CN111620691B - Al based on azeotropic distillation2O3/ZrO2Composite ceramic and preparation method and application thereof - Google Patents
Al based on azeotropic distillation2O3/ZrO2Composite ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002131 composite material Substances 0.000 claims abstract description 82
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 238000005452 bending Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003746 yttrium Chemical class 0.000 claims abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 6
- 229910009523 YCl3 Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000013001 point bending Methods 0.000 claims description 6
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 5
- 235000015895 biscuits Nutrition 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000009694 cold isostatic pressing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical group OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical class [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052593 corundum Inorganic materials 0.000 abstract description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 7
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000007246 mechanism Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 11
- 238000005054 agglomeration Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910017414 LaAl Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 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 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007656 fracture toughness test Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium 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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- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
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- B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
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- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
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- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
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- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
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Abstract
The invention discloses Al based on an azeotropic distillation method2O3/ZrO2The preparation method comprises preparing nanometer composite powder from zirconium salt, yttrium salt, aluminum salt and lanthanum salt by coprecipitation method and azeotropic distillation method, molding, calcining, and sintering at high temperature to obtain Al2O3/ZrO2Composite ceramics. The composite powder obtained by the invention is nano-scale, basically spherical, uniform in particle size distribution and wide in sintering temperature range; ZrO (ZrO)2Al is dispersed in the matrix2O3Grains and in-situ grown long-rod LaAl11O18The crystal grains are simultaneously introduced with phase change toughening, particle toughening and whisker toughening mechanisms, so that the fracture toughness, bending strength and hardness of the ceramic material are improved, the composite material also has good ageing resistance, integrates good mechanical properties and high stability, can be used for 5G mobile phone ceramic back plates, and is simple in preparation method, easy to operate and beneficial to large-scale production.
Description
Technical Field
The invention belongs to the technical field of oxide ceramic materials, and particularly relates to Al based on an azeotropic distillation method2O3/ZrO2Composite ceramic and a preparation method and application thereof.
Background
With the advent of the 5G era, the requirement for the mobile terminal, a mobile phone, which is indispensable to everyone is higher and higher. The mobile phone back plate in the current market mainly adopts metal, glass engineering plastics and the like. Only metals of these mainstream materials can satisfy the requirements of strength and appearance, but the metals can generate interference and shielding effects on mobile phone signals, which is undoubtedly fatal to the development of the 5G era of communication. The ceramic material has the characteristics of high strength, high hardness and high wear resistance, has a soft texture like jade, and can be used as a mobile phone back plate to integrate practicality and attractiveness, and particularly can not influence signals. The ceramic mobile phone backboard is a good opportunity for the development of the ceramic mobile phone backboard, and also makes higher requirements on the mechanical property and the stability of the ceramic material.
The material of the back plate of the existing ceramic mobile phone in the market is zirconia ceramic, and most of the materials are 3Y-TZP (stabilizer Y)2O3Tetragonal zirconia polycrystalline ceramics with a content of 3 mol%), in paper [ J.Cui, Z.Gong, M.Lv, P.Rao, Determination of fractional hardness of Y-TZP ceramics, center.Int.43 (2017) 16319-.]The real fracture toughness of the 3Y-TZP is accurately measured to be 4.4 MPa.m by using a modified SEVNB method1/2The bending strength is 627MPa, and the lower value is also the reason for causing the wide application of the ceramic mobile phone backboard. In this paper it was also accurately determined that the true fracture toughness of 2.5Y-TZP and 2Y-TZP were 5.3 MPa.m, respectively1/2And 6.4MPa · m1 /2The bending strength is 817MPa and 994MPa respectively, the reduction of the content of the stabilizer is beneficial to improving the fracture toughness and the bending strength, but the tetragonal phase zirconia is unstable and is easy to spontaneously change phase to generate microcracks, and the microcracks greatly influence the yield of the ceramic back plate of the mobile phone in preparation and processing. In addition, Y-TZP has a fatal weakness that stable tetragonal phase zirconium oxide can spontaneously change into monoclinic phase zirconium oxide at low temperature, especially in water vapor or humid environment, which is called as low-temperature aging effect, and the main reason is that Y3+Into ZrO2The crystal lattice simultaneously forms H which introduces oxygen vacancy and water molecule decomposes+And O2-Contact to ZrO2Will have precedence over Y3+Reacting to form YO (OH) defects and fill oxygen vacancies such that the stabilizer content is reduced, t-ZrO2Will grow gradually and spontaneously transform into m-ZrO when reaching the critical dimension2Macro and micro cracks are initiated. The generation of the phenomenon can cause the reduction of the mechanical property of the material, and if the unmodified single-phase Y-TZP is directly used for the mobile phone ceramic back plate, the stability of the mobile phone ceramic back plate cannot be ensured. Therefore, a new generation of 5G mobile phone ceramic back plate is needed to integrate good mechanical properties and high stability.
