CN112979311B - Nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering and method thereof - Google Patents
Nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering and method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermal barrier coating materials, and discloses a nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering and a preparation method thereof, wherein the structural formula of the ceramic is A 4 B 2 O 9 Wherein A is one or more of Ni, co, mg, ca, sr, ba or Zn, and B is Ta; the preparation method of the ceramic comprises mixing A (OH) 2 、ACO 3 And the tantalum oxalate is respectively subjected to thermal decomposition for 1 to 2 hours at the temperature of between 350 and 900 ℃ to obtain AO and Ta with high reaction activity 2 O 5 Powder; then adding AO and Ta 2 O 5 Grinding the powder to obtain a nano-scale highly reactive powder mixture; and finally, performing discharge plasma sintering on the high-reactivity powder mixture to prepare blocky A4B2O9 type tantalate ceramic. The invention solves the problem of higher cost of the existing thermal barrier coating and environmental barrier coating materials.
Description
Technical Field
The invention belongs to the technical field of thermal barrier coating materials, and particularly relates to nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering and a method thereof.
Background
In recent years, the rapid development of thermal barrier coatings and environmental barrier coating materials has led to the development and application of oxide ceramics of different types of crystal structures. Wherein the rare earth tantalate (RETaO) 4 、RE 3 TaO 7 And Reta 3 O 9 ) Due to excellent thermo-mechanical properties (low thermal conductivity, high coefficient of thermal expansion, high fracture toughness, low modulus, high temperature stability, corrosion resistance, etc.), they are continuously studied and applied. But do notThe main raw material of the rare earth tantalate is rare earth element, and the rare earth element is protected as strategic resource in China, so that the exploitation amount of the rare earth element is small, and the price of the rare earth element is very high, so that the manufacturing cost of the rare earth tantalate is high.
In order to reduce the cost of the thermal barrier coating and the environmental barrier coating, the inventor researches the materials of the thermal barrier coating and the environmental barrier coating to form A4B2O9 type tantalate ceramics.
Disclosure of Invention
The invention aims to provide a nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering and a method thereof, so as to solve the problem that the existing thermal barrier coating and environmental barrier coating materials are high in manufacturing cost.
In order to realize the purpose, the invention provides the following technical scheme that the nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering has a structural formula A 4 B 2 O 9 Wherein A is one or more of Ni, co, mg, ca, sr, ba or Zn, and B is Ta.
The A4B2O9 type tantalate ceramic provided by the technical scheme has the characteristics of high compactness, high purity and nanocrystalline, and the hardness, fracture toughness and modulus of the ceramic material are very high, so that the thermophysical properties of the ceramic material can be regulated and controlled, and the A4B2O9 type tantalate ceramic can be used as a thermal barrier coating and an environmental barrier coating; moreover, the A4B2O9 type tantalate ceramics do not contain rare earth elements, so the manufacturing cost is relatively low.
The invention also provides another basic scheme, and a method for preparing nanocrystalline A4B2O9 type tantalate ceramics by ultralow temperature sintering comprises the following steps:
in the first step of the method,
a (OH) 2 、ACO 3 And the tantalum oxalate are respectively thermally decomposed at the temperature of 350-900 ℃ for 1-2h to obtain AO and Ta with high reaction activity 2 O 5 Powder;
in the second step, the first step is that,
reacting AO with Ta 2 O 5 Grinding the powder to obtain a nano-scale highly reactive powder mixture;
step three, performing a first step of cleaning the substrate,
and (3) performing discharge plasma sintering on the highly reactive powder mixture to prepare blocky A4B2O9 type tantalate ceramics.
The beneficial effects of the technical scheme are as follows:
1. the bulk A4B2O9 type tantalate ceramic prepared by the technical scheme has the purity of more than 99 percent, the density of more than 98 percent and the average grain size of less than 300nm, and because the A4B2O9 type tantalate ceramic has fine and uniform nano crystals, phonons can be effectively scattered, the thermal conductivity of the material is reduced, and the heat insulation and protection capability of the material is improved; the hardness, the fracture toughness and the modulus of the A4B2O9 type tantalate ceramic prepared by the method can be improved by high compactness, high purity and nanocrystalline, so that the A4B2O9 type tantalate ceramic has better thermal physical properties;
2. according to the technical scheme, the raw materials are subjected to thermal decomposition to form powder with high reactivity, so that the temperature required by the reaction between oxides during sintering can be reduced, the time can be shortened, the energy can be saved, and the efficiency can be improved; in addition, the problems of overburning and excessive growth of crystal grains caused by a common sintering method can be avoided, and the problems of high porosity and poor thermal-mechanical property of the material in the produced ceramic block are further avoided.
Further, in the second step, alcohol with the concentration of 99.99% is added during grinding, and the mass ratio of the powder to the alcohol is 1:6-10.
