CN110204328A - A kind of preparation method of high entropy oxide ceramics - Google Patents

A kind of preparation method of high entropy oxide ceramics Download PDF

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CN110204328A
CN110204328A CN201910485418.9A CN201910485418A CN110204328A CN 110204328 A CN110204328 A CN 110204328A CN 201910485418 A CN201910485418 A CN 201910485418A CN 110204328 A CN110204328 A CN 110204328A
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high entropy
oxide ceramics
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entropy oxide
powder
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刘金铃
刘佃光
赵科
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Southwest Jiaotong University
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Abstract

The invention discloses a kind of preparation methods of high entropy oxide ceramics, comprising the following steps: step 1: weighing 4 kinds or 5 kinds or less metal-oxide powders respectively according to the ratio that metallic atom molar ratio is 1:1:1:1 or 1:1:1:1:1；Oxide powder includes: MgO, ZnO, NiO, CuO, CaO, CoO, ZrO2、CeO2、Al2O3、Gd2O3、La2O3、Er2O3、Y2O3、Fe2O3、Co3O4、CaCO3；Step 2: ball milling, drying, granulation are carried out to powder weighed in step 1；Step 3: the powder after granulation being pressed, green compact are obtained；Step 4: the green compact that step 3 is obtained are heat-treated；Step 5: the green compact heating after step 4 heat treatment is reached into preset temperature, apply the electric field of default electric field strength to sample, power supply is changed into constant current state by pressure constant state after appearance flash burning, and 1~60 min is kept the temperature under predetermined current density, and required high entropy oxide ceramics can be obtained in subsequent quenching；The present invention prepares high entropy oxide ceramics using flash burning, significantly reduces sintering temperature and shortens sintering time.

