CN112142450B - Zirconia composite alumina ceramic sintered body and preparation method and application thereof - Google Patents
Zirconia composite alumina ceramic sintered body and preparation method and application thereof Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 232
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 16
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 14
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002210 silicon-based material Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 17
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 14
- 235000012255 calcium oxide Nutrition 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
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- 150000003755 zirconium compounds Chemical class 0.000 claims 1
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 238000000280 densification Methods 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
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- 230000000694 effects Effects 0.000 description 22
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- 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 13
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates to a zirconia composite alumina ceramic sintered body, which comprises the following components in percentage by mass: 0.01-19.0 wt% of zirconium-containing compound (calculated in the form of zirconium oxide), 0.01-1 wt% of yttrium-containing compound (calculated in the form of yttrium oxide), 0.16-4.6 wt% of silicon-containing compound (calculated in the form of silicon oxide), 0.035-1.0 wt% of calcium-containing compound (calculated in the form of calcium oxide), 0.07-2.0 wt% of magnesium-containing compound (calculated in the form of magnesium oxide), and the balance of aluminum oxide. The zirconia-alumina composite ceramic sintered body of the present invention is formed of 3Y-ZrO2The additive is used for realizing the synergistic effect of various toughening modes such as phase change toughening, microcrack toughening, internal crystal structure strengthening toughening, surface strengthening toughening and the like; with CaCO3、SiO2MgO is used as a sintering aid, the sintering temperature of the alumina ceramic is reduced, the sintering rate is accelerated, and sintering densification is promoted through liquid phase sintering, and the alumina substrate prepared by the zirconia composite alumina ceramic sintered body has good fracture toughness and bending strength.
Description
Technical Field
The invention relates to a zirconia composite alumina (ZTA) ceramic sintered body, a preparation method and application thereof, belonging to the technical field of alumina ceramics.
Background
ZTA, namely Zirconia-Toughened Alumina, is a novel composite ceramic material which uses alpha Alumina as a main crystal phase and metastable and phase-changeable tetragonal Zirconia as a reinforcing and toughening phase. Wherein zirconia is added to the alumina matrix as an additive to promote densification of the alumina during sintering; or the zirconium oxide particles are dispersed in the alumina matrix, and the comprehensive performance of the alumina is improved by utilizing the phase transition process of the zirconium oxide from a tetragonal phase → a monoclinic phase (t → m). The toughening mechanism of the zirconia for the alumina ceramic is refined and comprises phase change toughening, microcrack toughening, internal crystal structure strengthening toughening, surface strengthening toughening and the like. The method utilizes the martensite phase transformation toughening effect of the zirconia to uniformly disperse the metastable zirconia particles into the alumina ceramic, thereby not only inhibiting the phenomenon of abnormal growth of crystal grains generated during the sintering of the alumina ceramic. When the ceramic body is subjected to external stress, the metastable zirconia generates martensite phase transformation from tetragonal phase to monoclinic phase, and can absorb external stress energy. The ZTA ceramic has more excellent performances than single-component ceramic of alumina, can greatly improve the fracture toughness of the alumina ceramic, improve the bending strength of the alumina ceramic, and simultaneously increase the hardness of the zirconia ceramic and is lower than pure zirconia ceramic in cost. The series of excellent properties of ZTA ceramics make the ZTA ceramics have attractive prospect in the aspects of aerospace, aviation, engine wear-resistant parts and cutters, and are also the preferred materials in the fields. Therefore, the ZTA composite ceramic material becomes a research hotspot in the field of modern ceramics. For example:
addition of Al is reported in DE1020040122312O391-97.96% by weight of ZrO2Weight ratio of 2-9%, Y2O3And/or when the weight proportion of CaO is 0.04-1%, the produced ZTA composite ceramic layer has bending strength of more than 500MPa and thermal conductivity of more than 20W/mK. Patent CN201380056024.2 reports on alpha-Al2O3ZrO addition to ceramic matrices in amounts of 2 to 15% by weight2And 0.01 to 1 wt% of Y2O3When the grain size of the controlled alumina is 2-8um, the bending strength of the ceramic can be increased; DE102004012231 reports on alpha-Al2O3ZrO addition to ceramic matrices in amounts of 2 to 9% by weight20.04-1 wt% of Y2O3And 0.04-1 wt% of CaO, so that the purpose of improving the bending strength of the ceramic can be realized, and the thicknesses of the metal layer and the ceramic layer can be reduced to improve the heat conduction efficiency of the metal-ceramic-base material. Rogers patent CN104755445B reports that when the ratio of zirconium-containing compound (calculated as zirconium oxide) is 2-15 wt%, the ratio of yttrium-containing compound (calculated as yttrium oxide) is 0.01-1 wt%, and Al is regulated2O3When the average particle diameter of (2) to (8) um; al (Al)2O3When the ratio of the grain boundary length of the crystal grains to the total length of all the grain boundaries is more than 0.6, the ZTA composite ceramic of more than 500MPa can be prepared.
