CN116768607A - Wear-resistant zirconium-aluminum composite ceramic ball with gradient structure and preparation method thereof - Google Patents
Wear-resistant zirconium-aluminum composite ceramic ball with gradient structure and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 173
- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 68
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 47
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003247 decreasing effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000009694 cold isostatic pressing Methods 0.000 claims description 11
- 239000008188 pellet Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 36
- 238000000227 grinding Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 121
- 239000011734 sodium Substances 0.000 description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- 239000012792 core layer Substances 0.000 description 18
- 239000002344 surface layer Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 239000010453 quartz Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 235000010216 calcium carbonate Nutrition 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 239000000454 talc Substances 0.000 description 10
- 229910052623 talc Inorganic materials 0.000 description 10
- 235000012222 talc Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000010433 feldspar Substances 0.000 description 9
- 229940072033 potash Drugs 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 235000015320 potassium carbonate Nutrition 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052661 anorthite Inorganic materials 0.000 description 4
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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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Abstract
The invention discloses a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure and a preparation method thereof, and belongs to the technical field of grinding media. The ceramic ball comprises at least three composite layers; the composite layer comprises the following chemical components in percentage by mass: zrO (ZrO) 2 ＝0‑50wt％，Al 2 O 3 ＝45～95wt％，SiO 2 +CaO+MgO＝2～10wt％，Na 2 O+K 2 O=0 to 2wt%. The content of alumina in the wear-resistant zirconium-aluminum composite ceramic ball is changed in a gradual increasing way from the surface composite layer to the core composite layer, and the content of zirconia in the wear-resistant zirconium-aluminum composite ceramic ball is changed in a gradual decreasing way from the surface composite layer to the core composite layer. The invention relates to a wear-resistant zirconium-aluminum composite with a gradient structureThe ceramic ball has strong wear resistance, low cost and long service life.
Description
Technical Field
The invention belongs to the technical field of grinding media, and particularly relates to a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure and a preparation method thereof.
Background
Many kinds of grinding medium balls in the modern ball milling process have developed over the years, among which are high-chromium steel balls, zirconia balls, zirconium silicate balls, zirconium-aluminum composite ZTA balls, alumina balls and the like. The high-chromium steel ball is mainly applied to the rough cement and mine industries by the strong impact crushing capability, and the alumina ceramic ball is mainly applied to the fields of building ceramics, daily ceramics and the like. Zirconia balls, zirconium silicate balls, zirconium aluminum composite ZTA balls and the like only play an important role in the field of fine grinding due to their high wear resistance and high cost. The existing high-alumina composite ZTA ball mostly adopts rare earth materials to be composited with zirconia and alumina, and has high cost and general wear resistance.
Disclosure of Invention
The invention aims to solve the technical problem of providing the wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which has low cost and good wear resistance.
The invention also solves the technical problem of providing a preparation method of the wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure.
In order to solve the technical problems, the invention provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises at least three composite layers; the composite layer comprises the following chemical components in percentage by mass:
ZrO 2 ＝0～50wt％，Al 2 O 3 ＝45～95wt％，SiO 2 +CaO+MgO＝2～10wt％，Na 2 O+K 2 O＝0～2wt％。
the content of alumina in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is increased and changed from the surface composite layer to the core composite layer, and the content of zirconia in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is decreased and changed from the surface composite layer to the core composite layer.
As an improvement of the technical proposal, the composite material comprises three composite layers; wherein the thickness of the composite layer positioned on the core accounts for more than or equal to 50 percent of the total thickness of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure.
As improvement of the technical scheme, the thickness ratio of the three composite layers from the surface of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure to the core is (0.5-1.2): 1: (5.5-8).