Adding higher valent metal oxides as stabilizers, e.g. CeO2Or a second phase of high elastic modulus such as Al2O3The low temperature aging of the Y-TZP can be effectively inhibited, but the fracture toughness of the zirconium oxide is lower as the zirconium oxide is more stable. The mechanism of inhibiting low-temperature aging by adding the second phase with high elastic modulus is that ZrO can be inhibited2And (5) growing crystal grains. Meanwhile, researches show that the addition of the second relative matrix with high elastic modulus plays a role in toughening and reinforcing, and the toughening mechanism comprises particle toughening and whisker or fiber toughening, namely nanoparticles or whiskers (fibers) are required to be added into the matrix, but the added nanoparticles or whiskers (fibers) are difficult to prepare and complex in process, and are easy to agglomerate, so that the sintering performance is reduced, and the nanoparticles or whiskers (fibers) are difficult to uniformly disperse in the matrix, and further the mechanical properties of the nanoparticles or whiskers (fibers) are greatly influenced.
Lanthanum hexaaluminate (LaAl)11O18) Is La2O3And Al2O3The crystal structure of the product generated at high temperature is composed of a spinel structure separated by cation and oxygen ion layers, and is very stable. Due to the structural characteristics of the alumina, long rod-shaped crystal grains are easily formed in an alumina matrix, and the effects of deflection, bridging, crystal grain extraction and the like are achieved in the fracture process, so that the brittleness of the alumina can be improved. Chinese patent CN1513803A introduces lanthanum hexaaluminate and single-phase Al into alumina matrix2O3Compared with the ceramic, the fracture toughness is improved by 30 percent. The preparation method of the composite powder comprises the step of coating alpha-Al2O3Adding the powder into inorganic salt solution of Al, La, Zr and Y, dripping ammonia water to generate precipitate, filtering, washing and calcining to obtain the productThe junction temperature range is very narrow, which is not beneficial to industrial production.
The paper [ Fei Zhang,
Chevalier,Christian Olagnon,Bart Van Meerbeek,Jef Vleugels, Slow crack growth and hydrothermal aging stability of an alumina-toughened zirconia composite made from La2O3-doped 2Y-TZP,J.Eur.Ceram.Soc.,37(2017)1865-1871]mixing LaAl11O18Incorporated in zirconia-based ceramics, in ZrO2Adding 20 wt% of Al2O3And 0.4 mol% La2O3The obtained complex phase ceramic contains t-ZrO2、 c-ZrO2、m-ZrO2、Al2O3、LaAl11O18The composite powder is prepared by wet ball milling, compared with coprecipitation method, the components can not be mixed uniformly, and the particle size distribution of the powder is wide and is 0.3-6 μm, so that the sintered ZrO2、Al2O3The range of the grain size is larger, and XRD results show that the sintered body contains more m-ZrO2And c-ZrO2，t-ZrO2The reduction of the content greatly weakens the phase change toughening effect, and Al is generated in the sintering process2O3Agglomeration also occurs to make LaAl11O18The dispersion is uneven, the fracture toughness is greatly reduced, and the dispersion is only 5.1 MPa.m1/2And the fracture toughness is lower than that of 2Y-TZP, so that the requirement of the ceramic back plate of the mobile phone cannot be met.
Disclosure of Invention
The invention aims to provide Al based on an azeotropic distillation method, which is suitable for large-scale and industrial production2O3/ZrO2The composite material has high strength, high fracture toughness and good low-temperature aging resistance, and the fracture toughness measured by an SEVNB method is 6.3-7.1 MPa.m1/2The bending strength measured by the three-point bending method is 900-1100MPa, the Vickers hardness is 13.5-14.5GPa, and the alloy material has good low-temperature aging resistance.
Another object of the present invention is to provide the saidAzeotropic distillation of Al2O3/ZrO2The composite ceramic is applied to the ceramic back plate of the mobile phone.