Description

A kind of preparation method of high entropy oxide ceramics
Technical field
The present invention relates to ceramic materials preparation technology fields, and in particular to a kind of preparation method of high entropy oxide ceramics.
Background technique
High entropy ceramic material refer to three kinds or more metallic elements and a kind of nonmetalloid composition with single crystal structure Ceramic material.Wherein, the mole percent of each metallic element is almost the same.Currently, the high entropy ceramics having been reported mainly include High entropy oxide, high entropy boride, high entropy carbide and high entropy silicide.High entropy ceramic material is because of entropy with higher, tool There is larger distortion of lattice, it is shown that unique mechanics, electrical and optical performance.
The method for preparing high entropy oxide ceramics at present is usually solid-phase sintering, binary oxide powder is mixed and in height The lower sintering of temperature, allows atom that adequately diffusion and mixing occurs.But this solid-phase sintering generally requires longer time；For example, Using powders such as MgO, NiO, CoO, CuO, ZnO 1000oMg is synthesized under the conditions of C0.2Ni0.2Co0.2Cu0.2Zn0.2O needs 12 are small When [C.M. Rost, E. Sachet, T. Borman, et al., Entropy-stabilized oxides, Nat. Commun. 6 (2015) 8485.].In addition, atomisation pyrolysis, flame spray pyrolysis and the anti-communism precipitation method are also used for synthesizing High entropy oxide powder [A. Sarkar, R. Djenadic, N.J. Usharani, et al., Nanocrystalline multicomponent entropy stabilised transition metal oxides, J. Eur. Ceram. Soc. 37(2) (2017) 747-754.].Atomisation pyrolysis, flame spray pyrolysis short, the quick quenching with generated time Etc. advantages, be suitble to the high entropy oxide powder of synthesis.But the above method is only applicable to synthesize high entropy oxide powder, is not suitable for The preparation of high entropy oxide ceramics.
Summary of the invention
The present invention provides a kind of system for the high entropy oxide ceramics that preparation process is simple, sintering temperature is low, sintering time is short Preparation Method.
The technical solution adopted by the present invention is that: a kind of preparation method of high entropy oxide ceramics, comprising the following steps:
Step 1: weighing 4 kinds or 5 kinds or less gold respectively according to the ratio that metallic atom molar ratio is 1:1:1:1 or 1:1:1:1:1 Belong to oxide powder；Oxide powder includes: MgO, ZnO, NiO, CuO, CaO, CoO, ZrO2、CeO2、Al2O3、Gd2O3、La2O3、 Er2O3、Y2O3、Fe2O3、Co3O4、CaCO3；
Step 2: ball milling, drying, granulation are carried out to powder weighed in step 1；
Step 3: the powder after granulation being pressed, green compact are obtained；
Step 4: the green compact that step 3 is obtained are heat-treated；
Step 5: the green compact heating after step 4 heat treatment is reached into preset temperature, applies the electric field of default electric field strength to sample, Power supply is changed into constant current state by pressure constant state after appearance flash burning, and 1~60 min, subsequent quenching are kept the temperature under predetermined current density Required high entropy oxide ceramics can be obtained；
Default electric field strength is 10-1000 V/cm, and predetermined current density is 10-3000 mA/mm2。
Further, the ball milling in the step 2 uses planetary type ball-milling, and drum's speed of rotation is 50~180 r/min, ball Time consuming is 10~50h.
Further, preset temperature is room temperature~0.7 Tm in the step 5, and heating rate is 10~30 DEG C/min, is reached 10 min are kept the temperature after to preset temperature.
Further, it is granulated in the step 2, PVA is added in ceramic powder and is granulated, the concentration of PVA is 3 wt%。
Further, compression moulding uses secondary compacting in the step 3, is first 100~200 MPa conditions in pressure Lower 30~60 s of pressure maintaining；Then secondary pressurized under the conditions of pressure is 200~300 MPa.
Further, heat treatment process is as follows in the step 4:
2 h are heat-treated under the conditions of 0.5 Tm, heating rate is 2~5 DEG C/min.
Further, drying temperature is 100 DEG C in the step 2, and soaking time is 10~30 h.
The beneficial effects of the present invention are:
(1) present invention prepares high entropy oxide ceramics using flash burning, significantly reduces synthesis temperature and shortens sintering time；
(2) the quick movement and mixing of metallic atom can be realized in a short time using the method for the present invention, obtaining has single crystalline substance The high entropy oxide ceramics of body structure.
Detailed description of the invention
Fig. 1 is the XRD diagram for the high entropy oxide ceramics that the embodiment of the present invention 1 is prepared.
Fig. 2 is the XRD diagram for the high entropy oxide ceramics that the embodiment of the present invention 2 is prepared.
Fig. 3 is the EDS figure for the high entropy oxide ceramics that the embodiment of the present invention 1 is prepared.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
A kind of preparation method of high entropy oxide ceramics, comprising the following steps:
Step 1: weighing 4 kinds or 5 kinds or less gold respectively according to the ratio that metallic atom molar ratio is 1:1:1:1 or 1:1:1:1:1 Belong to oxide powder；Oxide powder includes: MgO, ZnO, NiO, CuO, CaO, CoO, ZrO2、CeO2、Al2O3、Gd2O3、La2O3、 Er2O3、Y2O3、Fe2O3、Co3O4、CaCO3；
Step 2: ball milling, drying, granulation are carried out to powder weighed in step 1；
Deionized water will be added in load weighted powder, mixed in planetary ball mill, the revolving speed of ball mill is 50~180r/ Min, Ball-milling Time are 10~50 h.Drying and processing is carried out to obtained slurry, drying temperature is 100 DEG C, soaking time 10 ~30 h obtain uniformly mixed ceramic powder.PVA is added in ceramic powder after drying to be granulated, the concentration of PVA is 3 wt%。
Step 3: the powder after granulation being pressed, green compact are obtained；
