CN116283240A - Ruby type high-strength Cr-ZTA ceramic material and preparation method thereof - Google Patents
Ruby type high-strength Cr-ZTA ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 33
- 239000010979 ruby Substances 0.000 title claims abstract description 15
- 229910001750 ruby Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 68
- 239000000919 ceramic Substances 0.000 claims abstract description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005452 bending Methods 0.000 claims abstract description 5
- 235000015895 biscuits Nutrition 0.000 claims description 39
- 239000004576 sand Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 235000014820 Galium aparine Nutrition 0.000 description 6
- 240000005702 Galium aparine Species 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZSBXGIUJOOQZMP-JLNYLFASSA-N Matrine Chemical compound C1CC[C@H]2CN3C(=O)CCC[C@@H]3[C@@H]3[C@H]2N1CCC3 ZSBXGIUJOOQZMP-JLNYLFASSA-N 0.000 description 1
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 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
- C04B35/01—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
- C04B35/10—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 aluminium oxide
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract
The invention relates to a ruby type high-strength Cr-ZTA ceramic material and a preparation method thereof, belonging to the technical field of Cr-doped zirconia toughened alumina ceramic material ZTA. The Cr-ZTA ceramic material is prepared from the following raw materials, by mass, 80-90% of alumina powder, 10-20% of zirconia powder and Cr 3+ The addition amount of the solution is 0.1-0.4% of the sum of the mass of the alumina powder and the mass of the zirconia powder. The Cr-ZTA ceramic prepared by the method has fine grains and uniform size distribution, and the volume density is more than or equal to 4.15g/cm 3 The bending strength is more than 1000MPa, and the Vickers hardness is more than or equal to 18GPa. The Cr-ZTA ceramic prepared by the method can be applied to the semiconductor packaging industry.
Description
Technical Field
The invention relates to the technical field of Cr-doped zirconia toughened alumina ceramic material ZTA, in particular to a ruby type high-strength Cr-ZTA ceramic material and a preparation method thereof.
Background
Zirconia toughened alumina ceramics (ZTA) are one of the advanced ceramics widely studied in recent years, and ZTA has excellent mechanical properties such as high hardness, high strength, and the like. In addition, the material is chemically inert and has greater compressive strength. Despite such versatility, the lack of fracture toughness and impact resistance has prevented its use on a large scale. Ceramic cleavers of ZTA materials also have a major limitation in service life.
Alumina and chromia follow the Vegard law and can form an equivalent solid solution with a similar corundum structure, with atoms or ions exchangeable. In the alumina rich phase, the ceramic assumes the color of pink ruby.
The Kroger-Vink law suggests that certain material inclusions may have an effect on lattice parameters or thermal properties, and that anion vacancies or cation vacancies are also caused by the addition of certain ionic materials that affect ZTA performance.
Integrated circuits are the core of the information technology industry, and are the focus of developing strategically emerging industries. At present, wafer factories still mainly use mature processes above 40nm, gradually develop to 28nm and 10nm processes, and the requirements on packaging technology are rapidly improved. Bonding is a core link of chip packaging, and the bonding is used for connecting an internal integrated circuit and an external pin by gold wires or copper wires, so that the structural design, manufacturing and processing technology has extremely high bottleneck, and is currently monopoly overseas and urgent in self-development requirement.
Wire bonding is the creation of electrical interconnections between the chip and the package. To form the interconnections, a ceramic cleaver is required as a tool for the leads. Ceramic cleavers are mainly imported, and manufacturers include SPT in Switzerland, GAISER in USA, PECO in Korea, TOTO corporation in Japan and the like; enterprises in the domestic integrated circuit sealing and testing link rise gradually, and the sealing and testing field is hopeful to realize comprehensive domestic substitution. Therefore, the material and the product of the neck-blocking are needed to realize domestic substitution.
The main stream of Zirconia Toughened Alumina (ZTA) ceramic cleaver in the market at present belongs to the manufacturing of precision ceramics (microstructures). But domestic related enterprises do not have the preparation technology of high-end ZTA ceramic materials and ceramic cleavers.
