CN119038989A - Cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium and preparation method thereof - Google Patents
Cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium and preparation method thereof Download PDFInfo
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- 238000000227 grinding Methods 0.000 title claims abstract description 89
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 26
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 238000000465 moulding Methods 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 61
- 239000003381 stabilizer Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 5
- 238000000498 ball milling Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 description 36
- 238000002441 X-ray diffraction Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C09K3/00—Materials not provided for elsewhere
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
本发明提供一种氧化铈/氧化钇复合稳定氧化锆研磨介质及制备方法，该方法包括：步骤一、将氧化锆、氧化铈、氧化钇和高岭土混合，再加入适量分散剂和水研磨得到浆料；步骤二、浆料进行离心喷雾干燥得到氧化铈/氧化钇复合稳定氧化锆粉；步骤三、再将氧化铈/氧化钇复合稳定氧化锆粉加入粘结剂，滚动成型制得球形研磨介质生坯；步骤四、球形研磨介质生坯烧结、抛光后得到氧化铈/氧化钇复合稳定氧化锆研磨介质。该方法通过高温球磨获得低粒径、高比表的同时也通过热处理促进稳定剂固溶到氧化锆晶格中，从而提高烧结活性、降低烧结温度，降低生产成本。
The present invention provides a cerium oxide/yttrium oxide composite stabilized zirconia grinding medium and a preparation method thereof, the method comprising: step 1, mixing zirconia, cerium oxide, yttrium oxide and kaolin, and then adding an appropriate amount of dispersant and water to grind to obtain a slurry; step 2, centrifugal spray drying the slurry to obtain cerium oxide/yttrium oxide composite stabilized zirconia powder; step 3, adding a binder to the cerium oxide/yttrium oxide composite stabilized zirconia powder, and rolling forming to obtain a spherical grinding medium green body; step 4, spherical grinding medium green body sintering, polishing to obtain cerium oxide/yttrium oxide composite stabilized zirconia grinding medium. The method obtains low particle size and high specific surface area through high-temperature ball milling, and also promotes the solid solution of the stabilizer into the zirconia lattice through heat treatment, thereby improving the sintering activity, reducing the sintering temperature, and reducing the production cost.
Description
Technical Field
The invention relates to the technical field of zirconia ceramics, in particular to a ceria/yttria composite stabilized zirconia grinding medium and a preparation method thereof.
Background
Tetragonal zirconia ceramics (TZP) are the most representative ceramics, and are widely used in various fields due to their advantages of high strength, high hardness, high fracture toughness, and good biocompatibility. The tetragonal zirconia has excellent wear resistance as the grinding medium, and is widely applied to the fields of paint, printing ink, anode material grinding and the like.
Yttria-stabilized tetragonal zirconia ceramics (Y-TZP) are TZP materials which are the most studied, and the content of yttria is critical to the performance of zirconia ceramics, for example, when the content of yttria is lower than 2mol percent, tetragonal zirconia with higher content is difficult to obtain, the toughness of the material is the best when the content is 2mol percent, and the strength of the material is the highest when the content is 2-3 mol percent. However, Y-TZP is used in a low-temperature and humid environment, particularly in a temperature range of 65-400 ℃, is extremely easy to generate low-temperature aging phenomena, and is mainly characterized by micro or macro microcracks on the surface, so that the mechanical properties of the material are affected to a certain extent, and the application of the material in a special environment is limited. Therefore, it is important to prevent Y-TZP from low temperature aging. TZP ceramic using CeO 2 as stabilizer has excellent fracture toughness and ageing resistance, but compared with Y-TZP, densification of Ce-TZP requires higher sintering temperature and longer heat preservation time, and Ce-TZP grains are thicker, so that strength and hardness are lower.
