | - |
Fe2O3 | K2MoO4 | InGaZnO4 | - |
SiO2 | Bi2Mo2O9 | K0.5Na0.5NbO3 | - |
CsBr | Gd2(MoO4)3 | LiFePO4 | - |
MgO | Li2WO4 | Li2Mg3TiO6 | - |
PbTe | Na2WO4 | Na0.5Bi0.5MoO4 | - |
Bi2Te3 | LiVO3 | Na0.5Bi0.5TiO3 | - |
NaCl | BiVO4 | YBa2Cu3O7-x | - |
ZnTe | AgVO3 | - | - |
AgI | Na2ZrO3 | - | - |
CuCl | BaTiO3 | - | - |
ZrF4 | NaNO2 | - | - |
ZrO2 | Mg2P2O7 | - | - |
Al2O3 | BaMoO4 | - | - |
CeO2 | Cs2WO4 | - | - |
MnO | NaxCO2O4 | - | - |
SnO | Ca3Co4O9 | - | - |
TiO2 | KPO3 | - | - |
MoS2 | Al2SiO5 | - | - |
- | Ca3Co4O9 | - | - |
- | CaCO3 | - | - |
- | BaFe12O19 | - | - |
- | ZrW2O8 | - | - |
- | NaNbO3 | - | - |
- | SrTiO3 | - | - |
表2 通过冷烧结技术制备的陶瓷材料[29,38,50]
Table 2 Ceramic materials prepared by CSP[29,38,50]
Binary compound | Ternary compound | Quaternary compound | Quinary compound |
---|---|---|---|
MoO3 | Li2CO3 | LiFePO4 | LiAl0.5Ge1.5(PO4)3 |
WO3 | CsSO4 | LiCoPO4 | Li0.5xBi1-0.5xMoxV1-xO4 |
V2O3 | Li2MoO4 | KH2PO4 | (Bi0.95Li0.05)(V0.9Mo0.1)O4 |
V2O5 | Na2Mo2O7 | Ca5(PO4)3(OH) | Li1.5Al0.5Ge1.5(PO4)3 |
ZnO | K2Mo2O7 | (LiBi)0.5MoO4 | - |
Bi2O3 | ZnMoO4 | CsH2PO4 | - |
Fe2O3 | K2MoO4 | InGaZnO4 | - |
SiO2 | Bi2Mo2O9 | K0.5Na0.5NbO3 | - |
CsBr | Gd2(MoO4)3 | LiFePO4 | - |
MgO | Li2WO4 | Li2Mg3TiO6 | - |
PbTe | Na2WO4 | Na0.5Bi0.5MoO4 | - |
Bi2Te3 | LiVO3 | Na0.5Bi0.5TiO3 | - |
NaCl | BiVO4 | YBa2Cu3O7-x | - |
ZnTe | AgVO3 | - | - |
AgI | Na2ZrO3 | - | - |
CuCl | BaTiO3 | - | - |
ZrF4 | NaNO2 | - | - |
ZrO2 | Mg2P2O7 | - | - |
Al2O3 | BaMoO4 | - | - |
CeO2 | Cs2WO4 | - | - |
MnO | NaxCO2O4 | - | - |
SnO | Ca3Co4O9 | - | - |
TiO2 | KPO3 | - | - |
MoS2 | Al2SiO5 | - | - |
- | Ca3Co4O9 | - | - |
- | CaCO3 | - | - |
- | BaFe12O19 | - | - |
- | ZrW2O8 | - | - |
- | NaNbO3 | - | - |
- | SrTiO3 | - | - |
图4 以不同溶剂冷烧结制备ZnO陶瓷的SEM照片[54]
Fig. 4 SEM images of cold sintered ZnO ceramics with different solvents[54] (a) Water; (b) 0.1 mol/L acetic acid; (c) 1 mol/L acetic acid
图5 300 ℃保温12 h冷烧结的BaTiO3陶瓷[56]
Fig. 5 Cold sintered BaTiO3 ceramics obtained by holding at 300 ℃ for 12 h[56] TEM images with grain size of 150 nm (a) and 75 nm (b); (c) Dielectric temperature spectra at 1 MHz
图6 150 ℃下保温15 h冷烧结的BaTiO3陶瓷[57]
Fig. 6 Cold sintered BaTiO3 ceramics obtained by holding at 150 ℃ for 15 h[57] (a) SEM images; (b) Dielectric temperature spectra at 1 MHz
Ceramic-polymer composite | Solvent | Processing conditions | Relative density | Application | Ref. |
---|---|---|---|---|---|
Li2MoO4-PTFE | Deionized (DI) water | 120 ℃, 350 MPa, 15-20 min | 96%-97% | Dielectrics | [19] |
Li1.5Al0.5Ge1.5(PO4)3/PVDF-HFP | DI water | 120 ℃, 400 MPa, 60 min | 80%-86% | Li-ion battery electrolytes | [ |
V2O5-PEDOT:PSS | DI water | 120 ℃, 350 MPa, 20-30 min | 91%-93% | Negative-temperature-resistance sensors | [ |
(LiBi)0.5MoO4-PTFE | DI water | 120 ℃, 250-350 MPa, 20 min | >85% | Dielectrics | [ |
Na2Mo2O7-PEI | DI water | 120 ℃, 175-350 MPa, 20 min | >90% | Dielectrics | [ |
SiO2-PTFE | TEOS/NaOH | 270 ℃, 430 MPa, 60 min | 90%-99% | Dielectrics | [ |
BaTiO3-PTFE | Ba(OH)2·8H2O | 225 ℃, 350 MPa, 120 min | >90% | Dielectrics | [ |
ZnO-PTFE | Acetic acid | 300 ℃, 350 MPa, 30 min | 93%-99% | Varistors | [ |