Disclosure of Invention
In view of the problems and the defects existing in the prior art, the invention aims to provide a ruby type high-strength Cr-ZTA ceramic material and a preparation method thereof, which meet the use requirements of the integrated circuit packaging industry on high-strength ceramic cleavers.
The technical scheme adopted for realizing the purpose of the invention is as follows: the ruby type high-strength Cr-ZTA ceramic material is prepared from (by mass) alumina powder 80-90%, zirconia powder 10-over20%，Cr 3+ The addition amount of the solution is 0.1-0.4% of the sum of the mass of the alumina powder and the mass of the zirconia powder.
Preferably, the Cr-ZTA ceramic material is prepared by the following steps: mixing alumina powder and zirconia powder through powder ball milling, sand grinding, rotary evaporating drying, dry pressing, isostatic pressing, presintering and Cr 3+ Solution impregnation and sintering.
Preferably, the purity of the alumina powder is more than or equal to 99.9 percent, and the particle size is 200-800 nm; the purity of the zirconia powder is more than or equal to 99.9 percent, and the grain diameter is 50-200 nm.
Preferably, the Cr of the present invention 3+ The solution adopts Cr (NO) 3 ) 3 •9H 2 Cr prepared from O 3+ Solution, solvent is deionized water, cr 3+ The concentration of the solution is 0.50-0.72 g/mL.
Preferably, the volume density of the Cr-ZTA ceramic material is more than or equal to 4.15g/cm 3 The bending strength is more than or equal to 7000MPa, and the Vickers hardness is more than or equal to 18GPa.
The technical scheme adopted for realizing the other purpose of the invention is as follows: the preparation method of the ruby type high-strength Cr-ZTA ceramic material comprises the following preparation steps:
1) Adding alumina powder, zirconia powder and a ball milling medium into a ball milling tank according to the formula amount, and mixing on a ball mill to prepare slurry;
2) Sieving the slurry prepared in the step 1) through a 100-200 mesh screen, and sanding on a vertical sand mill;
3) Filtering out the slurry which is uniformly sanded, and putting the slurry on a rotary evaporator for rotary evaporation to dryness to prepare dry powder;
4) Sieving the dried powder prepared in the step 3) through a 60-80 mesh screen, and carrying out dry press molding under 50-78 MPa and isostatic press molding under 180-200 MPa to prepare a ceramic biscuit;
5) Placing the ceramic biscuit into a silicon-molybdenum rod furnace for presintering, wherein the presintering temperature is 1000-1200 ℃ and the presintering time is 1-3 hours, so as to obtain a ZTA ceramic biscuit;
6) Mixing ZTA ceramic biscuit prepared in the step 5) with Cr 3+ Dipping in the solutionThe Cr is 3+ The adding amount of the solution is 6-10 times of the quality of the ZTA ceramic biscuit, then vacuum drying is carried out, the drying temperature is 20-25 ℃, the vacuum degree is minus 1-minus 2Pa, the vacuum is pumped for 3-6 hours, and then the residual Cr is processed 3+ Pouring out the solution, placing the impregnated ZTA ceramic biscuit on oilpaper, maintaining the vacuum degree to be-1 to-2 Pa, and vacuumizing for 20 to 24 hours;
7) And (3) carrying out high-temperature sintering on the ZTA ceramic biscuit subjected to vacuum pumping in the step (6), wherein the sintering temperature is 1500-1580 ℃, and the heat preservation time is 1-3 hours, so that the ruby type high-strength Cr-ZTA ceramic material is prepared.
Preferably, the ball milling medium in the step 1) of the invention is absolute ethyl alcohol, the addition amount of the absolute ethyl alcohol is 280-320% of the total weight of the alumina powder and the zirconia powder, the grinding balls are zirconia balls with the diameter of 5mm and alumina balls with the diameter of 10mm, the mass of the zirconia balls with the diameter of 5mm is 100-150% of the total weight of the alumina powder and the zirconia powder, and the mass of the alumina balls with the diameter of 10mm is 150-200% of the total weight of the alumina powder and the zirconia powder.