Powder after granulation is pressed into sample using the method for molding, and sample is bone type sample, and pressure is 100~200 MPa, protects Press 30~60 s；Then sample is placed in cold isostatic press and secondary pressure testing is carried out with the pressure of 200~300 MPa.
Step 4: the green compact that step 3 is obtained are heat-treated；
Obtained green compact are heat-treated 2 h in 0.5 Tm, heating rate is 2~5 DEG C/min.
Step 5: by step 4 heat treatment after green compact, sample is connected with the platinum electrode in flash burning furnace, with 10~30 DEG C/ The heating rate of min is warmed to room temperature~0.7 Tm, after reaching preset temperature, keeps the temperature 1 ~ 10 min at such a temperature, so that Specimen temperature is consistent with furnace temperature.
The electric field for applying default electric field strength to sample applies electric field and keeps constant until power supply is by constant pressure after there is flash burning State is changed into constant current state, and 1~60 min is kept the temperature under predetermined current density, sample is then put into quenching in ice water High entropy oxide ceramics needed for obtaining；
Default electric field strength is 10-1000 V/cm, and predetermined current density is 10-3000 mA/mm2。
Embodiment 1
A kind of preparation method of high entropy oxide ceramics, comprising the following steps:
Step 1: weighing oxide powder, ZnO:MgO:NiO:CuO:Co by following molar ratio3O4=3:3:3:3:1 weighs powder, Total 21.37 g.
Step 2: 200 mL of deionized water will be added in load weighted powder, is mixed in planetary ball mill, ball mill Revolving speed is 180 r/min, and Ball-milling Time is 12 h；Obtained slurry is dried, drying temperature is 98 DEG C, and 24 h of time is obtained Uniformly mixed ceramic powder；PVA is added in ceramic powder after drying to be granulated, the concentration of PVA is 3 wt%.
Step 3: powder after granulation using the method for molding be pressed into dog bone shape sample (facilitate sample in flash burning furnace with electricity Extremely it is connected)；Under the conditions of pressure is 200 MPa, 60 s of pressure maintaining.Sample is placed in cold isostatic press with the pressure of 290 MPa Carry out secondary pressure.
Step 4: the green compact that step 3 obtains are heat-treated 2 h, heating rate 2 under the conditions of 500 DEG CoC/min.For Facilitate sample to connect with platinum filament wire, at the both ends of sample opens the hole of 1.6 ± 0.1 mm of Φ.The gauge length of sample having a size of 16.52 mm ×2.85 mm×1.50 mm。
Step 5: after green compact prepare, sample being connected with the platinum electrode in flash furnace.At room temperature, setting electricity Current density is 100 mA/mm2, then apply the electric field of 250 V/cm.Application electric field strength, which is kept constant until there is flash burning, to be showed As power supply is changed into constant current state by pressure constant state.In 100 mA/mm21 min is kept the temperature under constant current state, then removes application Sample is placed in quenching in ice water rapidly by electric field, obtains high entropy oxide ceramics.
From figure 1 it appears that ZnO, MgO, NiO, CuO, Co that crystal structure is different3O4Five kinds of ceramic material warps It crosses after flash burning processing, has realized the quick movement and mixing of metallic atom in a short time, obtained with single crystalline substance Five yuan of body structure high entropy oxide ceramics.As can be seen from Figure 3 at room temperature, by flash burning technique make ZnO, MgO, NiO, CuO, Co3O4Zn, Mg, Ni, Cu and Co element in five kinds of ceramic materials fully achieves uniform mixing in the soaking time of 1min, Do not occur the enrichment of metal cation in energy spectrum diagram.
Embodiment 2
A kind of preparation method of high entropy oxide ceramics, comprising the following steps:
Step 1: weighing oxide powder, ZnO:NiO:CuO:Co by following molar ratio3O4=3:3:3:1 weighs powder, amounts to 20 g。
Step 2: 200 mL of deionized water will be added in load weighted powder, is mixed in planetary ball mill, ball mill Revolving speed is 180 r/min, and Ball-milling Time is 12 h；Obtained slurry is dried, drying temperature is 98 DEG C, and 24 h of time is obtained Uniformly mixed ceramic powder；PVA is added in ceramic powder after drying to be granulated, the concentration of PVA is 3 wt%.
Step 3: powder after granulation using the method for molding be pressed into dog bone shape sample (facilitate sample in flash burning furnace with electricity Extremely it is connected)；Under the conditions of pressure is 200 MPa, 60 s of pressure maintaining.Sample is placed in cold isostatic press with the pressure of 290 MPa Carry out secondary pressure.
Step 4: the green compact that step 3 obtains are heat-treated 2 h, heating rate 2 under the conditions of 500 DEG CoC/min.For Facilitate sample to connect with platinum filament wire, at the both ends of sample opens the hole of 1.6 ± 0.1 mm of Φ.The gauge length of sample having a size of 16.52 mm ×2.85 mm×1.50 mm。
Step 5: after green compact prepare, sample being connected with the platinum electrode in flash furnace.At room temperature, setting electricity Current density is 200 mA/mm2, then apply the electric field of 60 V/cm.Application electric field strength, which is kept constant until there is flash burning, to be showed As power supply is changed into constant current state by pressure constant state.In 200 mA/mm25 min are kept the temperature under constant current state, then remove application Sample is placed in quenching in ice water rapidly by electric field, obtains high entropy oxide ceramics.
From figure 2 it can be seen that ZnO, NiO, CuO, Co that crystal structure is different3O4Four kinds of ceramic materials are by dodging After burning processing, the quick movement and mixing of metallic atom have been realized in a short time, has been obtained with single crystal knot The high entropy oxide ceramics of structure quaternary.
Flash burning sintering technology is used for the preparation of high entropy oxide ceramics by the present invention, can significantly reduce sintering temperature and shortening Sintering time.