As an improvement of the technical scheme, the composite layer on the surface comprises the following chemical components in percentage by mass:
ZrO 2 ＝35～50wt％，Al 2 O 3 ＝42～55wt％，SiO 2 +CaO+MgO＝6～10wt％，Na 2 O+K 2 O＝1～2wt％；
wherein CaO+MgO/SiO 2 ＝(0.2～0.5):1。
As an improvement of the technical scheme, the middle composite layer comprises the following chemical components in percentage by mass:
ZrO 2 ＝10～20wt％，Al 2 O 3 ＝72～85wt％，SiO 2 +CaO+MgO＝4～8wt％，Na 2 O+K 2 O＝0～1wt％；
wherein CaO+MgO/SiO 2 ＝(0.5～1):1。
As an improvement of the technical scheme, the composite layer at the core comprises the following chemical components in percentage by mass:
ZrO 2 ＝0～10wt％，Al 2 O 3 ＝88～98wt％，SiO 2 +CaO+MgO＝2～5wt％，Na 2 O+K 2 O＝0～1.5wt％；
wherein CaO+MgO/SiO 2 ＝(2～3):1。
Correspondingly, the invention also discloses a preparation method of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure, which is used for preparing the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure and comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
(2) Drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
wherein, the preset firing curve is:
the temperature is increased to be between room temperature and T1, and the temperature rising rate is 10-20 ℃/min;
preserving heat for 1-2 h at T1;
heating from T1 to T2 at a heating rate of 5-8 ℃/min;
preserving heat for 1-3 h at T2;
heating from T2 to the firing temperature, wherein the heating rate is 3-5 ℃/min;
preserving heat for 1-3 h at the firing temperature;
wherein, T1 is 100-200 ℃, T2 is 1100-1150 ℃ and the firing temperature is 1350-1500 ℃.
As an improvement of the technical scheme, in the step (4), the blank is sintered according to a preset sintering curve and then cooled according to a preset cooling curve;
wherein, preset cooling curve is:
the temperature is reduced from the firing temperature to 1150 ℃ at a cooling rate of 5-15 ℃/min;
the temperature reduction rate is 10-20 ℃/min from 1150 ℃ to 800 ℃;
the temperature reduction rate is 5-15 ℃/min from 800 ℃ to 600 ℃;
the temperature reduction rate is 15-20 ℃/min from 600 ℃ to 500 ℃;
the temperature reduction rate is 20-40 ℃/min from 500 ℃ to room temperature.
As an improvement of the above-mentioned technical means, the particle size of the industrial zirconia used in the intermediate composite layer is 2 to 3 times that of the industrial zirconia used in the surface-core composite layer.
As an improvement of the above technical scheme, in the step (3), a cold isostatic pressing method or a pellet forming method is adopted for forming.
The implementation of the invention has the following beneficial effects:
1. the invention discloses a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises at least three composite layers, wherein the content of aluminum oxide of the wear-resistant zirconium-aluminum composite ceramic ball is increased and changed from a surface composite layer to a core composite layer, and the content of zirconium oxide is decreased and changed from the surface composite layer to the core composite layer. Based on the gradient structure, the residual stress generated by the composite layer close to the core and the core effectively improves the wear resistance of the ceramic ball. Meanwhile, the consumption of zirconia is reduced, and the production cost is reduced.
2. The invention gives the characteristics of light surface weight core and hard surface toughness core to the ceramic ball by controlling the content of each component in each layer of composite layer in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure, improves the running stability of the ceramic ball and prolongs the service life.
Detailed Description
The present invention will be described in further detail below for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
The invention discloses a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises at least three composite layers; the composite layer comprises the following chemical components in percentage by mass:
ZrO 2 ＝0-50wt％，Al 2 O 3 ＝45～95wt％，SiO 2 +CaO+MgO＝2～10wt％，Na 2 O+K 2 O＝0～2wt％。
the content of alumina in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is increased and changed from the surface composite layer to the core composite layer, and the content of zirconia in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is decreased and changed from the surface composite layer to the core composite layer. Based on the gradient structure, residual stress generated by the composite layer close to the core and the core can effectively improve the overall hardness of the ceramic ball and the wear resistance of the ceramic ball.
Wherein ZrO 2 The main source of the raw material is industrial zirconia, which is in monoclinic phase ZrO 2 Mainly. In the high temperature treatment process, a certain volume shrinkage exists, especially at 800-1000 ℃; on the one hand, stress accumulation can be improved, and the wear resistance of the ceramic balls is further improved. However, if the volume shrinkage is too large during the firing temperature rise, cracking and peeling between different layers are likely to occur, and it is difficult to form a complete ceramic ball structure. Thus, zrO in each layer is maintained 2 The content of (C) is 0-50wt%, and is exemplified by 5wt%, 10wt%, 15wt%, and,20wt%, 25wt%, 30wt%, 35wt%, 40wt% or 45wt%, but is not limited thereto. In addition, small amounts of K are also included in the technical zirconia 2 O、Na 2 Impurities such as O, and trace amounts of CaO.