Preferably, in the step 2) of the present invention, the sanding time is 1 to 3 hours, the sand ball is zirconia ball with the diameter of 0.5mm, the mass of the sand ball is the mass sum of the alumina powder and the zirconia powder, and the sanding rotational speed is 1800 to 2700r/min.
Preferably, the rotary evaporation in the step 3) is carried out at a rotation speed of 30-50 r/min, an evaporation temperature of 50-65 ℃ and a rotary evaporation time of 1.5-2.5 h.
Compared with the prior art, the invention has the following technical advantages:
(1) The Cr-ZTA ceramic material prepared by the method can obviously reduce the grain size of aluminum oxide and zirconium oxide through powder sanding treatment, has fine grains and uniform size distribution, and has obvious effect on improving the strength of the ceramic material. The volume density of the ceramic material prepared by the invention is more than or equal to 4.15g/cm 3 The bending strength is more than 1000MPa, and the Vickers hardness is more than 18GPa.
(2) The invention adds Cr by dipping method 3+ Can reduce Cr in the direct mixing process 3+ Is of the type that simplifies the preparation of the powderThe hardness is improved to more than 18GPa by the process.
(3) The invention utilizes the impregnation technology, and by means of the open pores of the ceramics, the purpose of introducing chromium is realized on the ceramic blank through a series of specific process settings, thereby having positive effect on the mechanical properties of ceramic riving knife products.
(4) The ceramic riving knife made of the ruby ceramic material has wear resistance higher than that of the current ZTA ceramic riving knife product, and the service life is prolonged by more than 20 percent.
Description of the embodiments
The invention will be further illustrated with reference to the following specific examples, it being understood that the following examples are given by way of illustration only and are not intended to be limiting.
The invention relates to a ruby type high-strength Cr-ZTA ceramic material which is prepared from the following raw materials, by mass, 80-90% of alumina powder, 10-20% of zirconia powder and Cr 3+ The addition amount of the solution is 0.1-0.4% of the sum of the mass of the alumina powder and the mass of the zirconia powder.
The Cr-ZTA ceramic adopts high-purity superfine alumina powder and zirconia powder as raw materials, and is prepared by ball milling, mixing, sanding, rotary evaporation drying, dry pressing, isostatic pressing, degreasing, presintering and Cr 3+ Dipping and sintering the solution to prepare the ruby type high-strength Cr-ZTA ceramic material.
Examples
The alumina content is selected to be more than 99.9 percent, and the grain diameter D 50 80 g of high-purity alumina powder with the grain diameter D and the zirconia content of more than 99.9 percent 50 For 20 g of high-purity alumina powder with the diameter of 50nm, 280 g (about 354.4 mL) of absolute ethyl alcohol serving as a ball milling medium is selected, 100 g of zirconia balls with the diameter of 5mm and 150 g of alumina balls with the diameter of 10mm are selected, the mixture is added into a ball milling tank, and the ball milling and mixing are carried out on a planetary ball mill for 12 hours.
After passing through a 100-mesh screen, the slurry obtained in the step 1) is sanded on a vertical sand mill, wherein the sanding time is 1 hour, the sand ball is zirconia balls with the thickness of 0.5mm, the mass of the sand ball is 100 grams, and the sanding rotating speed is 1800r/min;
filtering out the slurry uniformly sanded in the step 2), and putting the slurry on a rotary evaporator for rotary evaporation to dryness, wherein the rotary speed is 30r/min, the evaporation temperature is 65 ℃, and the rotary evaporation time is 1.5h, so as to obtain dry powder;
sieving the dried powder obtained in the step 3) through a 60-mesh screen, and carrying out dry press molding under 50MPa and isostatic press molding under 180MPa to obtain the ceramic biscuit.
And (3) placing the ceramic biscuit prepared in the step (4) into a silicon-molybdenum rod furnace, and presintering for 3 hours at the presintering temperature of 1000 ℃ to obtain the ceramic biscuit of the impregnated zirconia toughened alumina, namely the ZTA ceramic biscuit.