However, in the current ZTA ceramic preparation process, the ZTA complex phase ceramic is Al2O3Adding into the powder ZrO2The powder is obtained by granulation molding, high-temperature sintering and post processing after mechanical mixing. The preparation method has simple process and low cost, but always has ZrO2Powder of Al2O3The problem of agglomeration due to uneven dispersion in the matrix; the method mainly shows that the secondary phase is unevenly distributed after main firing, partial main crystalline phase particles grow up abnormally, and the like, so that phase separation defects such as over firing in partial areas and residual internal stress among crystal grains are easy to occur, and the performance of the ZTA complex phase ceramic is greatly reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a zirconia-alumina composite (ZTA) ceramic sintered body, a preparation method and application thereof, and the invention uses 3Y-ZrO2The additive is used for realizing the synergistic effect of various toughening modes such as phase change toughening, microcrack toughening, internal crystal structure strengthening toughening, surface strengthening toughening and the like; with CaCO3、SiO2MgO is used as a sintering aid, and the sintering temperature of the alumina ceramic is reduced, the sintering rate is increased and the sintering densification is promoted through liquid phase sintering.
The additive of the ZTA composite ceramic sintered body is ZrO2Belongs to the technical field of synergistic action of various toughening modes such as phase change toughening, microcrack toughening and the like. When the ceramic is sintered, the zirconia is formed of a monoclinic phase (rho. 5.68 g/cm)3) Tetragonal phase (rho: 6.10 g/cm)3) During the transformation process of the crystal form, partial heat is absorbed, and the ceramic has more volume shrinkage (about 3-5%) along with the increase of the density, thereby being beneficial to the compactness of the ceramic. However, in the cooling process of the ceramic, because the tetragonal zirconia has instability, the tetragonal zirconia is converted into a monoclinic phase from a tetragonal phase, and at the moment, the volume expansion occurs and the variation quantity exceeds the ZrO2When the elasticity of the crystal grains is endured, the crystal grains are subjected to phase change at the time of cooling and are induced to generate a large number of cracks, so that the ceramic is broken and cannot be used. Therefore, Y is often added to zirconia ceramics2O3As a stabilizer, tetragonal zirconia can exist stably in the ceramic cooling process, and the tetragonal zirconia is subjected to phase change under the action of external force to toughen the ceramic (3Y-Z is added in the invention)rO2(ii) a I.e. Y2O3And ZrO2In a molar ratio of 3: 97). In addition, the mechanism of zirconia transformation toughening in ZTA also comprises that metastable tetragonal zirconia grains are inhibited by alumina, so that the zirconia ceramic is in a compressive stress state, and the like. When the ceramic material is impacted by force, tensile stress can be generated in the ceramic material, the constraint of the zirconia in a compressive stress state can be reduced, phase change can further occur, the energy of external force is absorbed in the phase change process, the volume is increased, stress is generated again, the two methods play a role in preventing or delaying crack propagation, and therefore the fracture toughness and the strength of the ceramic are improved. At present, in addition to stress induced phase transition toughening, the toughening mechanisms in ZTA ceramics include microcrack toughening, intra-crystalline structure toughening, and surface toughening.
(1) The microcracks toughen, the microcracks in ZTA play a toughening role mainly through two modes, one mode is that in the ceramic sintering process, the grain size of zirconia grains is larger than a critical dimension dc, so that in the ceramic cooling process, the volume expansion is generated by the phase change effect, and then the ceramic is broken to generate a large number of microcracks. The other is due to the thermal expansion mismatch between the zirconia particles and the alumina phase, which causes microcracking. When the stress acts on the microcrack area, the microcrack can absorb partial energy and reduce the stress concentration at the end part of the main crack, thereby slowing or controlling the continuous diffusion of the main crack and achieving the purpose of increasing the toughness of the material.