Wherein Al is 2 O 3 The main raw material source is industrial alumina, which has high hardness, strong wear resistance, but relatively poor toughness. Al in each composite layer 2 O 3 The content of (2) is 45 to 95wt%, and is exemplified by 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 85wt%, but not limited thereto.
Wherein SiO is 2 The main source of the raw materials is quartz, and also can be anorthite, talcum and potash feldspar minerals, preferably quartz, siO in the quartz 2 Can be combined with Al at high temperature 2 O 3 React to form mullite, or react with CaO and Al 2 O 3 The anorthite is formed by the joint reaction, and has a great effect on adjusting the difference of the thermal expansion coefficients of the layers. Furthermore, siO of quartz crystal form 2 And the stress accumulation in the finished ceramic ball can be improved, and the wear resistance of the ceramic ball is improved. Specifically, siO in each composite layer 2 The content of (2) is 1 to 9wt%, and is exemplified by but not limited to 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt% or 8.5 wt%.
Wherein, the main raw material sources of CaO and MgO are calcium carbonate, talcum, dolomite and/or anorthite, but are not limited to the above. The CaO and the MgO mainly can form a liquid phase in the sintering process, so that each composite layer is not easy to crack and deform in the sintering process. Preferably, the source of CaO is calcium carbonate, which decomposes at high temperatures to produce expansion, reducing the adverse effects of zirconia shrinkage at high temperatures on the bonding of the composite layers. Specifically, in the present invention, siO is controlled 2 +CaO+MgO＝2～10wt％。
Wherein K is 2 O、Na 2 The source of the O-major raw material includes, but is not limited to, impurities of industrial alumina, impurities of industrial zirconia, potassium feldspar, sodium feldspar, and the like. K (K) 2 O、Na 2 O can also be burnt afterIn the process, a liquid phase is formed, so that each composite layer is not easy to crack and deform in the sintering process. Specifically, na is controlled in the present invention 2 O+K 2 O is 0 to 2wt%.
In a preferred embodiment of the invention, the wear-resistant zirconium aluminum composite ceramic ball with the gradient structure comprises three composite layers, namely a surface layer, a middle layer and a core layer in sequence; wherein, the thickness ratio of the surface layer, the middle layer and the core layer is (0.5-1.2): 1: (5.5-8), on the basis of the above thickness ratio, the yield of the ceramic balls can be ensured, and the wear resistance can be improved.
Specifically, in the above embodiment, the composite layer (surface layer) located on the surface has the following chemical components in percentage by mass:
ZrO 2 ＝35～50wt％，Al 2 O 3 ＝42～55wt％，SiO 2 +CaO+MgO＝6～10wt％，Na 2 O+K 2 o=1 to 2wt%; wherein CaO+MgO/SiO 2 ＝(0.2～0.5):1。
Specifically, in the surface layer, zrO is controlled 2 35 to 50 weight percent, controlling SiO 2 +CaO+MgO=6 to 10wt% and CaO+MgO/SiO 2 = (0.2 to 0.5): 1. ZrO, zrO 2 The content is increased, the volume shrinkage is increased at 800-1000 ℃, so that more CaO, mgO, K is added 2 O、Na 2 And O can generate more liquid phase, make up the thermal expansion difference between the middle layer and the core layer in the high-temperature sintering process and prevent cracking. Both by lifting SiO 2 The content of the ceramic balls can improve the wear resistance of the ceramic balls.
Specifically, in the above embodiment, the chemical components of the intermediate composite layer (intermediate layer) in mass percent are:
ZrO 2 ＝10～20wt％，Al 2 O 3 ＝72～85wt％，SiO 2 +CaO+MgO＝4～8wt％，Na 2 O+K 2 o=0 to 1wt%; wherein CaO+MgO/SiO 2 ＝(0.5～1):1。
Specifically, in the intermediate layer, zrO is controlled 2 10 to 20 weight percent of SiO is controlled 2 +cao+mgo=4 to 8wt%, one, zrO 2 The content is increased inThe volume shrinkage at 800-1000 ℃ is increased, so that more SiO is added 2 Which can be combined with Al 2 O 3 The mullite is formed by reaction, and anorthite is formed by reaction with CaO, so that the thermal expansion coefficient of the whole intermediate layer is reduced, and the volume shrinkage is reduced. Both are controlled and CaO+MgO/SiO 2 1, which improves SiO to a certain extent 2 The content of the quartz phase is improved, so that the compressive stress on the surface layer is improved, and the wear resistance of the ceramic ball is improved.