Claims (7)

1. a kind of preparation method of high entropy oxide ceramics, which comprises the following steps:
Step 1: weighing 4 kinds or 5 kinds or less gold respectively according to the ratio that metallic atom molar ratio is 1:1:1:1 or 1:1:1:1:1 Belong to oxide powder；Oxide powder includes: MgO, ZnO, NiO, CuO, CaO, CoO, ZrO2、CeO2、Al2O3、Gd2O3、La2O3、 Er2O3、Y2O3、Fe2O3、Co3O4、CaCO3；
Step 2: ball milling, drying, granulation are carried out to powder weighed in step 1；
Step 3: the powder after granulation being pressed, green compact are obtained；
Step 4: the green compact that step 3 is obtained are heat-treated；
Step 5: the green compact heating after step 4 heat treatment is reached into preset temperature, applies the electric field of default electric field strength to sample, Power supply is changed into constant current state by pressure constant state after appearance flash burning, and 1~60min, subsequent quenching are kept the temperature under predetermined current density Required high entropy oxide ceramics can be obtained；
Default electric field strength is 10-1000V/cm, and predetermined current density is 10-3000mA/mm2。
2. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 2 Ball milling use planetary type ball-milling, drum's speed of rotation be 50~180r/min, Ball-milling Time be 10~50h.
3. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 5 Preset temperature is room temperature~0.7Tm, and heating rate is 10~30 DEG C/min, keeps the temperature 10min after reaching preset temperature.
4. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 2 It is granulated, PVA is added in ceramic powder and is granulated, the concentration of PVA is 3wt%.
5. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 3 Compression moulding uses secondary compacting, first 30~60s of pressure maintaining under the conditions of pressure is 100~200MPa；It then is 200 in pressure Secondary pressurized under the conditions of~300MPa.
6. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 4 Heat treatment process is as follows:
2h is heat-treated under the conditions of 0.5Tm, heating rate is 2~5 DEG C/min.
7. a kind of preparation method of high entropy oxide ceramics according to claim 1, which is characterized in that in the step 2 Drying temperature is 100 DEG C, and soaking time is 10~30h.
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CN110818430A (en) * 2019-11-12 2020-02-21 西安交通大学 Uniform high-entropy oxide ceramic submicron spherical powder and preparation method thereof
CN110903084A (en) * 2019-11-12 2020-03-24 西安交通大学 High-entropy oxide submicron powder and preparation method thereof
CN110950654A (en) * 2019-12-16 2020-04-03 东南大学 High-entropy magnesium aluminate spinel type complex oxide and preparation method thereof
CN111924899A (en) * 2020-08-11 2020-11-13 中钢集团南京新材料研究院有限公司 Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application
CN112341160A (en) * 2020-11-06 2021-02-09 南京工业大学 Broadband high-Q low-temperature coefficient barium-magnesium-calcium-niobium-tantalum composite ceramic and preparation method thereof
CN113041398A (en) * 2021-03-16 2021-06-29 上海大学绍兴研究院 High-entropy ceramic composite collagen material, preparation method and application thereof, and high-entropy ceramic composite collagen artificial bone
CN113461415A (en) * 2021-07-19 2021-10-01 中国科学院兰州化学物理研究所 Hydrothermal method for preparing high-entropy oxide material (MAlFeCuMg)3O4Method (2)
CN113912396A (en) * 2021-11-11 2022-01-11 江苏金石研磨有限公司 High-entropy ceramic grinding ball and preparation method thereof
CN113929449A (en) * 2021-11-25 2022-01-14 西南科技大学 Nano high-entropy oxide ceramic powder and preparation method thereof
CN114907102A (en) * 2022-04-18 2022-08-16 国网江西省电力有限公司电力科学研究院 Ceramic material and room-temperature ultrafast reactive sintering method thereof
CN115093214A (en) * 2022-07-21 2022-09-23 南京信息工程大学 Ultrafast preparation method of high-entropy oxide
CN115159974A (en) * 2022-06-24 2022-10-11 东莞理工学院 SrFeO 3-x Reactive flash firing preparation method of ceramic
CN115196968A (en) * 2022-06-10 2022-10-18 华南理工大学 High-entropy boride ceramic powder and preparation method and application thereof
CN115286389A (en) * 2022-07-07 2022-11-04 华南理工大学 High-entropy carbide ceramic powder and preparation method and application thereof
CN115340361A (en) * 2021-05-14 2022-11-15 郑州大学 High-entropy ceramic for microwave kiln and preparation method and application thereof
CN115594494A (en) * 2021-07-08 2023-01-13 武汉苏泊尔炊具有限公司（Cn） Non-stick material, preparation method thereof, non-stick coating and cooking utensil
CN115838993A (en) * 2022-12-13 2023-03-24 南京邮电大学 High-infrared-radiation fiber felt and preparation method thereof
CN116354407A (en) * 2023-03-20 2023-06-30 南京航空航天大学 High-entropy oxide and preparation method and application thereof

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CN113461415A (en) * 2021-07-19 2021-10-01 中国科学院兰州化学物理研究所 Hydrothermal method for preparing high-entropy oxide material (MAlFeCuMg)3O4Method (2)
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CN113912396A (en) * 2021-11-11 2022-01-11 江苏金石研磨有限公司 High-entropy ceramic grinding ball and preparation method thereof
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CN114907102A (en) * 2022-04-18 2022-08-16 国网江西省电力有限公司电力科学研究院 Ceramic material and room-temperature ultrafast reactive sintering method thereof
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CN115159974A (en) * 2022-06-24 2022-10-11 东莞理工学院 SrFeO 3-x Reactive flash firing preparation method of ceramic
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