Has the advantages that: can keep the powder moist, conveniently grind.
Further, in the second step, the grinding speed is 2200 to 3000rpm, and the grinding time is 12 to 20 hours.
Has the advantages that: by controlling the rotating speed and the grinding time, the nano-scale powder meeting the requirement can be obtained.
Further, in the second step, after grinding, taking out the powder, and preserving heat for 6-10h at 65-80 ℃.
Has the advantages that: and (3) carrying out heat preservation treatment on the powder after grinding to realize volatilization of alcohol mixed in the powder, and drying the powder.
Further, in the third step, the sintering temperature is 620-700 ℃, the heat preservation time is 6-10min, and the heat preservation pressure is 100-300Mpa.
Has the advantages that: sintering the powder into blocky A4B2O9 type tantalate ceramics can be realized by controlling the sintering temperature, the heat preservation time and the heat preservation pressure; meanwhile, the sintering temperature is low, the phenomena of overburning and excessive growth of crystal grains can be prevented, the formation and the maintenance of nano crystals are facilitated, and the energy consumption is low; and the time cost is also lower.
And further, in the third step, before sintering, spraying BN on the die.
Has the advantages that: and BN is sprayed before sintering, so that carbon in a sintering die can be prevented from permeating into the powder, and the high purity of the prepared blocky A4B2O9 type tantalate ceramic can be ensured. Meanwhile, the annealing and decarbonization process after sintering is avoided, and pores and cracks are introduced into the block body during annealing and decarbonization, so that the density of the material is reduced, and the technical scheme can ensure that the prepared massive A4B2O9 type tantalate ceramic has high density.
Further, sintering the high-reactivity powder mixture obtained in the step two at 700 ℃ for 1-5h, cooling, and preparing the A in a spray granulation mode 4 B 2 O 9 And (3) forming tantalate spherical powder.
Has the advantages that: because the powder has high reactivity, the energy required by sintering is lower, the sintering can be completed at lower temperature, and the energy consumption is reduced; at the same time, the agglomeration phenomenon among the powders can be inhibited, so that the prepared A 4 B 2 O 9 The type tantalate spherical powder can be used as an atmospheric plasma spraying raw material for preparing a coating without grinding and sieving.
Description of the figures/tables
FIG. 1 is a comparison of the XRD diffractogram of example 1 of the present invention with a standard card;
FIG. 2 shows Ca provided in example 1 of the present invention 4 Ta 2 O 9 A surface micro-topography of the bulk ceramic;
FIG. 3 shows Ca provided in example 8 of the present invention 2 Mg 2 Ta 2 O 9 Thermal conductivity of (2) shows as a function of temperatureIntention is.
Detailed Description
The following is further detailed by way of specific embodiments:
a nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering, the structural formula of the ceramic is A 4 B 2 O 9 Wherein A is one or more of Ni, co, mg, ca, sr, ba or Zn, and B is Ta. The purity of the ceramic is more than 99%, the density is more than 98%, and the average grain size is less than 300nm.
Example 1:
a nanocrystalline A4B2O9 type tantalate ceramic prepared by ultralow temperature sintering, the structural formula of the ceramic is Ca 4 Ta 2 O 9 The preparation method comprises the following steps:
in the first step of the method,
mixing Ca (OH) 2 、CaCO 3 And respectively keeping the temperature of the oxalic acid till the temperature is 350-900 ℃ for 1-2h, and performing thermal decomposition on the raw materials in the heat preservation process to obtain CaO and Ta with high reactivity 2 O 5 And (3) powder. In the embodiment, the heat preservation temperature is preferably 900 ℃, and the heat preservation time is preferably 1h.
In the second step, the first step is that,
according to Ca 4 Ta 2 O 9 The structural formula of (A) is to weigh CaO and Ta with high reactivity 2 O 5 Powdering and mixing highly reactive CaO and Ta 2 O 5 Putting the powder into a high-energy ball mill, putting 99.99 percent alcohol into the high-energy ball mill, wherein the weight ratio of the powder to the alcohol is 1:6-10, and performing reaction on CaO and Ta at the rotating speed of 2200-3000rpm 2 O 5 Grinding the powder for 12-20h, taking out the powder, and preserving heat at 65-80 ℃ for 6-10h to obtain a nanoscale high-reactivity powder mixture. In the embodiment, the weight ratio of the powder to the alcohol during grinding is 1:8, the rotation speed during grinding is preferably 2200rpm, and the grinding time is preferably 16h; after grinding, the temperature of heat preservation is preferably 75 ℃, and the heat preservation time is preferably 6h.