The ZrO 2 ceramics stabilized by a single stabilizer have certain limitations in practical application. By adding two or more stabilizers to the ZrO 2 matrix, zrO 2 composite ceramic with better comprehensive properties can be obtained. Several scholars have also conducted a series of studies on zirconia ceramics co-stabilized with various stabilizers. Yin Bangyue et al adopts a coprecipitation process to prepare YCe-TZP ceramics with different proportions in low-temperature aging of YCe-TZP ceramics, and performs a low-temperature aging test after sintering at 1450 ℃, wherein 3Y4Ce-TZP hardly causes aging phenomenon, and a CeO 2 protective layer is formed on the surface of 3Y4Ce-TZP in the aging process to prevent Y-OH bond formation, thereby effectively inhibiting t (tetragonal phase) to m (monoclinic phase) aging phase transition. However, the introduction of cerium oxide as a stabilizer results in higher sintering temperature of zirconium oxide and reduced mechanical properties, thereby affecting the wear resistance of the zirconium oxide as a grinding medium. At present, the application report of the cerium oxide and yttrium oxide composite stable zirconia material in the grinding medium is less, and how to ensure the cerium oxide and yttrium oxide composite stable zirconia material to have excellent low-temperature aging resistance and wear resistance is a crucial point for pushing the cerium oxide and yttrium oxide composite stable zirconia material to be applied in the field of the grinding medium. Sintering of the grinding media is also the link with the greatest energy consumption ratio, so reducing the sintering temperature is also an important research point for zirconia grinding media.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium and the preparation method thereof, and the cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium which can be sintered compactly at low temperature and has excellent ageing resistance and wear resistance and the preparation method thereof can prolong the service life and reduce the production cost.
In order to achieve the above purpose, the invention provides a cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium and a preparation method thereof, wherein the preparation method comprises the following steps:
Step one, mixing zirconium oxide, cerium oxide, yttrium oxide and kaolin according to a certain adding proportion, adding a proper amount of dispersing agent and deionized water, and grinding to obtain uniformly mixed slurry;
Centrifugal spray drying is carried out on the evenly mixed slurry to obtain cerium oxide and yttrium oxide composite stable zirconia powder, the rotating speed of a spray drying atomizing disc is 9000-11000r/min, the inlet temperature is 240-260 ℃, the outlet temperature is 95-110 ℃, and good sphericity and fluidity of the granulated powder are ensured;
Thirdly, adding the cerium oxide and yttrium oxide composite stable zirconia powder into a binder for rolling forming to obtain a spherical grinding medium green body;
And step four, polishing after sintering the grinding medium green body to obtain the cerium oxide and yttrium oxide composite stable zirconium oxide grinding medium.
Preferably, in the first step, the addition amount of zirconia, ceria, yttria and kaolin is 85-90wt%,10-15wt%,1-2 wt% and 0.1-0.5wt%.
Preferably, in the first step, the dispersant is Dolapix ce to 64, and the addition amount is 0.5wt%.
Preferably, in the first step, the deionized water is added in an amount of 50wt% and the solid content of the slurry is 50wt%.
Preferably, in the first step, the slurry temperature is maintained at 70-90 ℃ during the grinding process.
Preferably, in the first step, the mixed slurry has a grinding particle size D50 controlled in a range of 0.15 to 0.2um.
Preferably, in the third step, the binder is a combination of PVA, glycerol and water.
Preferably, in the fourth step, the temperature of the grinding medium green body is raised to 1300-1350 ℃ by adopting the temperature raising speed of 2 ℃ per min in the sintering process, the temperature is kept for 2 hours under the condition of no pressure in the air atmosphere, and then the temperature is naturally lowered to the room temperature.
Preferably, in the fourth step, the sintered grinding medium is polished by a sand mill at a linear speed of 8m/s, and the polishing material is white corundum with an addition amount of 2wt%.
The beneficial effects of the invention are as follows:
The invention obtains low grain diameter and high specific surface by high temperature ball milling, and simultaneously promotes the stabilizer to be solid-dissolved into the zirconia crystal lattice by heat treatment, thereby improving the sintering activity, and obtaining the stable tetragonal phase zirconia by low temperature (1300-1350 ℃) sintering, and the density is as high as 6.13-6.14g/m 3. The surface roughness is reduced by polishing treatment in the later stage, the performances are combined, the polishing agent has excellent wear resistance in the grinding process, the self-abrasion is lower than 10ppm/h, and the service life is prolonged.