Putting the ZTA ceramic biscuit prepared in the step 5) into a plastic box, and adding Cr with the mass 6 times of that of the ZTA ceramic biscuit 3+ Impregnating with Cr (NO) 3 ) 3 •9H 2 Cr prepared from O 3+ Solution, solvent is deionized water, cr 3+ The concentration of the solution is 0.50g/mL, then the solution is put into a vacuum drier, the drying temperature is 20 ℃, the vacuum degree is-2 Pa, the vacuum is pumped for 3 hours, and then the residual Cr is added 3+ Pouring out the solution, placing the impregnated biscuit on oilpaper, maintaining the original vacuum degree, vacuumizing to-2 Pa, vacuumizing for 20 hours, and taking out and placing on a burning plate;
and (3) putting the ZTA ceramic biscuit on the firing plate into a high-temperature muffle furnace for sintering, wherein the sintering temperature is 1500 ℃, and the heat preservation time is 3 hours, so that the ruby-type high-strength Cr-ZTA ceramic material with pink color is prepared.
Examples
1) The alumina content is selected to be more than 99.9 percent, and the grain diameter D 50 90 g of high-purity alumina powder with the grain diameter D and the zirconia content of more than 99.9 percent 50 For 10 g of high-purity alumina powder with the diameter of 50nm, 320 g (about 405.1 mL) of absolute ethyl alcohol serving as a ball milling medium is selected, 150 g of zirconia balls with the diameter of 5mm and 200 g of alumina powder and zirconia powder with the diameter of 10mm are selected, added into a ball milling tank, and put on a planetary ball mill for ball milling and mixing for 24 hours.
2) After passing through a 200-mesh screen, the slurry obtained in the step 1) is sanded on a vertical sand mill for 3 hours, wherein the sand grinding balls are zirconia balls with the diameter of 0.5mm, the mass of the sand grinding balls is 100 g, and the sand grinding rotating speed is 2700r/min;
3) Filtering out the slurry uniformly sanded in the step 2), and putting the slurry on a rotary evaporator for rotary evaporation to dryness, wherein the rotary speed is 50r/min, the evaporation temperature is 50 ℃, and the rotary evaporation time is 2.5h, so as to obtain dry powder;
4) Sieving the dried powder obtained in the step 3) by a 80-mesh screen, and carrying out dry press molding under 78MPa and isostatic press molding under 200MPa to obtain the ceramic biscuit.
5) And (3) placing the ceramic biscuit prepared in the step (4) into a silicon-molybdenum rod furnace, and presintering for 1 hour at the presintering temperature of 1200 ℃ to obtain a ceramic biscuit of the impregnated zirconia toughened alumina, namely the ZTA ceramic biscuit.
6) Putting the ZTA ceramic biscuit prepared in the step 5) into a plastic box, and adding Cr with the mass 10 times of that of the ZTA ceramic biscuit 3+ Impregnating with Cr (NO) 3 ) 3 •9H 2 Cr prepared from O 3+ Solution, solvent is deionized water, cr 3+ The concentration of the solution is 0.72g/mL, then the solution is placed into a vacuum dryer, the drying temperature is 25 ℃, the vacuum degree is-1 Pa, the vacuum is pumped for 6 hours, and then the residual Cr is added 3+ Pouring out the solution, placing the impregnated biscuit on oilpaper, maintaining the original vacuum degree, vacuumizing to-1 Pa, vacuumizing for 24 hours, and taking out and placing on a burning plate;
7) And (3) putting the ZTA ceramic biscuit on the firing plate into a high-temperature muffle furnace for sintering, wherein the sintering temperature is 1580 ℃, and the heat preservation time is 1 hour, so that the ruby-type high-strength Cr-ZTA ceramic material with pink color is prepared.