The third step is that,
spraying BN on the graphite mould for sintering, and shaping in the second stepPutting the obtained nanoscale highly reactive powder mixture into a graphite mold for sintering at 620-700 deg.C under 100-300Mpa for 6-10min to obtain block Ca 4 Ta 2 O 9 A ceramic. In this embodiment, the sintering temperature is preferably 620 ℃, the heat preservation time is preferably 10min, and the heat preservation pressure is preferably 150MPa.
Example 2:
example 2 differs from example 1 in that the A4B2O9 type tantalate ceramic in this example has a structural formula of Ni 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 3:
example 3 is different from example 1 in that the A4B2O9 type tantalate ceramic in this example has a structure of Co 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 4:
example 4 differs from example 1 in that the A4B2O9 type tantalate ceramic in this example has the structural formula of Mg 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 5:
example 5 differs from example 1 in that the A4B2O9 type tantalate ceramic in this example has a structural formula of Sr 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 6:
example 6 is different from example 1 in that the structural formula of the A4B2O9 type tantalate ceramic in this example is Ba 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 7:
example 7 is different from example 1 in that the A4B2O9 type tantalate ceramic in this example has a structure of Zn 4 Ta 2 O 9 The preparation process is identical to example 1.
Example 8:
example 8 differs from example 1 in that this practiceIn the examples, the structure of the A4B2O9 type tantalate ceramic is Ca 2 Mg 2 Ta 2 O 9 (ii) a The preparation method is different from the embodiment 1 in that the heat preservation temperature of the thermal decomposition in the step one is 545 ℃, and the heat preservation time is 2h; in the second step, the rotation speed during grinding is 2800rpm, the grinding time is 20h, the heat preservation temperature after grinding is 80 ℃, and the heat preservation time is 8h; the sintering temperature in the third step is 650 ℃, the heat preservation time is 8min, and the heat preservation pressure is 200Mpa.
Example 9:
example 9 differs from example 8 in that the structure of the A4B2O9 type tantalate ceramic in this example is CaMgZnBaTa 2 O 9 (ii) a The preparation method is different from the embodiment 1 in that the heat preservation temperature of the thermal decomposition in the step one is 350 ℃, and the heat preservation time is 1h; in the second step, the rotation speed during grinding is 3000rpm, the grinding time is 12 hours, the heat preservation temperature after grinding is 65 ℃, and the heat preservation time is 10 hours; in the third step, the sintering temperature is 680 ℃, the heat preservation time is 6min, and the heat preservation pressure is 230Mpa.
Example 10:
the difference between the embodiment 10 and the embodiment 9 is that, in the third step of the present embodiment, the nano-scale highly reactive powder mixture in the second step is put into a high temperature sintering furnace, and is sintered for 1 to 5 hours under the temperature of 700 ℃, and then the sintered powder is taken out and cooled, and finally the CaMgZnBaTa is prepared by using a spray granulation method 2 O 9 The ceramic powder prepared is spherical, can be used as an air plasma spraying raw material for preparing a coating, and the sintering time is preferably 1h in the embodiment. The purity of the powder can be obtained by XRD test, and the result is consistent with that of figure 1.
Experiment:
nanocrystalline A4B2O 9-type tantalate ceramics provided in examples 1-9 were selected and subjected to the following experiment:
XRD characterization
The A4B2O 9-type tantalate ceramic blocks obtained in examples 1 to 9 were examined using an X-ray diffractometer, wherein the XRD pattern of example 1 is shown in fig. 1. According to the results shown in FIG. 1, ca 4 Ta 2 O 9 Derivatives of ceramicsThe peak shooting corresponds to the standard PDF #31-0308 one by one.
SEM characterization
The A4B2O 9-type tantalate ceramic blocks obtained in examples 1-9 were examined by scanning electron microscopy, wherein the surface micro-topography of example 1 is shown in FIG. 2. As can be seen from FIG. 2, ca 4 Ta 2 O 9 The grain size of the ceramic is uniform, the grain size is less than 300nm, the grain boundary is clear, no obvious air holes and cracks exist on the surface, and the density is as high as 99.5%.
3. Thermal conductivity detection
The ceramic blocks obtained in examples 1 to 9 were polished into round sheets having a diameter of 6X 1mm, and the thermal conductivity thereof was measured by a laser thermal conductivity meter, wherein the thermal conductivity of each of the ceramic blocks of examples 1 to 9 at 900 ℃ is shown in Table 1, and the Ca provided in example 8 at room temperature to 900 ℃ is measured 2 Mg 2 Ta 2 O 9 The thermal conductivity curve of the ceramic block is shown in fig. 3. As can be seen from fig. 3, the thermal conductivity of the ceramic block decreases sharply with increasing temperature, and decreases slowly after 600 ℃. At a temperature of 900 ℃ Ca 2 Mg 2 Ta 2 O 9 The thermal conductivity of the ceramic block is reduced to 1.4W.m -1 .K -1 Thus, the material has excellent heat insulation capability in high-temperature environment.