Compared with a solid phase method of wet mixing and ball milling, the coprecipitation method is a method for adding a precipitator capable of generating hydroxide radicals into a metal salt solution, filtering, drying and calcining the precipitate to obtain composite powder, and the composite powder obtained by the method is fine in granularity, uniform in component dispersion and still incapable of avoiding agglomeration because a large amount of coordinated water molecules and hydroxyl groups exist on the surface of precursor particles formed by liquid phase precipitation reaction, so that bridging and agglomeration among the particles are caused, and the sintering performance of the precursor particles is influenced.
The invention utilizes the azeotropic distillation method to effectively remove a large amount of hard agglomeration caused by coordination water molecules and hydroxyl groups on the surfaces of precursor particles on the basis of preparing the composite powder by the traditional coprecipitation method, the obtained composite powder has the advantages of uniform dispersion of components, good sphericity, uniform particle size distribution of 30-200nm, expanded junction temperature range to 1350-1500 ℃, and no c-ZrO in a sintered body2And only a very small amount of m-ZrO2(ii) a Using La2O3With Al2O3Reacting at high temperature to generate long rod-shaped LaAl11O18The long rod-shaped crystal grains grown in situ are tightly combined with the matrix and are uniformly dispersed, a toughening mechanism of crack deflection, bridging and crystal grain extraction is introduced into the composite ceramic material, the fracture toughness of the material is improved, and Al exists in the matrix2O3With LaAl11O18Effectively inhibit ZrO2Crystal grains grow, so that the low-temperature aging resistance is improved; la on the other hand2O3Can be used as a sintering aid, reduces the sintering temperature, can obtain a product with high density by normal pressure sintering, and has simple production process and low production cost.
The purpose of the invention is realized by the following technical scheme:
al based on azeotropic distillation method2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps of:
1) mixing zirconium salt, yttrium salt, aluminum salt, lanthanum salt and ethanol to obtain mixed solutionLiquid; zr in the mixed solution4+、Al3+The molar ratio of (5-8) to (1-3), Y3+With Zr4+The molar ratio of (2-3) to 100, La4+With Zr4+And Al3+The molar ratio of the total amount is (0.2-0.4): 100;
2) adding a surfactant into the mixed solution, mechanically stirring, dropwise adding ammonia water to generate a precipitate, and stopping dropwise adding until the pH value is 9-10 to form sol; the surfactant is PEG400 and/or PEG 2000;
3) standing and aging the obtained semitransparent sol, performing centrifugal separation, and sequentially cleaning with deionized water and ethanol to obtain gel;
4) adding n-butyl alcohol into the obtained gel, mechanically stirring, obtaining pre-sintered powder by using an azeotropic distillation method, and calcining at low temperature to obtain composite powder; the azeotropic distillation method comprises heating to gel boiling point, and continuing distillation for 20-30min until n-butanol is completely volatilized;
5) molding to obtain a pre-sintered blank;
6) sintering at normal pressure to obtain Al based on azeotropic distillation method2O3/ZrO2Composite ceramics.
To further achieve the object of the present invention, preferably, the zirconium salt in step 1) is ZrOCl2Yttrium salt being YCl3The aluminium salt is AlCl3The lanthanum salt is LaCl3The cation concentration of the prepared mixed solution is 0.3-0.6 mol/L.
Preferably, in the step 2), the addition amount of the surfactant is 2-4% of the total mass of the zirconium salt, the yttrium salt, the aluminum salt and the lanthanum salt; the mechanical stirring speed and time are respectively 500-800r/min and 5-10 min.
Preferably, the standing and aging time in the step 3) is 18-24 h; aging, cleaning until AgNO is used3No Cl was detected in the solution-Until now.
Preferably, in the step 4), the volume ratio of the addition amount of the n-butanol to the gel obtained in the step 3) is 1.5-2: 1; the mechanical stirring speed and the time are respectively 1200-1500r/min and 5-10 min.
Preferably, in the step 4), the temperature of the low-temperature calcination is 600-800 ℃, and the heat preservation time is 20-30 min.
Preferably, in the step 5), the molding is completed on an automatic press, the pressure is 5-8MPa, the pressure maintaining time is 3-5s, then the obtained biscuit is placed into a sealing bag, and cold isostatic pressing is performed after vacuum pumping, the pressure is 200-250MPa, and the pressure maintaining time is 120-180s, so as to obtain the pre-sintered blank.
Preferably, the sintering temperature of the atmospheric sintering in the step 6) is 1350-.