Further, in the present invention, the grain size of the industrial zirconia used in the intermediate layer is 2 to 3 times the grain sizes of the industrial zirconia used in the surface layer and the core layer. I.e. such that in the finished product ZrO in the intermediate layer 2 The grain size is ZrO in the surface layer and the core layer 2 2-3 times of the grain size. The intermediate layer can further improve the bonding stability among the layers and the yield of the ceramic balls.
Specifically, in the above embodiment, the composite layer (core layer) located at the core comprises the following chemical components in percentage by mass:
ZrO 2 ＝0～10wt％，Al 2 O 3 ＝88～98wt％，SiO 2 +CaO+MgO＝2～5wt％，Na 2 O+K 2 o=0 to 1.5wt%; wherein CaO+MgO/SiO 2 ＝(2～3):1。
Specifically, in the core layer, zrO is controlled 2 0 to 10wt%, based on this composition, no substantial volume shrinkage at 800 to 1000 ℃; in addition, control its SiO 2 +CaO+MgO=2 to 5wt% and CaO+MgO/SiO 2 1, so that more liquid phase is generated under high temperature condition and the surface layer, the middle layer and the core layer are not cracked or deformed.
Correspondingly, the invention also discloses a preparation method of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure, which comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, raw materials are provided according to chemical components of a composite layer, then various raw materials are mixed, water and a dispersing agent are added, and ball milling is carried out to obtain composite layer slurry; wherein, the water content in the composite layer slurry is 45-55wt% and the dispersant content is 0.3-0.7wt%. CMC may be used as the dispersing agent, but is not limited thereto.
Specifically, each composite layer slurry is prepared separately to control the particle size of the particles in each composite layer slurry. Specifically, the D90 of particles in the slurry of the composite layer corresponding to each composite layer is less than or equal to 3 mu m; for different composite layer sizing agents, the specific particle size can be controlled according to the requirement of the finished product crystal grain. For example, in one embodiment of the present invention, the particle size of the composite layer slurry of the intermediate layer is controlled to be 2 times that of the composite slurry of the other layers, to obtain ZrO in the intermediate layer in the final product 2 The grain size is ZrO in the surface layer and the core layer 2 2-3 times of the grain size.
Specifically, in one embodiment of the invention, the particle size of each raw material is controlled below 10 mu m, and the ball milling only plays a role in mixing. In another embodiment of the invention, the particle size of each raw material is larger, and the ball milling plays roles of mixing and grinding at the same time.
(2) Drying and granulating the composite layer slurry to obtain powder;
specifically, the slurry may be granulated using a spray tower, but is not limited thereto.
(3) Molding the powder, and drying to obtain a blank;
specifically, the cold isostatic pressing process or the pellet forming process may be used, but is not limited thereto. Drying at 60-90 deg.c for 12-36 hr after forming.
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to T1 (100-200 ℃), and the temperature rising rate is 10-20 ℃/min; preserving heat for 1-2 h at T1 (100-200 ℃); heating from T1 (100-200 ℃) to T2 (1100-1150 ℃) at a heating rate of 5-8 ℃/min; preserving heat for 1-3 h at the temperature of T2 (1100-1150 ℃); heating from T2 (1100-1150 ℃) to sintering temperature (1350-1500 ℃) at a heating rate of 3-5 ℃/min; preserving heat for 1-3 h at the firing temperature (1350-1500 ℃).
Preferably, in one embodiment of the present invention, the blank is cooled according to a preset cooling curve after being fired according to a preset firing curve; wherein, preset cooling curve is: the temperature is reduced from the firing temperature to 1150 ℃ at a cooling rate of 5-15 ℃/min; the temperature reduction rate is 10-20 ℃/min from 1150 ℃ to 800 ℃; the temperature reduction rate is 5-15 ℃/min from 800 ℃ to 600 ℃; the temperature reduction rate is 15-20 ℃/min from 600 ℃ to 500 ℃; the temperature reduction rate is 20-40 ℃/min from 500 ℃ to room temperature. Based on the cooling curve, the wear resistance of the ceramic balls can be further improved.