(2) The internal crystal structure strengthens and toughens, the generation of the nanocrystallization effect is caused by the internal crystal structure, and the final result can cause the internal crystal structure to toughen in the ceramic. However, it is difficult to control the grain size of the alumina and zirconia grains to be less than 100nm in the process of preparing ZTA nano composite ceramic, so that the zirconia grains can be controlled to be only nano-scale. The ZTA nano complex-phase ceramic is characterized in that zirconia nano particles are introduced into an alumina matrix in the ceramic sintering process, and the final sintering result is that not only zirconia grains exist among alumina grains, but also a part of the zirconia grains are surrounded in the grains by the alumina, so that the toughening of an inner crystal form is initiated when external force is applied.
(3) The surface strengthening and toughening refer to that when zirconium oxide undergoes a phase transition from a tetragonal phase to a monoclinic phase in the ZTA nano composite ceramic, a compressive stress layer capable of improving the strength of the ZTA ceramic can be formed on the surface of the ZTA nano composite ceramic due to volume expansion. Currently, there are many factors and methods for inducing this phase change, such as sandblasting, grinding, surface coating, cryogenic treatment, and chemical treatment.
In order to achieve the purpose, the invention adopts the technical scheme that: a zirconia-alumina composite ceramic sintered body comprises the following components in percentage by mass: 0.01-19.0 wt% of zirconium-containing compound (calculated in the form of zirconium oxide), 0.01-1 wt% of yttrium-containing compound (calculated in the form of yttrium oxide), 0.16-4.6 wt% of silicon-containing compound (calculated in the form of silicon oxide), 0.035-1.0 wt% of calcium-containing compound (calculated in the form of calcium oxide), 0.07-2.0 wt% of magnesium-containing compound (calculated in the form of magnesium oxide), and the balance of aluminum oxide. The zirconium-containing compound and the yttrium-containing compound of the present invention are prepared by adding 3Y-ZrO2To obtain a sintered zirconia composite alumina ceramic containing 3Y-ZrO20.01-20 wt% of powder.
As a preferred embodiment of the alumina ceramic sintered body of the present invention, the ceramic sintered body contains the following components in percentage by mass: 6.65-13.3 wt% of zirconium-containing compound (calculated in the form of zirconium oxide), 0.35-0.7 wt% of yttrium-containing compound (calculated in the form of yttrium oxide), 0.16-2.76 wt% of silicon-containing compound (calculated in the form of silicon oxide), 0.035-0.6 wt% of calcium-containing compound (calculated in the form of calcium oxide), 0.07-1.2 wt% of magnesium-containing compound (calculated in the form of magnesium oxide), and the balance of aluminum oxide. The zirconium-containing compound and the yttrium-containing compound of the present invention are prepared by adding 3Y-ZrO2To obtain a sintered zirconia composite alumina ceramic containing 3Y-ZrO27-14 wt% of powder.
As a preferred embodiment of the alumina ceramic sintered body of the present invention, the ceramic sintered body contains the following components in percentage by mass: zirconium-containing compounds (in the form of zirconium oxide)Calculated) 6.65-10.45 wt%, yttrium-containing compound (calculated as yttrium oxide) 0.35-0.55 wt%, silicon-containing compound (calculated as silicon oxide) 0.23-0.92 wt%, calcium-containing compound (calculated as calcium oxide) 0.05-0.2 wt%, magnesium-containing compound (calculated as magnesium oxide) 0.1-0.4 wt%, and the balance being aluminum oxide. The zirconium-containing compound and the yttrium-containing compound of the present invention are prepared by adding 3Y-ZrO2To obtain a sintered zirconia composite alumina ceramic containing 3Y-ZrO27-11 wt% of powder. When the alumina ceramic sintered body contains the components in percentage by mass, the bending strength of the prepared alumina substrate is more than 800 Mpa.
Preferably, the Al is2O3、ZrO2、Y2O3、CaO、SiO2All are high purity powders of 99.99%.
As a preferred embodiment of the alumina ceramic sintered body of the present invention, the alumina ceramic sintered body contains the following components in percentage by mass: 8.55 wt% zirconium containing compound (calculated as zirconium oxide), 0.45 wt% yttrium containing compound (calculated as yttrium oxide), 0.92 wt% silicon containing compound (calculated as silicon oxide), 0.2 wt% calcium containing compound (calculated as calcium oxide), 0.4 wt% magnesium containing compound (calculated as magnesium oxide), 89.48 wt% alumina, the best fracture toughness and flexural strength are obtained. The zirconium-containing compound and the yttrium-containing compound of the above alumina ceramic sintered body are added with 3Y-ZrO2To obtain a sintered zirconia composite alumina ceramic containing 3Y-ZrO2Powder 9.0 wt%.