Al based on azeotropic distillation method2O3/ZrO2The composite ceramic is prepared by the preparation method; ZrO of composite ceramics2Second phase Al is uniformly distributed on the substrate2O3Crystal grain and long rod shaped LaAl11O18Grain, long rod-like LaAl11O18The crystal grains are grown in situ and tightly combined with the matrix, and the fracture toughness of the composite ceramic measured by an SEVNB method is 6.3-7.1 MPa.m1/2The bending strength measured by the three-point bending method is 900-1100MPa, and the Vickers hardness is 13.5-14.5 GPa.
The Al based on azeotropic distillation method2O3/ZrO2The composite ceramic can be applied to a ceramic back plate of a mobile phone.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts a coprecipitation method and an azeotropic distillation method to prepare the nano-scale composite powder in one step, and effectively removes hard agglomeration caused by a large amount of coordinated water molecules and hydroxyl groups existing on the surfaces of precursor particles, so that the obtained composite powder has the advantages of uniform dispersion of components, good sphericity, uniform particle size distribution, wide sintering range and sintered matrix ZrO2Fine and uniform in size of crystal grains and free from c-ZrO2And only a very small amount of m-ZrO2(ii) a Sintered Al2O3The crystal grains are uniformly dispersed without agglomeration.
2) La of the invention2O3With Al2O3Reacting at high temperature to generate long rod-shaped LaAl11O18The in-situ grown long rod-like crystal grains are tightly combined with the matrix compared with the externally added crystal whiskers (or fibers)Dense and uniformly dispersed, reducing the complex preparation process of the crystal whisker, ZrO2Al is dispersed in the matrix2O3Grains and in-situ grown long-rod LaAl11O18The crystal grains are simultaneously introduced with the mechanisms of phase change toughening, particle toughening and whisker toughening, so that crack deflection, bridging and crystal grain extraction toughening can be effectively introduced into the composite ceramic material, and the fracture toughness, bending strength and hardness of the material are improved; the composite material obtained by the invention also has good ageing resistance, integrates good mechanical property and high stability, and can be used for 5G mobile phone ceramic back plates.
3) The Al coexists in the matrix of the present invention2O3And LaAl11O18Effectively inhibit ZrO2The crystal grains grow up, and the low-temperature failure resistance of the alloy is improved.
4) La of the invention2O3Can be used as a sintering aid, the sintering temperature is reduced, and a product with high density can be obtained by normal pressure sintering.
5) The invention has simple production process, low production cost and easy operation, and is beneficial to large-scale production.
Drawings
FIG. 1 shows Al obtained by azeotropic distillation in example 12O3/ZrO2SEM photograph of the micro-morphology of the surface of the composite ceramic.
FIG. 2 shows Al obtained by azeotropic distillation in example 12O3/ZrO2Spectrum 1 grain EDS analysis of the composite ceramic in fig. 1.
FIG. 3 shows Al obtained by azeotropic distillation in example 12O3/ZrO2Spectrum 2 grain EDS analysis of the composite ceramic in fig. 1.
FIG. 4 shows Al obtained by azeotropic distillation in example 12O3/ZrO2The XRD pattern of the surface of the composite ceramic is (5-90 degrees).
FIG. 5 shows Al obtained by azeotropic distillation in example 12O3/ZrO2The XRD pattern (33 ° -37 °) of the composite ceramic at zone 1 in FIG. 4.
FIG. 6 shows A by azeotropic distillation in example 1l2O3/ZrO2The XRD pattern (42-44) of the composite ceramic at region 2 in FIG. 4.
FIG. 7 shows Al obtained by azeotropic distillation in example 12O3/ZrO2The XRD pattern (44.5 deg. -45.5 deg.) of the composite ceramic at region 3 in FIG. 4.
FIG. 8 shows Al obtained by azeotropic distillation in example 12O3/ZrO2Fracture morphology after fracture toughness test of the composite ceramic.
FIG. 9 shows Al obtained by azeotropic distillation in example 12O3/ZrO2SEM photograph of composite ceramic polished surface indentation crack propagation.
FIG. 10 shows Al based on azeotropic distillation in example 12O3/ZrO2The composite ceramic, the commercial 3Y-TZP sample and the 2Y-20Al-La sample are subjected to aging treatment in water at 134 ℃ for 144 hours to obtain m-ZrO2Content diagram.
Detailed Description
For a better understanding of the invention, reference is made to the following description of the invention in connection with the accompanying drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples described.