The invention is further illustrated by the following examples:
example 1
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises four composite layers; the thickness ratio from the outside to the inside is 1:1:1:3;
the chemical components of the first layer on the outermost surface are as follows:
ZrO 2 ＝32.9wt％，Al 2 O 3 ＝59.5wt％，SiO 2 +CaO+MgO＝6.2wt％，Na 2 O+K 2 O＝1.4wt％。
the chemical components of the intermediate layer close to the surface are as follows:
ZrO 2 ＝20.4wt％，Al 2 O 3 ＝71.3wt％，SiO 2 +CaO+MgO＝7.3wt％，Na 2 O+K 2 O＝1wt％。
the intermediate layer near the core has the chemical composition:
ZrO 2 ＝11.5wt％，Al 2 O 3 ＝80.5wt％，SiO 2 +CaO+MgO＝7.5wt％，Na 2 O+K 2 O＝0.5wt％。
the chemical components of the core layer are as follows:
ZrO 2 ＝5.1wt％，Al 2 O 3 ＝91.3wt％，SiO 2 +CaO+MgO＝3.5wt％，Na 2 O+K 2 o=0.1 wt%. The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; preserving heat for 3h at 1350 ℃; and then cooled with the furnace.
Example 2
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises three composite layers; the thickness ratio from the outside to the inside is 0.5:1:10;
the chemical components of the surface layer are as follows:
ZrO 2 ＝43.9wt％，Al 2 O 3 ＝46.6wt％，SiO 2 +CaO+MgO＝8.5wt％，Na 2 O+K 2 o=1 wt%, and (cao+mgo)/SiO 2 ＝1.5；
The chemical components of the middle layer are as follows:
ZrO 2 ＝11.8wt％，Al 2 O 3 ＝85.5wt％，SiO 2 +CaO+MgO＝2.5wt％，Na 2 O+K 2 o=0.2 wt%, and (cao+mgo)/SiO 2 ＝1.2；
The chemical components of the core layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; preserving heat for 3h at 1350 ℃; and then cooled with the furnace.
Example 3
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises three composite layers; the thickness ratio from the outside to the inside is 0.8:1:7;
the chemical components of the surface layer are as follows:
ZrO 2 ＝39.8wt％，Al 2 O 3 ＝52.5wt％，SiO 2 +CaO+MgO＝6.5wt％，Na 2 O+K 2 o=1.2 wt%, and (cao+mgo)/SiO 2 ＝1；
The chemical components of the middle layer are as follows:
ZrO 2 ＝16.5wt％，Al 2 O 3 ＝76.7wt％，SiO 2 +CaO+MgO＝6.3wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝1.2；
The chemical components of the core layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; preserving heat for 3h at 1350 ℃; and then cooled with the furnace.
Example 4
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises three composite layers; the thickness ratio from the outside to the inside is 0.8:1:7;
the chemical components of the surface layer are as follows:
ZrO 2 ＝39.8wt％，Al 2 O 3 ＝52.5wt％，SiO 2 +CaO+MgO＝6.6wt％，Na 2 O+K 2 o=1.1 wt%, and (cao+mgo)/SiO 2 ＝0.4；
The chemical components of the middle layer are as follows:
ZrO 2 ＝16.5wt％，Al 2 O 3 ＝76.7wt％，SiO 2 +CaO+MgO＝6.3wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝0.8；
The chemical components of the core layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; preserving heat for 3h at 1350 ℃; and then cooled with the furnace.
Example 5
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises three composite layers; the thickness ratio from the outside to the inside is 0.8:1:7;
the chemical components of the surface layer are as follows:
ZrO 2 ＝39.8wt％，Al 2 O 3 ＝52.5wt％，SiO 2 +CaO+MgO＝6.6wt％，Na 2 O+K 2 o=1.1 wt%, and (cao+mgo)/SiO 2 ＝0.4；
The chemical components of the middle layer are as follows:
ZrO 2 ＝16.5wt％，Al 2 O 3 ＝76.7wt％，SiO 2 +CaO+MgO＝6.3wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝0.8；
The chemical components of the core layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve, and then cooling according to a preset cooling curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; the temperature was maintained at 1350℃for 3h.
The preset cooling curve is: the temperature reduction rate is 8 ℃/min from 1350 ℃ to 1150 ℃; the temperature reduction rate is 12 ℃/min from 1150 ℃ to 800 ℃; the temperature reduction rate is 10 ℃/min from 800 ℃ to 600 ℃; the temperature reduction rate is 19 ℃/min from 600 ℃ to 500 ℃; the temperature reduction rate is 35 ℃/min from 500 ℃ to room temperature.