LiFePO4-C-PVDF | LiOH | 240 ℃, 30-750 MPa, 30 min | 89% | Li-ion electrodes | [ |
NaNbO3-PVDF | DI water | 180 ℃, 550 MPa, 10 min | 97% | Dielectrics | [ |
ZnO-PEEK | Acetic acid | 330 ℃, 300 MPa, 120 min | >98% | Varistors | [ |
ZnO-PDMS | Acetic acid | 250 ℃, 320 MPa, 60 min | >90% | Varistors | [ |
ZnO/PVDF-TrFE | Acetic acid | 140 ℃, 300 MPa, 240 min | >95% | Varistors | [ |
ZnO-PEI-Mn2O3-CoO | Acetic acid | 150 ℃, 27 MPa, 60 min | 88% | Varistors | [ |
LiFePO4-Li6.95Mg0.15La2.75Sr0.25Zr2O12-PPC-LiClO4 | DMF | 100-140℃, 400 MPa, 90-180 min | >85% | Li-ion battery electrolytes | [ |
表3 通过冷烧结技术制备的复合材料
Table 3 Composites prepared by CSP
Ceramic-polymer composite | Solvent | Processing conditions | Relative density | Application | Ref. |
---|---|---|---|---|---|
Li2MoO4-PTFE | Deionized (DI) water | 120 ℃, 350 MPa, 15-20 min | 96%-97% | Dielectrics | [19] |
Li1.5Al0.5Ge1.5(PO4)3/PVDF-HFP | DI water | 120 ℃, 400 MPa, 60 min | 80%-86% | Li-ion battery electrolytes | [ |
V2O5-PEDOT:PSS | DI water | 120 ℃, 350 MPa, 20-30 min | 91%-93% | Negative-temperature-resistance sensors | [ |
(LiBi)0.5MoO4-PTFE | DI water | 120 ℃, 250-350 MPa, 20 min | >85% | Dielectrics | [ |
Na2Mo2O7-PEI | DI water | 120 ℃, 175-350 MPa, 20 min | >90% | Dielectrics | [ |
SiO2-PTFE | TEOS/NaOH | 270 ℃, 430 MPa, 60 min | 90%-99% | Dielectrics | [ |
BaTiO3-PTFE | Ba(OH)2·8H2O | 225 ℃, 350 MPa, 120 min | >90% | Dielectrics | [ |
ZnO-PTFE | Acetic acid | 300 ℃, 350 MPa, 30 min | 93%-99% | Varistors | [ |
LiFePO4-C-PVDF | LiOH | 240 ℃, 30-750 MPa, 30 min | 89% | Li-ion electrodes | [ |
NaNbO3-PVDF | DI water | 180 ℃, 550 MPa, 10 min | 97% | Dielectrics | [ |
ZnO-PEEK | Acetic acid | 330 ℃, 300 MPa, 120 min | >98% | Varistors | [ |
ZnO-PDMS | Acetic acid | 250 ℃, 320 MPa, 60 min | >90% | Varistors | [ |
ZnO/PVDF-TrFE | Acetic acid | 140 ℃, 300 MPa, 240 min | >95% | Varistors | [ |
ZnO-PEI-Mn2O3-CoO | Acetic acid | 150 ℃, 27 MPa, 60 min | 88% | Varistors | [ |
LiFePO4-Li6.95Mg0.15La2.75Sr0.25Zr2O12-PPC-LiClO4 | DMF | 100-140℃, 400 MPa, 90-180 min | >85% | Li-ion battery electrolytes | [ |
图8 三种冷烧结复合材料的电性能[19]
Fig. 8 Electrical properties of three composites prepared by cold sintering process[19] (a-c) εr, Q×f, TCF of (1-x)Li2MoO4-xPTFE; (d) Conductivity of (1-x)LAGP/xPVDF-HFP; (e) Conductivity of (1-x)V2O5-xPEDOT:PSS
图10 冷烧结BaTiO3-PTFE复合材料[57]
Fig. 10 Cold sintered BaTiO3-PTFE composites[57] (a) SEM image; (b) TEM image; (c) EDS image; (d) Relationship between resistivity and electric field strength comparing with BaTiO3 ceramics; (e) Dielectric temperature spectra
图11 冷烧结ZnO和LAGP陶瓷的大尺寸试样[69]
Fig. 11 Cold sintered ZnO and LAGP ceramic samples with large size[69] (a) Photograph of ZnO; (b) Photograph of LAGP; (c) SEM image of LAGP
图12 冷烧结ZnO陶瓷的明显不均匀性[69]
Fig. 12 Obvious inhomogeneity of cold sintered ZnO ceramics[69] (a) SEM image of opaque area; (b) Photograph; (c) SEM image of translucent area; (d) XRD pattern of opaque area; (e) XRD pattern of translucent area
图13 反应水热液相致密化技术[72]
Fig. 13 Reactive hydrothermal liquid phase densification process[72] (a) Schematic of the HLPD process; (b) SEM image of BaTiO3/TiO2 ceramics prepared by rHLPD
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