Example 1
Al based on azeotropic distillation method2O3/ZrO2The preparation method of the composite ceramic comprises the following steps:
1) ZrOCl2、YCl3、AlCl3、LaCl3Mixing with ethanol to obtain a mixed solution with a cation concentration of 0.3mol/L, wherein Zr is contained in the mixed solution4+With Al3+The molar ratio is 5:3, Y3+With Zr4+The molar ratio of La to 3:1003+With Zr4+And Al3+The molar ratio of the total amount is 0.4:100,.
2) Adding surfactant PEG400 accounting for 1 percent of the total mass and PEG2000 accounting for 1 percent of the total mass into the mixed solution, and then mechanically stirring at the rotating speed of 800r/min for 5 min. Then, ammonia was added dropwise until the pH was 9.5.
3) And standing and aging the obtained semitransparent sol for 18h, performing centrifugal separation, and sequentially cleaning with deionized water and ethanol to obtain the sol.
4) Adding n-butyl alcohol into the gel, then mechanically stirring, pouring the mixture into a three-neck flask for azeotropic distillation at the rotation speed of 1200r/min and the time of 10min, wherein the adding amount of the n-butyl alcohol is 1.5:1 to the volume ratio of the gel, the azeotropic temperature of water and the n-butyl alcohol is 90 ℃, when no water exists, heating to the boiling point of the n-butyl alcohol of above 117 ℃, continuously distilling for 25min until the n-butyl alcohol is completely volatilized to obtain pre-sintered powder, calcining at the low temperature of 700 ℃ and preserving heat for 25min to obtain composite powder.
5) And (3) dry-pressing and molding the composite powder obtained in the step 4) at 8MPa for 3s, putting the obtained biscuit into a sealing bag, vacuumizing, and then carrying out cold isostatic pressing at the molding pressure of 200MPa for 180s to obtain a pre-sintered blank.
6) And sintering the blank at 1350 ℃ under normal pressure, and preserving heat for 2 hours to obtain the Al2O3/ZrO2 composite ceramic based on the azeotropic distillation method.
FIG. 1 shows Al obtained in example 1 by azeotropic distillation2O3/ZrO2SEM photograph of the polished surface of the composite ceramic sample shows that the material has very good sintering performance, and the densification is realized at the sintering temperature of 1500 ℃. In the figure, it can be seen that the white grains are ZrO2The crystal grains have narrow size distribution and no abnormal long crystal grains, the black second phase crystal grains are uniformly distributed in the matrix, and the black crystal grains are in two forms, namely long rods and polygons. Fig. 2 is an EDS analysis result of the crystal grain indicated by the spectrum 1 in fig. 1, showing that the crystal grain contains Al, La, and O elements, and fig. 3 is an EDS analysis result of the crystal grain indicated by the spectrum 2 in fig. 1, showing that the crystal grain contains only Al and O elements. FIG. 4 is an XRD pattern (5-90 deg.) of a polished surface of an Al2O3/ZrO2 composite ceramic sample based on azeotropic distillation obtained in example 1, the phase composition being t-ZrO2、m-ZrO2、Al2O3And LaAl11O18FIGS. 5, 6 and 7 show LaAl detected in regions 1, 2 and 3 of FIG. 4, respectively11O18The enlarged view of the characteristic peak, combined with FIGS. 2 and 3, can obtain LaAl as the black long rod-shaped crystal grain in FIG. 111O18The black polygonal crystal grain is Al2O3. The phase composition was calculated to be 95.3 wt% t-ZrO using the refinement software2，1.7wt％m-ZrO2，0.9wt％Al2O3，2.1wt％LaAl11O18The results of the paper [ Fei Zhang,
Chevalier,Christian Olagnon,Bart Van Meerbeek,Jef Vleugels,Slow crack growth and hydrothermal aging stability of an alumina-toughened zirconia composite made from La2O3-doped 2Y-TZP,J.Eur.Ceram.Soc.,37(2017)1865-1871]compared with the phase composition result in no c-ZrO2And contains only a very small amount of m-ZrO2。
FIG. 8 shows Al obtained by azeotropic distillation in example 12O3/ZrO2Fracture morphology after fracture toughness test of composite ceramic, FIG. 9 is Al based on azeotropic distillation method in example 12O3/ZrO2SEM photograph of composite ceramic polished surface indentation crack propagation. The fracture morphology of fig. 8 and the crack propagation of fig. 9 indicate that the crack deflects when it encounters a long rod-like grain. The Al obtained as described above was determined to be based on azeotropic distillation2O3/ZrO2The fracture toughness of the composite ceramic sample measured by SEVNB method is 7.1MPa m1/2The three-point bending strength is 958MPa, and the hardness is 14.5 GPa. LaAl used in Chinese invention patent CN1513803A11O18Improved Al2O3Based on composite ceramic, since the matrix is Al2O3So that the fracture toughness is far lower than that of ZrO2The base composite ceramic can not meet the requirement of the ceramic mobile phone backboard on fracture toughness. The paper [ Fei Zhang,
Chevalier, Christian Olagnon,Bart Van Meerbeek,Jef Vleugels,Slow crack growth and hydrothermal aging stability of an alumina-toughened zirconia composite made from La2O3-doped 2Y-TZP,J.Eur. Ceram.Soc.,37(2017)1865-1871]preparation of ZrO by wet ball milling2、Al2O3、La2O3The components of the composite powder can not be completely and uniformly mixed, the granularity range of the powder is too large, and Al is generated in the sintering process2O3Agglomeration also occurs, so that c-ZrO in the sintered body is more abundant2With m-ZrO2Weaken t-ZrO2The phase change toughening effect and the fracture toughness are 20 percent lower than those of the invention.