Example 6
The embodiment provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which comprises three composite layers; the thickness ratio from the outside to the inside is 0.8:1:7;
the chemical components of the surface layer are as follows:
ZrO 2 ＝39.8wt％，Al 2 O 3 ＝52.5wt％，SiO 2 +CaO+MgO＝6.6wt％，Na 2 O+K 2 o=1.1 wt%, and (cao+mgo)/SiO 2 ＝0.4；
The chemical components of the middle layer are as follows:
ZrO 2 ＝16.5wt％，Al 2 O 3 ＝76.7wt％，SiO 2 +CaO+MgO＝6.3wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝0.8；
The chemical components of the core layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials include industrial zirconia (the average particle diameter of the middle layer (d50=3.8 μm) is twice that of the surface layer and the core layer (d50=1.9 μm)), industrial alumina, quartz, calcium carbonate, talc and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve, and then cooling according to a preset cooling curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; the temperature was maintained at 1350℃for 3h.
The preset cooling curve is:
the preset cooling curve is: the temperature reduction rate is 8 ℃/min from 1350 ℃ to 1150 ℃; the temperature reduction rate is 12 ℃/min from 1150 ℃ to 800 ℃; the temperature reduction rate is 10 ℃/min from 800 ℃ to 600 ℃; the temperature reduction rate is 19 ℃/min from 600 ℃ to 500 ℃; the temperature reduction rate is 35 ℃/min from 500 ℃ to room temperature.
Comparative example 1
The comparative example provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which has a uniform structure and comprises the following chemical components:
ZrO 2 ＝33.8wt％，Al 2 O 3 ＝59.1wt％，SiO 2 +CaO+MgO＝6.1wt％，Na 2 O+K 2 o=1 wt%, and (cao+mgo)/SiO 2 ＝0.61；
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components, and obtaining slurry after ball milling;
specifically, the raw materials comprise industrial zirconia, industrial alumina, quartz, calcium carbonate, talcum and potash albite; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve, and then cooling according to a preset cooling curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; the temperature was maintained at 1350℃for 3h.
The preset cooling curve is:
the preset cooling curve is: the temperature reduction rate is 8 ℃/min from 1350 ℃ to 1150 ℃; the temperature reduction rate is 12 ℃/min from 1150 ℃ to 800 ℃; the temperature reduction rate is 10 ℃/min from 800 ℃ to 600 ℃; the temperature reduction rate is 19 ℃/min from 600 ℃ to 500 ℃; the temperature reduction rate is 35 ℃/min from 500 ℃ to room temperature.
Comparative example 2
The comparative example provides a wear-resistant zirconium-aluminum composite ceramic ball with a gradient structure, which is of a two-layer structure, and the thickness ratio of a surface layer to a core layer is 1:3;
the chemical components of the surface layer are as follows:
ZrO 2 ＝3.1wt％，Al 2 O 3 ＝94.2wt％，SiO 2 +CaO+MgO＝2.2wt％，Na 2 O+K 2 o=0.5 wt%, and (cao+mgo)/SiO 2 ＝2.2。
The chemical components of the core layer are as follows:
ZrO 2 ＝43.9wt％，Al 2 O 3 ＝46.6wt％，SiO 2 +CaO+MgO＝8.5wt％，Na 2 O+K 2 o=1 wt%, and (cao+mgo)/SiO 2 ＝1.5。
The preparation method comprises the following steps:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
specifically, the raw materials comprise industrial zirconia (the particle sizes of all layers are the same), industrial alumina, quartz, calcium carbonate, talcum and potash feldspar; in the composite layer slurry, the water content is 48wt% and the CMC content is 0.6wt%;
(2) Spray drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder by adopting a cold isostatic pressing process, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve, and then cooling according to a preset cooling curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
specifically, the preset firing curve is:
the temperature is increased to 150 ℃ at the speed of 10 ℃/min; preserving heat for 1h at 150 ℃; heating from 150 ℃ to 1100 ℃ at a heating rate of 8 ℃/min; preserving heat for 1h at 1100 ℃; heating from 1100 ℃ to 1350 ℃ at a heating rate of 5 ℃/min; the temperature was maintained at 1350℃for 3h.