As a preferable embodiment of the alumina ceramic sintered body of the present invention, when the sand grinding process is adopted, 3Y-ZrO can be ensured2The powder is more uniformly dispersed in the alumina matrix. When an external force acts, the zirconia phase change energy in the ceramic material can uniformly absorb the external energy, and microcracks are generated to avoid the failure of the material caused by the rapid concentration of stress in the loading process, so that the ceramic material has higher bending strength.
As a preferred embodiment of the alumina ceramic sintered body of the present invention, a sintered body containingZrO2And Y2O3As an additive for the toughening phase of alumina ceramics, wherein ZrO in ZTA powder2When the crystal grain sizes D50 are distributed in the range of 0.3-0.7um, the difference between D90 and D10 is 1.1-1.5 um; al (Al)2O3When the crystal grain sizes D50 are distributed in the range of 1.0-1.4um, the difference between D90 and D10 is 2.7-3.1 um; when the average grain diameter of the zirconia composite alumina ceramic crystal (ZTA crystal) is 0.9-1.3um, the bending strength of the prepared ZTA composite ceramic substrate reaches 938 MPa. The purpose of the difference control of D90 and D10 is to ensure Al2O3And ZrO2The centralization of each grain size, when the grain size is uniformly distributed, the toughening effect is strengthened. If the size dispersion is large, stress concentration is easily caused, and the material is easy to fail and break.
As a preferred embodiment of the alumina ceramic sintered body of the present invention, the zirconia composite alumina ceramic sintered body has ZrO per unit area2The area ratio of the particles is 2.2-4.3%. (note: the ratio of the area of the particles of zirconia per unit area means a value obtained by dividing the total area of zirconia present in the field of view by the total field of view area observed by SEM calculation.
More preferably, when the alumina ceramic sintered body comprises the following components in percentage by mass: 8.55 wt% of zirconium-containing compound (calculated as zirconia), 0.45 wt% of yttrium-containing compound (calculated as yttria), 0.92 wt% of silicon-containing compound (calculated as silica), 0.2 wt% of calcium-containing compound (calculated as calcia), 0.4 wt% of magnesium-containing compound (calculated as magnesia), 89.48 wt% of alumina, and the mixed powder is dispersed by sand milling; meanwhile, when the content of the aluminum oxide D50 is controlled to be 1.0-1.4um and the content of the zirconium oxide D50 is controlled to be 0.3-0.7 um; meanwhile, the ZTA composite ceramic material has the best mechanical property when the area percentage of zirconia particles in unit visual field is ensured to be 2.2-4.3%. The zirconium-containing compound and the yttrium-containing compound of the above alumina ceramic sintered body are added with 3Y-ZrO2To obtain a sintered zirconia composite alumina ceramic containing 3Y-ZrO2Powder 9.0 wt%.
The influence of the uniform distribution of the zirconium oxide on the mechanical property of the ceramic substrate is ensured to be larger. When the distribution density is too low, the zirconia is roughly filled between the grain boundaries of the alumina, and the contact area between the zirconia crystal and the grain boundary phase of the alumina is small, so that the function of absorbing external energy is limited, and the strength of the ceramic substrate is low. When the distribution density of zirconia is too high, the thermal expansion coefficients of zirconia and alumina are different, and when the contact area between the zirconia and alumina is too large, the grain boundary is easily deformed, residual stress is caused, and the strength of the ceramic material is low.
As a preferable embodiment of the alumina ceramic sintered body of the present invention, 90% or more of the number of the alumina crystal grains exhibit columnar appearance distribution, and the aspect ratio thereof is more than 3.
In a second aspect, the present invention provides an alumina substrate comprising the above zirconia composite alumina ceramic sintered body.
In a third aspect, the present invention provides a method for preparing the alumina substrate, including the following steps:
(1) the alumina powder, the zirconia powder and the yttria powder are proportioned and weighed, and the yttria powder and the zirconia powder are proportioned into 3Y-ZrO according to the molar ratio of 3:972Powder of alumina and 3Y-ZrO2Preparing 5wt% suspension of the powder and a solvent respectively, and mixing and dispersing;
(2) taking out the suspension obtained in the step (1), drying the suspension in a constant-temperature drying oven at 90 ℃, then crushing the materials, and sieving the materials by a 100-mesh sieve for later use;
(3) and adding the mixed powder into a dispersing agent, an adhesive, a plasticizer and a lubricant, carrying out ball milling and defoaming, then carrying out tape casting to obtain a green compact, placing the green compact at 1500-1600 ℃ for high-temperature sintering, and naturally cooling to room temperature along with a furnace after the sintering is finished to obtain the alumina ceramic substrate.