FIG. 10 shows Al obtained by azeotropic distillation in example 12O3/ZrO2And (3) the monoclinic phase content of the composite ceramic after aging treatment in water at 134 ℃ for 144 h. Example 1 had only 10% t-ZrO after 144h of low temperature ageing treatment2Conversion to m-ZrO2Compared with two samples, one of which is commercial 3Y-TZP and is also a material used for a 5G mobile phone ceramic back plate on the market at present, and the other is a paper [ Fei Zhang,
Chevalier,Christian Olagnon,Bart Van Meerbeek,Jef Vleugels,Slow crack growth and hydrothermal aging stability of an alumina-toughened zirconia composite made from La2O3-doped 2Y-TZP,J.Eur.Ceram.Soc.,37(2017)1865-1871]the obtained sample with the best anti-aging performance shows that the low-temperature aging curve of the example 1 is stable and flat in increment and shows excellent low-temperature aging resistance.
At present, 5G mobile phone back plate materials which can not generate signal shielding comprise ceramics, plastics and glass. The plastic has the lowest preparation cost but the lowest wear resistance, is easy to scrape and has low sensory grade; the glass has good texture, the bending strength is 400MPa, and the fracture toughness is only 3 MPa.m1/2The brittleness is high, the product is easy to be brittle when falling off in the using process, and the use cost is increased by frequent replacement; the ceramic has the best wear resistance, the texture is mild and moist like jade, and the ceramic gives noble and elegant sense, in the embodiment 1, the Al based on the azeotropic distillation method2O3/ZrO2The bending strength, especially the fracture toughness of the composite ceramic is far higher than that of a glass material, and the bending strength and the fracture toughness of the composite ceramic are higher than those of the 3Y-TZP component of the current ceramic mobile phone backboard materialRespectively improved by 53 percent and 61 percent, is higher than 2Y-TZP, simultaneously has better low-temperature aging resistance, integrates good mechanical property and high stability, has simple preparation method and is very beneficial to industrial production. Therefore, the ceramic back plate is very suitable for the new generation of 5G mobile phone ceramic back plates.
Example 2
Al based on azeotropic distillation method2O3/ZrO2The preparation method of the composite ceramic comprises the following steps:
1) ZrOCl2、YCl3、AlCl3、LaCl3Mixing with ethanol to obtain a mixed solution with the total cation concentration of 0.5mol/L, wherein Zr in the mixed solution4+With Al3+The molar ratio is 8:1, Y3+With Zr4+Molar ratio of 2.3:100, La3+With Zr4+And Al3+The molar ratio of the total amount was 0.3: 100.
2) Adding salt (ZrOCl) into the mixed solution2、YCl3、AlCl3、LaCl3) And 2.5 percent of surfactant PEG2000 by mass, and then mechanically stirring at the rotating speed of 500r/min for 8 min. Then, ammonia was added dropwise until the pH was 9.
3) And standing and aging the obtained semitransparent sol for 24 hours, then performing centrifugal separation, and sequentially cleaning with deionized water and ethanol to obtain gel.
4) Adding n-butyl alcohol into the gel, wherein the adding amount of the n-butyl alcohol and the volume ratio of the gel is 2:1, then mechanically stirring, pouring into a three-neck flask for azeotropic distillation at the rotation speed of 1500r/min for 5min, heating to the azeotropic temperature of water and the n-butyl alcohol of 90 ℃, heating to the boiling point of the n-butyl alcohol of more than 117 ℃ after no moisture exists, continuing to distill for 20min until the n-butyl alcohol is completely volatilized to obtain pre-sintered powder, calcining at the low temperature of 600 ℃, and preserving heat for 30min to obtain composite powder.