The preset cooling curve is:
the preset cooling curve is: the temperature reduction rate is 8 ℃/min from 1350 ℃ to 1150 ℃; the temperature reduction rate is 12 ℃/min from 1150 ℃ to 800 ℃; the temperature reduction rate is 10 ℃/min from 800 ℃ to 600 ℃; the temperature reduction rate is 19 ℃/min from 600 ℃ to 500 ℃; the temperature reduction rate is 35 ℃/min from 500 ℃ to room temperature.
The gradient structure wear-resistant zirconium-aluminum composite ceramic balls (diameter 25 mm) prepared in examples 1 to 6 and comparative examples 1 to 2 were taken and tested as follows:
(1) 5 composite ceramic balls are taken respectively, the warp diameter and the weft diameter of the composite ceramic balls are measured respectively by a micrometer, and the dimensional difference is judged;
(2) And 100 products are produced, and the yield is counted, wherein cracks, spots, bubbles, sticky damage and sand sticking are regarded as unqualified.
(3) The wear resistance was tested using the method in JC/T848.1-2010.
Specific results are shown in the following two tables:
the foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. The wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is characterized by comprising at least three composite layers; the composite layer comprises the following chemical components in percentage by mass:
ZrO 2 ＝0～50wt％，Al 2 O 3 ＝45～95wt％，SiO 2 +CaO+MgO＝2～10wt％，
Na 2 O+K 2 O＝0～2wt％。
the content of alumina in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is increased and changed from the surface composite layer to the core composite layer, and the content of zirconia in the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure is decreased and changed from the surface composite layer to the core composite layer.
2. The gradient structured wear resistant zirconium aluminum composite ceramic ball of claim 1, comprising three composite layers; wherein the thickness of the composite layer positioned on the core accounts for more than or equal to 50 percent of the total thickness of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure.
3. The gradient structured wear-resistant zirconium aluminum composite ceramic ball as claimed in claim 2, wherein the thickness ratio of the three composite layers from the surface of the gradient structured wear-resistant zirconium aluminum composite ceramic ball to the core is (0.5-1.2): 1: (5.5-8).
4. The gradient structured wear-resistant zirconium aluminum composite ceramic ball as claimed in claim 2, wherein the composite layer on the surface comprises the following chemical components in percentage by mass:
ZrO 2 ＝35～50wt％，Al 2 O 3 ＝42～55wt％，SiO 2 +CaO+MgO＝6～10wt％，
Na 2 O+K 2 O＝1～2wt％；
wherein CaO+MgO/SiO 2 ＝(0.2～0.5):1。
5. The gradient structured wear-resistant zirconium aluminum composite ceramic ball as claimed in claim 2, wherein the intermediate composite layer comprises the following chemical components in percentage by mass:
ZrO 2 ＝10～20wt％，Al 2 O 3 ＝72～85wt％，SiO 2 +CaO+MgO＝4～8wt％，
Na 2 O+K 2 O＝0～1wt％；
wherein CaO+MgO/SiO 2 ＝(0.5～1):1。
6. The gradient structured wear-resistant zirconium aluminum composite ceramic ball as claimed in claim 2, wherein the composite layer at the core comprises the following chemical components in percentage by mass:
ZrO 2 ＝0～10wt％，Al 2 O 3 ＝88～98wt％，SiO 2 +CaO+MgO＝2～5wt％，
Na 2 O+K 2 O＝0～1.5wt％；
wherein CaO+MgO/SiO 2 ＝(2～3):1。
7. A method for preparing a gradient structured wear-resistant zirconium-aluminum composite ceramic ball, which is used for preparing the gradient structured wear-resistant zirconium-aluminum composite ceramic ball as claimed in any one of claims 1 to 6, and is characterized by comprising:
(1) Providing raw materials according to chemical components of the composite layer, and obtaining composite layer slurry after ball milling;
(2) Drying and granulating the composite layer slurry to obtain powder;
(3) Molding the powder, and drying to obtain a blank;
(4) Sintering the blank according to a preset sintering curve to obtain a finished product of the wear-resistant zirconium-aluminum composite ceramic ball with the gradient structure;
wherein, the preset firing curve is:
the temperature is increased to be between room temperature and T1, and the temperature rising rate is 10-20 ℃/min;
preserving heat for 1-2 h at T1;
heating from T1 to T2 at a heating rate of 5-8 ℃/min;
preserving heat for 1-3 h at T2;
heating from T2 to the firing temperature, wherein the heating rate is 3-5 ℃/min;
preserving heat for 1-3 h at the firing temperature;
wherein, T1 is 100-200 ℃, T2 is 1100-1150 ℃ and the firing temperature is 1350-1500 ℃.