In a preferred embodiment of the method for producing an alumina substrate according to the present invention, in the step (1), the mixing and dispersing are performed by sand milling.
Compared with the prior art, the invention has the beneficial effects that: the zirconia-alumina composite ceramic sintered body of the present invention is formed of 3Y-ZrO2As an additive, realizes the toughening of phase change and microcrack and strong internal crystal structureThe synergistic effect of various toughening modes such as toughening and surface strengthening toughening; with CaCO3、SiO2MgO is used as a sintering aid, the sintering temperature of the alumina ceramic is reduced, the sintering rate is accelerated, and sintering densification is promoted through liquid phase sintering, and the alumina substrate prepared by the zirconia composite alumina ceramic sintered body has good fracture toughness and bending strength.
Drawings
FIG. 1 is a graph showing the dispersion of zirconia in an alumina matrix in accordance with the present invention in different dispersion processes (ball milling and sand milling) in examples 20 and 21, wherein (a) is a graph showing the dispersion of zirconia in an alumina matrix in example 20, and (b) is a graph showing the dispersion of zirconia in an alumina matrix in example 21.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a ceramic substrate after hot etching in example 25 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
(1) Effect of the amounts of the Experimental additives and flux Components of the invention on the Effect of the invention
Examples 1 to 10 and comparative example 1 were provided to examine the additive component (3Y-ZrO) in the final product of the present invention2) The mass fraction of (A) has an influence on the effect of the present invention, wherein the molar ratio of yttrium oxide to zirconium oxide is 3:97, i.e. 3Y-ZrO2. When 3Y-ZrO2When the content is determined, examples 11 to 19 and comparative example 2 are set to examine the influence of the mass fraction of the Ca-Mg-Si flux in the finished product of the invention on the effect of the invention. The mass fractions of the respective components of the composite ceramic material sintered bodies in examples 1 to 19 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
The specific preparation methods of examples 1 to 19 and comparative examples 1 to 2 include the steps of: weighing a certain amount of mixed powder according to a certain proportion, adding a dispersing agent, an adhesive, a plasticizer and a lubricant, carrying out ball milling and defoaming, then carrying out tape casting to obtain a green body, placing the green body at 1500-1600 ℃ for high-temperature sintering, naturally cooling the green body to room temperature along with a furnace after the sintering is finished, and carrying out post-processing to obtain the alumina ceramic substrate.
The fracture toughness and the flexural strength of examples 1 to 19 and comparative examples 1 to 2 were measured, respectively, and the test results are shown in Table 2. The method for testing the fracture toughness comprises the following steps: the fracture toughness of the composite material is measured by a three-point bending experiment through a unilateral notched beam method (SENB method) by adopting an electronic universal tester, and the loading rate is set to be 0.05 mm/min.
TABLE 2
As can be seen from examples 1 to 10 and comparative example 1, 3Y-ZrO was added2Can obviously improve the bending strength and the fracture toughness of the alumina-based ceramic substrate. And accompanied by 3Y-ZrO2The powder content is increased, the bending strength and the fracture toughness of the alumina ceramic substrate are firstly increased and then reduced, and the powder content is 3Y-ZrO2When the powder content is 9.0 wt%, namely the mass fraction of the zirconia is 8.55 wt%, and the mass fraction of the yttria is 0.45 wt%, the mechanical property of the ceramic substrate reaches the maximum value.
As can be seen from examples 1 to 10 and comparative example 1, when 3Y-ZrO2When the addition amount of (A) is lower, the phenomenon that the breaking and bending strength of the ceramic substrate is obviously lower occurs; when 3Y-ZrO2When the amount of (B) is too large, the fracture toughness of the ceramic substrate is also deteriorated.
Example 6 the above exampleBest results of the embodiment. Reason analysis: when 3Y-ZrO2When the content is lower, the amount of tetragonal zirconia having the phase change toughening effect is small, and the absorbed energy is limited when the tetragonal zirconia is acted by external force, so that the phase change toughening effect is poor. When 3Y-ZrO2At higher contents, on the one hand, ZrO2Uneven distribution in the alumina causes unevenness of the microstructure, thereby causing cracks inside the ZTA ceramic; on the other hand, the zirconia is distributed in the alumina in an overlapping way, the number of crystal boundaries is large, and the imbalance of the thermal expansion coefficient between the zirconia and the alumina causes poor compactness during sintering, thereby causing poor bending strength.