5) And (3) dry-pressing and molding the composite powder obtained in the step 4) at 5MPa for 5s, putting the obtained biscuit into a sealing bag, vacuumizing, and then carrying out cold isostatic pressing at the molding pressure of 250MPa for 120s to obtain a pre-sintered blank.
6) Mixing the blankSintering the body at 1500 ℃ under normal pressure, and keeping the temperature for 1.5h to obtain Al based on an azeotropic distillation method2O3/ZrO2Composite ceramics.
The Al obtained as described above was determined to be based on azeotropic distillation2O3/ZrO2The fracture toughness of the composite ceramic sample measured by SEVNB method is 6.5MPa m1/2The three-point bending strength is 1045MPa, the hardness is 13.5GPa, the bending strength and the fracture toughness are both improved, and the preparation method is simple and is very favorable for industrial production.
Example 3
Al based on azeotropic distillation method2O3/ZrO2The preparation method of the composite ceramic comprises the following steps:
1) ZrOCl2、YCl3、AlCl3、LaCl3Mixing with ethanol to obtain a mixed solution with a cation concentration of 0.6mol/L, wherein Zr is contained in the mixed solution4+With Al3+The molar ratio is 2:1, Y3+With Zr4+The molar ratio of La to 2:1003+With Zr4+And Al3+The molar ratio of the total amount is 0.2:100,.
2) Adding surfactant PEG400 accounting for 1% of the total mass and PEG2000 accounting for 3% of the total mass into the mixed solution, and then mechanically stirring at the rotating speed of 600r/min for 8 min. Then, ammonia was added dropwise until the pH was 10.
3) And standing and aging the obtained semitransparent sol for 22 hours, performing centrifugal separation, and sequentially cleaning with deionized water and ethanol to obtain gel.
4) Adding n-butyl alcohol into the gel, then mechanically stirring, pouring the mixture into a three-neck flask for azeotropic distillation at a speed of 1400r/min and a time of 7min, wherein the adding amount of the n-butyl alcohol is 1.8:1 to the volume ratio of the gel, heating to 90 ℃ of the azeotropic temperature of water and the n-butyl alcohol, heating to above 117 ℃ of the boiling point of the n-butyl alcohol after no moisture exists, continuing to distill for 30min until the n-butyl alcohol is completely volatilized, calcining at a low temperature of 800 ℃ and preserving heat for 20min to obtain the composite powder.
5) And (3) dry-pressing and molding the composite powder obtained in the step 4) at 6MPa for 4s, putting the obtained biscuit into a sealing bag, vacuumizing, and then carrying out cold isostatic pressing, wherein the molding pressure is 230MPa and the pressure maintaining time is 150s, so as to obtain a pre-sintered blank.
6) Sintering the blank at 1400 ℃ under normal pressure, and keeping the temperature for 1.8h to obtain Al based on an azeotropic distillation method2O3/ZrO2Composite ceramics.
The Al obtained as described above was determined to be based on azeotropic distillation2O3/ZrO2The fracture toughness of the composite ceramic sample measured by SEVNB method is 6.8MPa m1/2The three-point bending strength was 1101MPa, and the hardness was 14.2 GPa. The bending strength and the fracture toughness are both improved, and the preparation method is simple and is very beneficial to industrial production.
As can be seen from the above examples, the invention adopts the coprecipitation method and the azeotropic distillation method to prepare the nano-scale composite powder in one step, and effectively removes the hard agglomeration caused by a large amount of coordinated water molecules and hydroxyl groups existing on the surfaces of the precursor particles, so that the obtained composite powder has the advantages of uniform component dispersion, good sphericity, uniform particle size distribution, wide sintering range and sintered matrix ZrO2Fine and uniform in size of crystal grains and free from c-ZrO2And only a very small amount of m-ZrO2(ii) a Sintered Al2O3The crystal grains are uniformly dispersed without agglomeration.
La of the invention2O3With Al2O3Reacting at high temperature to generate long rod-shaped LaAl11O18Compared with the externally added crystal whisker (or fiber), the in-situ grown long rod-shaped crystal grain is tightly combined with the matrix and uniformly dispersed, thereby reducing the complex crystal whisker preparation process, namely ZrO2Al is dispersed in the matrix2O3Grains and in-situ grown long-rod LaAl11O18The crystal grains are simultaneously introduced with the mechanisms of phase change toughening, particle toughening and whisker toughening, so that crack deflection, bridging and crystal grain extraction toughening can be effectively introduced into the composite ceramic material, and the fracture toughness, bending strength and hardness of the material are improved; the composite material obtained by the invention also has good ageing resistance, integrates good mechanical property and high stability, and can be used for 5G mobile phone ceramic back plates.