The invention adopts a solid phase synthesis process, adds a small amount of yttrium oxide on the basis of cerium oxide stabilized zirconia ceramic to improve the mechanical property, adds kaolin as a sintering aid, and mainly comprises aluminum oxide and silicon oxide, and adds the kaolin to improve the sintering activity, reduce the sintering temperature to obtain excellent low-temperature aging resistance and reduce the production cost.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 1 before aging;
FIG. 2 is an X-ray diffraction pattern of example 1 after aging;
FIG. 3 is an X-ray diffraction pattern of example 2 before aging;
FIG. 4 is an X-ray diffraction pattern of example 2 after aging;
FIG. 5 is an X-ray diffraction pattern of comparative example 1 before aging;
FIG. 6 is an X-ray diffraction pattern of comparative example 1 after aging;
FIG. 7 is an X-ray diffraction pattern of comparative example 2 before aging;
FIG. 8 is an X-ray diffraction pattern of comparative example 2 after aging;
FIG. 9 is an X-ray diffraction pattern of comparative example 3 before aging;
FIG. 10 is an X-ray diffraction pattern of comparative example 3 after aging;
FIG. 11 is an X-ray diffraction pattern of comparative example 4 before aging;
FIG. 12 is an X-ray diffraction pattern of comparative example 4 after aging;
FIG. 13 is an X-ray diffraction pattern of comparative example 5 before aging;
FIG. 14 is an X-ray diffraction pattern of comparative example 5 after aging.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to the following specific examples.
The testing method comprises the following steps:
1. Grinding medium density, archimedes drainage method,
2. Grinding medium abrasion, 1L sand mill, grinding medium addition amount 2.6kg is recorded as m 0, the grinding medium addition amount is measured at a linear speed of 12m/s in clear water for 20 hours and is recorded as t, weight loss is calculated by weighing, weight before test is recorded as m 1, and weight after test is recorded as m 2,
;
3. Phase content X-ray diffractometer (XRD);
4. And (3) testing the low-temperature ageing resistance, namely placing the sample into a hydrothermal kettle, adding water to a filling rate of 80%, and carrying out hydrothermal treatment for 48 hours at 200 ℃.
Example 1:
Mixing zirconia, ceria, yttria and kaolin according to the proportion of 86.2wt%, 12wt%, 1.5wt% and 0.3wt%, adding pure water to the solid content of 50%, grinding by adopting a roller ball mill, adding 0.5wt%Dolapix ce64 as a dispersing agent, controlling the temperature at about 80 ℃ in the grinding process, transferring the slurry to a granulating tower for spray granulation when the particle size D 50 =0.15 um is ground, and obtaining the ceria and yttria composite stable zirconia powder at the inlet temperature of 250 ℃ and the outlet temperature of 105 ℃ at the rotating speed of 10000r/min of an atomizing disc.
The grinding medium ball green compact is prepared by adopting the powder to add the binder (the binder is PVA, glycerol and deionized water are mixed according to the proportion of 1:0.5:90) through rolling forming, and the addition amount of the binder is 8-10wt%. And (3) raising the temperature of the green body from room temperature to 1330 ℃ at a heating speed of 2 ℃ per minute in an air atmosphere, preserving heat for 2.5 hours, naturally cooling to room temperature, adding 2wt% of white corundum, and polishing in a sand mill at a linear speed of 8m/s until the surface is smooth, thus obtaining the finished product of the cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium ball. The grinding medium density 6.138g/m 3, the abrasion test result is 8.0ppm/h, and the grinding medium is aged for 48 hours under the hydrothermal condition of 200 ℃ and the tetragonal phase content is 100%. Fig. 1 and 2 show X-ray diffraction patterns before and after aging of the grinding medium, respectively, wherein the ordinate represents the relative intensity and the abscissa represents the diffraction angle 2θ.
Example 2:
Mixing zirconia, ceria, yttria and kaolin according to the proportion of 85wt%, 13.2wt%, 1.5wt% and 0.3wt%, adding pure water to the solid content of 50%, grinding by adopting a roller ball mill, adding 0.5wt%Dolapix ce64 Sima Huagong CE64 as a dispersing agent, controlling the temperature at about 80 ℃ in the grinding process, and transferring the slurry to a granulating tower for spray granulation when the particle size D50=0.15 um is ground, wherein the rotating speed of an atomizing disc is 10000r/min, the inlet temperature is 250 ℃, and the outlet temperature is 105 ℃ to obtain the ceria and yttria composite stable zirconia powder.