4. Density detection
The ceramic blocks provided in examples 1 to 9 were examined using archimedes' drainage.
The results of the experiments on the tantalate ceramics type A4B2O9 provided in examples 1 to 9 are shown in table 1.
TABLE 1
| Structural formula (I) | Young's modulus | Hardness of | Thermal conductivity | Compactness degree | |
| Example 1 | Ca 4 Ta 2 O 9 | 186 | 9.2 | 2.1-5.2 | 99.5 |
| Example 2 | Ni 4 Ta 2 O 9 | 163 | 7.6 | 1.5-4.3 | 99.0 |
| Example 3 | Co 4 Ta 2 O 9 | 201 | 10.9 | 2.3-6.0 | 99.7 |
| Example 4 | Mg 4 Ta 2 O 9 | 144 | 7.1 | 1.2-3.9 | 99.6 |
| Example 5 | Sr 4 Ta 2 O 9 | 169 | 8.0 | 1.8-4.6 | 99.0 |
| Example 6 | Ba 4 Ta 2 O 9 | 210 | 12.5 | 2.5-3.9 | 99.1 |
| Example 7 | Zn 4 Ta 2 O 9 | 152 | 6.6 | 2.0-4.3 | 99.3 |
| Example 8 | Ca 2 Mg 2 Ta 2 O 9 | 162 | 8.3 | 1.4-4.2 | 99.8 |
| Example 9 | CaMgZnBaTa 2 O 9 | 180 | 10.6 | 1.3-3.7 | 99.1 |
In conclusion, the A4B2O9 type tantalate ceramic provided by the invention has the purity of more than 99%, the compactness of more than 98%, the average grain size of less than 300nm, and low thermal conductivity at high temperature, and can be used as a thermal barrier coating material and an environmental barrier coating material. Compared with the existing rare earth tantalate thermal barrier coating material, the rare earth tantalate thermal barrier coating material does not use rare earth elements in raw materials, has low preparation cost and is more suitable for use and research.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and these changes and modifications should not be construed as affecting the performance of the invention and its practical application.
Claims (8)
1. Nanocrystalline A prepared by ultralow temperature sintering 4 B 2 O 9 The type tantalate ceramic is characterized in that: the structural formula of the ceramic is A 4 B 2 O 9 Wherein a consists of Mg, ca, ba and Zn in a molar ratio of 1; the average grain size is less than 300nm;
the preparation method comprises the following steps: a (OH) 2 、ACO 3 And respectively keeping the tantalum oxalate at 350-900 ℃ for 1-2h for thermal decomposition to obtain AO and Ta with high reactivity 2 O 5 Powder; reacting AO with Ta 2 O 5 Grinding the powder to obtain a nano-scale highly reactive powder mixture; and (3) performing discharge plasma sintering on the high-reactivity powder mixture to prepare blocky tantalate ceramics.
2. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 1 4 B 2 O 9 A method of forming a tantalate ceramic, comprising the steps of:
in the first step of the method,
a (OH) 2 、ACO 3 And the tantalum oxalate are respectively thermally decomposed at the temperature of 350-900 ℃ for 1-2h to obtain AO and Ta with high reaction activity 2 O 5 Powder;
in the second step, the first step is to perform the first step,
reacting AO with Ta 2 O 5 Grinding the powder to obtain a nano-scale highly reactive powder mixture;
the third step is that,
sintering the highly reactive powder mixture by spark plasma to obtain block A 4 B 2 O 9 A type tantalate ceramic.
3. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: in the second step, alcohol with the concentration of 99.99 percent is added during grinding, and the mass ratio of the powder to the alcohol is 1:6-10.
4. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: in the second step, the grinding speed is 2200 to 3000rpm, and the grinding time is 12 to 20 hours.
5. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: in the second step, after grinding, the powder is taken out and kept at 65-80 ℃ for 6-10h.
6. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: in the third step, the sintering temperature is 620-700 ℃, the heat preservation time is 6-10min, and the heat preservation pressure is 100-300MPa.
7. According to claimPreparation of nanocrystalline A by ultra-low temperature sintering as described in claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: in the third step, before sintering, spray BN to the mould.
8. The method for preparing the nanocrystalline A through ultralow-temperature sintering according to claim 2 4 B 2 O 9 A method of forming a tantalate ceramic, comprising: sintering the high-reactivity powder mixture obtained in the step two at 700 ℃ for 1-5h, cooling, and preparing A in a spray granulation mode 4 B 2 O 9 And (3) forming tantalate spherical powder.
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| CN113548891B (en) * | 2021-08-19 | 2022-10-18 | 陕西天璇涂层科技有限公司 | Two-phase cobalt tantalate ceramic block and preparation method thereof |
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