The Al coexists in the matrix of the present invention2O3And LaAl11O18Effectively inhibit ZrO2The crystal grains grow up, and the low-temperature failure resistance of the alloy is improved.
La of the invention2O3Can be used as a sintering aid, the sintering temperature is reduced, and a product with high density can be obtained by normal pressure sintering.
The invention has simple production process, low production cost and easy operation, and is beneficial to large-scale production.
The above-described embodiments are intended to be illustrative, rather than restrictive, and all such changes, modifications, substitutions, combinations, and simplifications that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. Al based on azeotropic distillation method2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps of:
1) mixing zirconium salt, yttrium salt, aluminum salt, lanthanum salt and ethanol to obtain a mixed solution; zr in the mixed solution4+、Al3+The molar ratio of (5-8) to (1-3), Y3+With Zr4+The molar ratio of (2-3) to 100, La4+With Zr4+And Al3+The molar ratio of the total amount is (0.2-0.4): 100;
2) adding a surfactant into the mixed solution, mechanically stirring, dropwise adding ammonia water to generate a precipitate, and stopping dropwise adding until the pH value is 9-10 to form sol; the surfactant is PEG400 and/or PEG 2000;
3) standing and aging the obtained semitransparent sol, performing centrifugal separation, and sequentially cleaning with deionized water and ethanol to obtain gel;
4) adding n-butyl alcohol into the obtained gel, mechanically stirring, obtaining pre-sintered powder by using an azeotropic distillation method, and calcining at low temperature to obtain composite powder; the azeotropic distillation method comprises heating to gel boiling point, and continuing distillation for 20-30min until n-butanol is completely volatilized;
5) molding to obtain a pre-sintered blank;
6) sintering at normal pressure to obtain Al based on azeotropic distillation method2O3/ZrO2Composite ceramics.
2. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: the zirconium salt in the step 1) is ZrOCl2Yttrium salt being YCl3The aluminium salt is AlCl3The lanthanum salt is LaCl3The cation concentration of the prepared mixed solution is 0.3-0.6 mol/L.
3. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: step 2), the addition amount of the surfactant is 2-4% of the total mass of the zirconium salt, the yttrium salt, the aluminum salt and the lanthanum salt; the mechanical stirring speed and time are respectively 500-800r/min and 5-10 min.
4. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: standing and aging for 18-24h in the step 3); aging, cleaning until AgNO is used3No Cl was detected in the solution-Until now.
5. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: in the step 4), the volume ratio of the addition amount of the n-butanol to the gel obtained in the step 3) is 1.5-2: 1; the mechanical stirring speed and the time are respectively 1200-1500r/min and 5-10 min.
6. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: in the step 4), the temperature of the low-temperature calcination is 600-800 ℃, and the heat preservation time is 20-30 min.
7. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: and 5), completing the molding on an automatic press, wherein the pressure is 5-8MPa, the pressure maintaining time is 3-5s, then filling the obtained biscuit into a sealing bag, vacuumizing, and performing cold isostatic pressing, wherein the pressure is 200-250MPa, and the pressure maintaining time is 120-180s, so as to obtain the pre-sintered blank.
8. Al according to claim 1 based on azeotropic distillation2O3/ZrO2The preparation method of the composite ceramic is characterized by comprising the following steps: the sintering temperature of the normal pressure sintering in the step 6) is 1350-.
9. Al based on azeotropic distillation method2O3/ZrO2Composite ceramic, characterized in that it is obtained by the production method according to any one of claims 1 to 8; ZrO of composite ceramics2Second phase Al is uniformly distributed on the substrate2O3Crystal grain and long rod shaped LaAl11O18Grain, long rod-like LaAl11O18The crystal grains are grown in situ and tightly combined with the matrix, and the fracture toughness of the composite ceramic measured by an SEVNB method is 6.3-7.1 MPa.m1/2The bending strength measured by the three-point bending method is 900-1100MPa, and the Vickers hardness is 13.5-14.5 GPa.
10. Al according to claim 9 based on azeotropic distillation2O3/ZrO2The composite ceramic can be applied to a ceramic back plate of a mobile phone.
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