The grinding medium ball green body is prepared by adopting the powder to add the binder (the binder is PVA, glycerol and deionized water are mixed according to the proportion of 1:0.5:90) and rolling and forming. And (3) raising the temperature of the green body from room temperature to 1330 ℃ at a heating speed of 2 ℃ per minute in an air atmosphere, preserving heat for 2.5 hours, naturally cooling to room temperature, adding 2wt% of white corundum, and polishing in a sand mill at a linear speed of 8m/s until the surface is smooth, thus obtaining the finished product of the cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium ball. The grinding medium density 6.140g/m3, the abrasion test result is 8.2ppm/h, the grinding medium is aged for 48h under the hydrothermal condition of 200 ℃, the tetragonal phase content is 100%, the X-ray diffraction patterns before and after the grinding medium aging are respectively shown in fig. 3 and 4, the ordinate of the X-ray diffraction patterns shows the relative intensity, and the abscissa of the X-ray diffraction patterns shows the diffraction angle 2 theta.
Comparative example 1:
Compared with example 1, zirconia, ceria, yttria and kaolin are mixed according to the proportion of 86.2wt%, 13.5wt%, 0wt% and 0.3wt%, and the rest conditions are the same, so that the grinding medium ball density 5.967g/m3 is obtained, the abrasion test result is 3961.4ppm/h, the grinding medium ball is aged for 48 hours under 200 ℃ hydrothermal condition, the tetragonal phase content is 12%, the X-ray diffraction patterns before and after the grinding medium aging are respectively shown in fig. 5 and 6, the ordinate of the X-ray diffraction patterns shows the relative intensity, and the abscissa of the X-ray diffraction pattern shows the diffraction angle 2 theta.
Comparative example 2:
Compared with example 1, zirconia, ceria, yttria and kaolin are mixed according to the proportion of 86.5wt%, 12wt%, 1.5wt% and 0wt%, and the rest conditions are the same, so that the grinding medium ball density 6.055g/m3 is obtained, the abrasion test result is 1807.0ppm/h, the grinding medium ball is aged for 48 hours under the hydrothermal condition of 200 ℃, the tetragonal phase content is 95%, the X-ray diffraction patterns before and after the grinding medium aging are respectively shown in fig. 7 and 8, the ordinate of the X-ray diffraction patterns shows the relative intensity, and the abscissa of the X-ray diffraction pattern shows the diffraction angle 2 theta.
Comparative example 3:
Compared with example 1, 0.13wt% of alumina and 0.17wt% of silicon oxide are adopted to replace kaolin, the other conditions are the same, the prepared grinding medium is sintered at 1330 ℃, the density is 6.101g/m 3, the abrasion test result is 55.6ppm/h, the grinding medium is aged for 48 hours under the hydrothermal condition of 200 ℃, the tetragonal phase content is 100%, the X-ray diffraction patterns before and after the grinding medium is aged are respectively shown in fig. 9 and 10, the ordinate of the X-ray diffraction patterns shows the relative intensity, and the abscissa of the X-ray diffraction patterns show the diffraction angle 2 theta.
Comparative example 4:
Compared with the method in example 1, the temperature of the powder grinding process is controlled to be about 30 ℃, the other conditions are the same, the ball density 6.109g/m3 of the grinding medium is obtained, the abrasion test result is 298.2ppm/h, the grinding medium is aged for 48 hours under the hydrothermal condition of 200 ℃, the tetragonal phase content is 92%, the X-ray diffraction patterns before and after the grinding medium is aged are respectively shown in fig. 11 and 12, the ordinate of the X-ray diffraction patterns shows the relative intensity, and the abscissa of the X-ray diffraction patterns shows the diffraction angle 2 theta.
Comparative example 5:
Compared with the example 1, the temperature of the powder grinding process is controlled to be about 50 ℃, the rest conditions are the same, the density of the prepared grinding medium ball is 6.120g/m 3, the abrasion test result is 205.0ppm/h, the grinding medium ball is aged for 48 hours under the hydrothermal condition of 200 ℃, the tetragonal phase content is 94%, the X-ray diffraction patterns before and after the grinding medium is aged are respectively shown in fig. 13 and 14, the ordinate of the graph shows the relative intensity, the abscissa of the graph shows the diffraction angle 2 theta,
Table 1 experimental parameters of examples, comparative examples
,
Table 2 performance test parameters for each example, comparative example
。
From example 1 and comparative example 1, the addition of yttria, in combination with ceria, stabilizes zirconia, helping to improve its wear resistance. The Y 3+ is segregated in the grain boundary in the sintering process in the cerium oxide and yttrium oxide composite stabilized zirconia, so that the growth of crystal grains is inhibited, and the strength, the hardness and the compactness of Ce-TZP are improved, thereby obtaining excellent wear resistance.