As can be seen from examples 11 to 19 and comparative example 2, when the content of the Ca-Mg-Si flux is changed, the bending strength and fracture toughness of the alumina ceramic substrate are significantly affected. And the bending strength and the fracture toughness of the alumina ceramic substrate are firstly increased and then reduced along with the increase of the content of Ca-Mg-Si, and the content of the Ca-Mg-Si is increased and then reduced in SiO2The mechanical properties of the ceramic substrate reach maximum values when the contents are 0.92 wt%, 0.2 wt% and 0.4 wt%.
Example 14 is the best effect of the above example. Reason analysis: the Ca-Mg-Si flux forms a molten glass phase that is distributed along the contact interface of each particle, and atoms fill the pores by liquid diffusion transport, promoting sintering densification. When the content of the Ca-Mg-Si fluxing agent is low, the molten glass phase is limited, and pores cannot be completely filled, so that the sintering is not compact enough. When the content of the Ca-Mg-Si flux is high, the excessive flux glass phase serves as an impurity component and is randomly distributed among alumina grain boundaries, so that adjacent alumina grains cannot be tightly combined, and the bending strength of the ceramic substrate is reduced.
In examples 5 to 7 and 11 to 16, when the ceramic sintered body includes the following components by mass percent: when the weight of the zirconium-containing compound (calculated by the form of zirconium oxide) is 6.65-10.45 wt%, the weight of the yttrium-containing compound (calculated by the form of yttrium oxide) is 0.35-0.55 wt%, the weight of the silicon-containing compound (calculated by the form of silicon oxide) is 0.23-0.92 wt%, the weight of the calcium-containing compound (calculated by the form of calcium oxide) is 0.05-0.2 wt%, the weight of the magnesium-containing compound (calculated by the form of magnesium oxide) is 0.1-0.4 wt%, and the balance is aluminum oxide, the bending strength of the prepared aluminum oxide substrate is more than 800 MPa.
When the alumina ceramic sintered body comprises the following components in percentage by mass: the ZTA composite ceramic substrate had the best fracture toughness (6.78MPa · m) with 8.55 wt% zirconium-containing compound (calculated as zirconia), 0.45 wt% yttrium-containing compound (calculated as yttria), 0.92 wt% silicon-containing compound (calculated as silica), 0.2 wt% calcium-containing compound (calculated as calcia), 0.4 wt% magnesium-containing compound (calculated as magnesia), and 89.48 wt% alumina1/2) And a flexural strength (916 MPa).
(2) Different ZrO of the invention2Influence of the Dispersion Process on the Effect of the invention
Examples 20 to 21 were provided to examine ZrO in the finished product of the present invention2The effect of the dispersion process of (2) on the present invention. The dispersion process of examples 20 to 21 is shown in Table 3.
TABLE 3
The preparation method of the embodiment 20-21 comprises the following steps:
1) weighing a certain amount of alumina powder (processed and added with a certain amount of silicon-containing compound and calcium-containing compound as sintering aids) and a certain amount of 3Y-ZrO according to the mixture ratio2(i.e., wherein Y is2O3And ZrO2The molar ratio of the alumina powder to the zirconia powder is 3:97), the alumina powder and the zirconia powder are respectively prepared into 5wt% suspension with a solvent, and the suspension is added into a planetary ball mill or a basket type sand mill for rotary mixing. Wherein the volume ratio of the powder material to the corundum balls to the solvent is 2:4: 7; the ball milling dispersion adopts a planetary ball mill, the sand mill adopts a basket type sand mill, the diameter of the corundum ball is at least one of phi 5 and phi 10, the ball-to-material ratio is controlled to be 3.5, the rotating speed of the ball mill is 1000r/min, the ball milling time is 36 hours, the solvent is one of isopropanol and toluene, and after the ball milling is finished, the suspension is taken out. Drying at 90 deg.C in constant temperature drying oven, pulverizing, and sieving with 100 mesh sieve；
2) And adding the mixed powder into a dispersing agent, an adhesive, a plasticizer and a lubricant, carrying out ball milling and defoaming, then carrying out tape casting to obtain a green compact, placing the green compact at 1500-1600 ℃ for high-temperature sintering, and naturally cooling to room temperature along with a furnace after the sintering is finished to obtain the alumina ceramic substrate.