8. The method according to claim 7, wherein in the step (4), the green body is cooled according to a preset cooling curve after being fired according to a preset firing curve;
wherein, preset cooling curve is:
the temperature is reduced from the firing temperature to 1150 ℃ at a cooling rate of 5-15 ℃/min;
the temperature reduction rate is 10-20 ℃/min from 1150 ℃ to 800 ℃;
the temperature reduction rate is 5-15 ℃/min from 800 ℃ to 600 ℃;
the temperature reduction rate is 15-20 ℃/min from 600 ℃ to 500 ℃;
the temperature reduction rate is 20-40 ℃/min from 500 ℃ to room temperature.
9. The method according to claim 7, wherein the particle size of the industrial zirconia used in the intermediate composite layer is 2 to 3 times the particle size of the industrial zirconia used in the surface-core composite layer.
10. The method of claim 7, wherein in step (3), the molding is performed by cold isostatic pressing or pellet molding.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01145367A (en) * | 1987-11-30 | 1989-06-07 | Kyocera Corp | Alumina sintered form and production thereof |
| US20050187638A1 (en) * | 2002-09-24 | 2005-08-25 | Wilfried Glien | Ceramic endoprosthesis components and processes for their production |
| CN102009175A (en) * | 2010-10-08 | 2011-04-13 | 李亚东 | Manufacturing method of multilayer shell-core composite structural part |
| CN205953917U (en) * | 2016-07-25 | 2017-02-15 | 中煤科工清洁能源股份有限公司 | Prepare wear -resisting attrition medium of superfine coal slurry |
| CN113800895A (en) * | 2021-08-24 | 2021-12-17 | 萍乡市金刚科技工业园有限公司 | Wear-resistant zirconium-aluminum composite ball and preparation method thereof |
| KR20220049020A (en) * | 2019-08-16 | 2022-04-20 | 이보클라 비바덴트 아게 | Gradient Composition Zirconia Dental Materials |
| CN114409383A (en) * | 2022-01-26 | 2022-04-29 | 苏州鼎安科技有限公司 | Surface-enhanced ceramic artificial joint convex-spherical friction part and preparation method thereof |
| WO2022252504A1 (en) * | 2021-05-31 | 2022-12-08 | 广东工业大学 | Zirconia toughened alumina ceramic plate and manufacturing method therefor |
| CN115784775A (en) * | 2022-12-02 | 2023-03-14 | 中国国检测试控股集团股份有限公司 | Zirconia and alumina gradient composite coating and preparation method thereof |
-
2023
- 2023-06-01 CN CN202310642281.XA patent/CN116768607A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01145367A (en) * | 1987-11-30 | 1989-06-07 | Kyocera Corp | Alumina sintered form and production thereof |
| US20050187638A1 (en) * | 2002-09-24 | 2005-08-25 | Wilfried Glien | Ceramic endoprosthesis components and processes for their production |
| CN102009175A (en) * | 2010-10-08 | 2011-04-13 | 李亚东 | Manufacturing method of multilayer shell-core composite structural part |
| CN205953917U (en) * | 2016-07-25 | 2017-02-15 | 中煤科工清洁能源股份有限公司 | Prepare wear -resisting attrition medium of superfine coal slurry |
| KR20220049020A (en) * | 2019-08-16 | 2022-04-20 | 이보클라 비바덴트 아게 | Gradient Composition Zirconia Dental Materials |
| WO2022252504A1 (en) * | 2021-05-31 | 2022-12-08 | 广东工业大学 | Zirconia toughened alumina ceramic plate and manufacturing method therefor |
| CN113800895A (en) * | 2021-08-24 | 2021-12-17 | 萍乡市金刚科技工业园有限公司 | Wear-resistant zirconium-aluminum composite ball and preparation method thereof |
| CN114409383A (en) * | 2022-01-26 | 2022-04-29 | 苏州鼎安科技有限公司 | Surface-enhanced ceramic artificial joint convex-spherical friction part and preparation method thereof |
| CN115784775A (en) * | 2022-12-02 | 2023-03-14 | 中国国检测试控股集团股份有限公司 | Zirconia and alumina gradient composite coating and preparation method thereof |
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