From examples 1 and comparative examples 2 and 3, the addition of kaolin can accelerate densification of zirconia as a sintering aid to obtain high densification. The main components in the kaolin are alumina, silica and a small amount of alkali metal oxide, the alumina plays a role of a sintering aid in the sintering process, the alumina inhibits the growth of crystal grains, and the silica can easily form a eutectic liquid phase with a stabilizing agent of the ZrO 2 ceramic, so that the efficiency of sintering mass transfer is improved, the densification of the ceramic is promoted, and the mechanical property of the ceramic is influenced.
From the results of examples 1, 4 and 5, the grinding process is carried out at 70-90 ℃ to obviously improve the compactness, wear resistance and ageing resistance, and it is supposed that the Y 3+ and Ce 4+ can be promoted to be solid-dissolved into zirconia crystal lattice under the action of high temperature, the content of stabilizer in crystal boundary is reduced, the free enthalpy of solid solution chemistry and the constraint energy among crystal grains are increased, so that the crystal form is stably kept as tetragonal phase, the phenomenon of microcrack caused by volume expansion caused by t-ZrO 2→m-ZrO2 conversion is reduced, and the wear resistance is improved. Most of the stabilizing agents in the composite stabilized zirconia prepared under the low-temperature condition are in crystal boundaries, and are easy to precipitate into aqueous solution under the low-temperature aging condition to cause phase change, so that the wear resistance is reduced, and the composite stabilized zirconia has lower ageing resistance.
The wear resistance of zirconia grinding media is primarily determined by external factors, i.e., conditions of use and environment, and internal factors, from which we can only start to improve wear resistance. The internal factors mainly include phase, grain size, toughness, elastic modulus, strength, hardness, and porosity (density). The Y 3+ has higher strength and hardness, the Ce 4+ has enhanced toughness and aging resistance, and cracks generated by phase change are not easy to occur under the action of external force for a long time. The addition of the sintering aid kaolin significantly reduces the sintering temperature, thereby reducing the grain size of the sintered body, the smaller grain size helping it to maintain a stable tetragonal phase. The high sintering activity promotes the densification process, accelerates the elimination of air holes and reduces the existence of the air holes, thereby obtaining the ultra-high density. Therefore, the cerium oxide and yttrium oxide composite stable zirconium oxide grinding medium has excellent comprehensive mechanical properties after sintering under the low-temperature condition, so that the wear resistance of the grinding medium is improved.
In summary, the preparation method of the ceria-yttria composite stabilized zirconia grinding medium provided by the invention has the advantages that the raw material proportion is adjusted, the sintering auxiliary agent and the ball milling process are controlled, so that the zirconia grinding medium has the ultra-low sintering temperature of 1300-1350 ℃, the prepared zirconia grinding medium has excellent low-temperature ageing resistance and wear resistance, and the ultra-high density is favorable for the use in a high-viscosity grinding environment.
The invention provides a cerium oxide/yttrium oxide composite stable zirconium oxide grinding medium and a preparation method thereof, wherein the preparation method comprises the following steps of firstly, mixing zirconium oxide, cerium oxide, yttrium oxide and kaolin, adding a dispersing agent and deionized water, and grinding to obtain evenly mixed slurry; and step two, carrying out centrifugal spray drying on the uniformly mixed slurry to obtain cerium oxide and yttrium oxide composite stable zirconium oxide powder, step three, adding a binder into the cerium oxide and yttrium oxide composite stable zirconium oxide powder, rolling and forming to obtain a spherical grinding medium green compact, and polishing the grinding medium green compact after sintering to obtain the cerium oxide and yttrium oxide composite stable zirconium oxide grinding medium. The yttrium oxide and cerium oxide are compounded to stabilize the zirconium oxide, and the zirconium oxide is matched with the heat treatment in the ball milling process, so that the tetragonal zirconium oxide can be kept stable for a long time in a low-temperature humid environment, the phase inversion is inhibited, the ageing resistance is more excellent, and the service life is prolonged. The particle size is controlled, kaolin is added as a sintering aid, the sintering temperature is reduced, pressureless sintering is used, and sintering is performed in an air atmosphere, so that high density can be obtained, and the cost is reduced. The prepared grinding medium has excellent comprehensive mechanical properties, good wear resistance, low abrasion and reduced use cost.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
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