Examples
1) The alumina content is selected to be more than 99.9 percent, and the grain diameter D 50 85 g of high-purity alumina powder with the grain diameter D and the zirconia content of more than 99.9 percent is selected 50 15g of high-purity alumina powder with the diameter of 50nm, 300 g of absolute ethyl alcohol (about 379.7 mL) serving as a ball milling medium, 120 g of zirconia balls with the diameter of 5mm and the mass of the alumina balls with the diameter of 10mm serving as the total weight of the alumina powder and the zirconia powder180 g of the mixture was put into a ball mill pot, and ball-milled and mixed in a planetary ball mill for 18 hours.
2) After passing through a 200-mesh screen, the slurry obtained in the step 1) is sanded on a vertical sand mill for 3 hours, wherein the sand grinding balls are zirconia balls with the diameter of 0.5mm, the mass of the sand grinding balls is 100 g, and the sand grinding rotating speed is 2700r/min;
3) Filtering out the slurry uniformly sanded in the step 2), and putting the slurry on a rotary evaporator for rotary evaporation to dryness, wherein the rotary speed is 50r/min, the evaporation temperature is 50 ℃, and the rotary evaporation time is 2.5h, so as to obtain dry powder;
4) Sieving the dried powder obtained in the step 3) by a 80-mesh screen, and carrying out dry press molding under 78MPa and isostatic press molding under 200MPa to obtain the ceramic biscuit.
5) And (3) placing the ceramic biscuit prepared in the step (4) into a silicon-molybdenum rod furnace, and presintering for 1 hour at the presintering temperature of 1200 ℃ to obtain a ceramic biscuit of the impregnated zirconia toughened alumina, namely the ZTA ceramic biscuit.
6) Putting the ZTA ceramic biscuit prepared in the step 5) into a plastic box, and adding Cr with the mass 10 times of that of the ZTA ceramic biscuit 3+ Impregnating with Cr (NO) 3 ) 3 •9H 2 Cr prepared from O 3+ Solution, solvent is deionized water, cr 3+ The concentration of the solution is 0.60g/mL, then the solution is put into a vacuum drier, the drying temperature is 25 ℃, the vacuum degree is-1 Pa, the vacuum is pumped for 6 hours, and then the residual Cr is added 3+ Pouring out the solution, placing the impregnated biscuit on oilpaper, maintaining the original vacuum degree, vacuumizing to-1 Pa, vacuumizing for 24 hours, and taking out and placing on a burning plate;
7) And (3) putting the ZTA ceramic biscuit on the firing plate into a high-temperature muffle furnace for sintering, wherein the sintering temperature is 1580 ℃, and the heat preservation time is 1 hour, so that the ruby-type high-strength Cr-ZTA ceramic material with pink color is prepared.
Step 6) is omitted, namely the ZTA ceramic biscuit is not subjected to Cr 3+ And (5) soaking in a solution. The procedure is as in example 2.
The ruby type high-strength Cr-ZTA ceramic material prepared by the invention is subjected to performance test, wherein the ceramic dimensional hardness test is carried out according to GB/T16534-2009, the bending strength test is carried out according to GB/T6569-2006, and the test results are shown in Table 1.
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Violet hardness (GPa) | 18.0 | 18.4 | 18.2 | 17.1 |
| Flexural Strength (Mpa) | 1015 | 1035 | 1024 | 856 |
| Bulk Density (g/cm) 3 ） | 4.25 | 4.26 | 4.25 | 4.11 |
Table 1.
Claims (10)
1. The ruby type high-strength Cr-ZTA ceramic material is characterized in that: is prepared from alumina powder (80-90 wt.%), zirconium oxide powder (10-20) and Cr (10-20) 3+ The addition amount of the solution is 0.1-0.4% of the sum of the mass of the alumina powder and the mass of the zirconia powder.
2. The ruby-type high-strength Cr-ZTA ceramic material according to claim 1, wherein: the Cr-ZTA ceramic material is prepared by the following steps: mixing alumina powder and zirconia powder through powder ball milling, sand grinding, rotary evaporating drying, dry pressing, isostatic pressing, presintering and Cr 3+ Solution impregnation and sintering.