The fracture toughness and the flexural strength of examples 20 to 21 were measured, and the results are shown in Table 3. In examples 20 to 21, the dispersion of zirconia in the alumina matrix is shown in FIG. 1, wherein (a) is the dispersion of zirconia in the alumina matrix in example 20, and (b) is the dispersion of zirconia in the alumina matrix in example 21. As shown in FIG. 1, it was found by SEM that ZrO obtained in the same field of view was obtained by the sand grinding process2More crystal grains and more uniform dispersion, and the mechanical property of the ceramic substrate is better under the sand grinding process obtained by the three-point bending test by adopting an electronic universal testing machine.
(3) Effect of average particle diameters of zirconia and alumina of the present invention on the Effect of the present invention
The inventors tried a lot of experiments, and found that the average particle size of zirconia and alumina during ball milling has a certain influence on the bending strength and fracture toughness of the ZTA composite ceramic substrate. Examples 22 to 27 and comparative example 3 were selected to observe the influence of the average particle size of zirconia on the effect of the present invention. The average particle diameters of the zirconia in examples 22 to 27 and comparative example 3 are shown in Table 4.
TABLE 4
Meanwhile, the alumina ceramic substrates prepared in examples 22 to 27 and comparative example 3 were subjected to performance tests, and the test results are shown in table 5.
TABLE 5
| Fracture toughness (MPa. m)1/2) | Flexural Strength (MPa) | |
| Example 22 | 5.21 | 654 |
| Example 23 | 5.68 | 645 |
| Example 24 | 6.29 | 931 |
| Example 25 | 6.50 | 938 |
| Example 26 | 6.26 | 893 |
| Example 27 | 5.54 | 698 |
| Comparative example 3 | 4.97 | 684 |
From examples 22 to 27 and comparative example 3, it can be seen that ZrO2And Al2O3The average grain size of (A) has a certain influence on the toughness and strength of the alumina ceramic substrate when ZrO2When the crystal grain sizes D50 are distributed in the range of 0.3-0.7um, the difference between D90 and D10 is 1.1-1.5 um; al (aluminum)2O3When the crystal grain sizes D50 are distributed in the range of 1.0-1.4um, the difference between D90 and D10 is 2.7-3.1 um; ZTA has an average particle size of 0.9-1.3 um; the method has obvious reinforcing effect on the fracture toughness and the bending strength of the alumina ceramic substrate. If the particle diameter falls outside the above range, the ceramic substrate is not significantly toughened.
Al2O3The crystal particle size D50 is distributed in 1.0-1.4um, when the particle size is larger, the intrinsic particle size of the particles is larger, the surface area is larger, and the ratio change is small, so the surface energy of the alumina particles is smaller and the alumina particles are relatively more inactive. Under the condition of the same flux, the sintering temperature is required to be higher. In addition, the ceramic chip is accumulated with large particles, and crystal grains grow up during sintering, so that the ceramic strength is reduced because the ceramic chip particles are not densely accumulated and corresponding air holes, gaps and cracks are increased.
When the particles are biased downward, the grain boundaries increase, which is detrimental to the transfer of heat between the alumina grains. When the particles are smaller, the accumulation is relatively more compact, the porosity is reduced, the thermal stress cannot be released, and the thermal shock resistance of the product is insufficient. Thus Al according to the invention2O3The crystal grain size D50 is distributed in 1.0-1.4um, and the strength and the heat conduction efficiency can be considered at the same time.
ZrO2The grain size D50 of the crystal is distributed in 0.3-0.7um, and the grain size of the zirconia crystal is controlled in 0.3-0.7um, so that the zirconia crystal can be fully wrapped by the alumina crystal during firing, and the toughening effect is triggered. Therefore, if the zirconia particle size is too large, the effect is not good.
When the particle size of zirconia is smaller, on one hand, the difficulty of uniform dispersion is higher, on the other hand, the particle size is smaller, the molecules are smaller and active, and the same zirconia particles absorb smaller external energy, so that the effect is poor.
Meanwhile, when the porcelain sample in example 25 is observed by a Scanning Electron Microscope (SEM) image, as shown in fig. 2, it can be clearly observed that alumina grains present a columnar appearance distribution and an aspect ratio greater than 3, zirconia (white particles in SEM, here, backscattered electron signals, because the atomic number contrast is white) is filled between alumina grain boundaries and alumina D50 is 1.5-2.0 um; zirconia D50 was 0.6-0.9um, and ZTA average particle size was 1.0-1.5um, as shown in Table 6.