3. The ruby-type high-strength Cr-ZTA ceramic material according to claim 1, wherein: the purity of the alumina powder is more than or equal to 99.9%, and the particle size is 200-800 nm; the purity of the zirconia powder is more than or equal to 99.9 percent, and the grain diameter is 50-200 nm.
4. The ruby-type high-strength Cr-ZTA ceramic material according to claim 1, wherein: the Cr 3+ The solution adopts Cr (NO) 3 ) 3 •9H 2 Cr prepared from O 3+ Solution, solvent is deionized water, cr 3+ The concentration of the solution is 0.50-0.72 g/mL.
5. The ruby-type high-strength Cr-ZTA ceramic material according to claim 1, wherein: the volume density of the Cr-ZTA ceramic material is more than or equal to 4.15g/cm 3 The bending strength is more than 1000MPa, and the Vickers hardness is more than 18GPa.
6. A method for preparing the ruby-type high-strength Cr-ZTA ceramic material according to any one of claims 1 to 5, which is characterized in that: the preparation method comprises the following steps:
1) Adding alumina powder, zirconia powder and a ball milling medium into a ball milling tank according to the formula amount, and mixing on a ball mill to prepare slurry;
2) Sieving the slurry prepared in the step 1) through a 100-200 mesh screen, and sanding on a vertical sand mill;
3) Filtering out the slurry which is uniformly sanded, and putting the slurry on a rotary evaporator for rotary evaporation to dryness to prepare dry powder;
4) Sieving the dried powder prepared in the step 3) through a 60-80 mesh screen, and carrying out dry press molding under 50-78 MPa and isostatic press molding under 180-200 MPa to prepare a ceramic biscuit;
5) Placing the ceramic biscuit into a silicon-molybdenum rod furnace for presintering, wherein the presintering temperature is 1000-1200 ℃ and the presintering time is 1-3 hours, so as to obtain a ZTA ceramic biscuit;
6) Mixing ZTA ceramic biscuit prepared in the step 5) with Cr 3+ Impregnating the solution with the Cr 3+ The adding amount of the solution is 6-10 times of the quality of the ZTA ceramic biscuit, then vacuum drying is carried out, the drying temperature is 20-25 ℃, the vacuum degree is minus 1-minus 2Pa, the vacuum is pumped for 3-6 hours, and then the residual Cr is processed 3+ Pouring out the solution, placing the impregnated ZTA ceramic biscuit on oilpaper, maintaining the vacuum degree to be-1 to-2 Pa, and vacuumizing for 20 to 24 hours;
7) And (3) carrying out high-temperature sintering on the ZTA ceramic biscuit subjected to vacuum pumping in the step (6), wherein the sintering temperature is 1500-1580 ℃, and the heat preservation time is 1-3 hours, so that the ruby type high-strength Cr-ZTA ceramic material is prepared.
7. The method of manufacturing according to claim 6, wherein: the ball milling medium in the step 1) is absolute ethyl alcohol, and the addition amount of the absolute ethyl alcohol is 280-320% of the total weight of the alumina powder and the zirconia powder.
8. The method of manufacturing according to claim 6, wherein: the grinding balls of the ball mill are zirconia balls with the diameter of 5mm and alumina balls with the diameter of 10mm, the mass of the zirconia balls with the diameter of 5mm is 100-150% of the total weight of the alumina powder and the zirconia powder, and the mass of the alumina balls with the diameter of 10mm is 150-200% of the total weight of the alumina powder and the zirconia powder.
9. The method of manufacturing according to claim 6, wherein: and 2) sanding, wherein the sanding time is 1-3 hours, the sand grinding balls are zirconia balls with the diameter of 0.5mm, the mass of the sand grinding balls is the mass sum of alumina powder and zirconia powder, and the sanding rotating speed is 1800-2700 r/min.
10. The method of manufacturing according to claim 6, wherein: and 3) rotary evaporation to dryness, wherein the rotary speed is 30-50 r/min, the evaporation temperature is 50-65 ℃, and the rotary evaporation time is 1.5-2.5 h.
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