TABLE 6
(4) Influence of the area of the zirconia of the present invention in alumina on the effect of the present invention
The inventors tried a lot of experiments and found that the area occupation ratio of zirconia in the alumina matrix has a certain influence on the bending strength and fracture toughness of the ZTA composite ceramic substrate. Examples 28 to 33 and comparative example 4 were selected to observe the effect of the average particle size of zirconia on the effect of the present invention. The area ratio of zirconia in examples 28 to 33 and comparative example 4 is shown in Table 7. When ZrO2When the area ratio of the zirconia grains in the alumina is 2.2-4.3%, the zirconia grains are uniformly dispersed and are not stacked, otherwise, the zirconia grains are locally excessive to play the role of impurities, thereby affecting the mechanical property of the ceramic material. ZrO of the invention2When the area ratio of the aluminum oxide is 2.2-4.3%, the aluminum oxide ceramic substrate obviously enhances the fracture toughness and the bending strength of the aluminum oxide ceramic substrate.
The area ratio test method comprises the following steps: the area fraction was roughly estimated by observing the backscattered electron image of a scanning electron microscope (contrast difference due to difference in atomic number) using analysis software. In combination with the mechanical property test results, the zirconia area fraction was found to be 2.2 to 4.3% in the preferred embodiment.
TABLE 7
| ZrO2Area ratio of | Fracture toughness (MPa. m)1/2) | Flexural Strength (MPa) | |
| Example 28 | 1.2 | 5.47 | 624 |
| Example 29 | 2.2 | 6.41 | 901 |
| Example 30 | 3.1 | 6.43 | 956 |
| Example 31 | 4.3 | 6.27 | 925 |
| Example 32 | 5.2 | 5.93 | 843 |
| Example 33 | 6.0 | 5.21 | 752 |
| Comparative example 4 | 0 | 3.78 | 381 |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The zirconia-alumina composite ceramic sintered body is characterized by comprising the following components in percentage by mass: a zirconium-containing compound in an amount of 6.65 to 13.3 wt% in terms of zirconia, an yttrium-containing compound in an amount of 0.35 to 0.7 wt% in terms of yttria, a silicon-containing compound in an amount of 0.16 to 2.76 wt% in terms of silica, a calcium-containing compound in an amount of 0.035 to 0.6 wt% in terms of calcia, a magnesium-containing compound in an amount of 0.07 to 1.2 wt% in terms of magnesia, and the balance being alumina;
wherein, in the zirconia composite alumina ceramic sintered body, the area ratio of the zirconium compound crystal particles in a unit area is 2.2-4.3%.
2. The zirconia composite alumina ceramic sintered body according to claim 1, wherein the ceramic sintered body contains the following components in percentage by mass: 6.65-10.45 wt% of zirconium-containing compound calculated in the form of zirconium oxide, 0.35-0.55 wt% of yttrium-containing compound calculated in the form of yttrium oxide, 0.23-0.92 wt% of silicon-containing compound calculated in the form of silicon oxide, 0.05-0.2 wt% of calcium-containing compound calculated in the form of calcium oxide, 0.1-0.4 wt% of magnesium-containing compound calculated in the form of magnesium oxide, and the balance of aluminum oxide.
3. The zirconia composite alumina ceramic sintered body according to claim 1, wherein the average particle diameter D50 of the zirconia composite alumina ceramic crystal is 0.9 to 1.3um, the average particle diameter D50 of the alumina crystal is 1.0 to 1.4um, and the average particle diameter D50 of the zirconia crystal is 0.3 to 0.7 um.
4. The zirconia composite alumina ceramic sintered body according to claim 3, wherein the difference between the alumina crystal particle diameters D90 and D10 is 2.7 to 3.1um, and the difference between the zirconia crystal particle diameters D90 and D10 is 1.1 to 1.5 um.
5. The zirconia composite alumina ceramic sintered body according to claim 1, wherein 90% or more of the number of alumina crystal grains exhibit columnar appearance distribution and an aspect ratio thereof is more than 3.
6. An alumina substrate comprising the zirconia composite alumina ceramic sintered body according to any one of claims 1 to 5.
7. The method for preparing the alumina substrate according to claim 6, comprising the steps of:
(1) weighing alumina powder, zirconia powder and yttria powder in a ratio of 3 to 97, and mixing the yttria powder and the zirconia powder into 3Y-ZrO2Powdering, and mixing alumina and 3Y-ZrO2Preparing 5wt% suspension of the powder and a solvent respectively, and mixing and dispersing;
(2) taking out the suspension obtained in the step (1), drying the suspension in a constant-temperature drying oven at 90 ℃, then crushing the material, and sieving the crushed material through a 100-mesh sieve for later use;
(3) and adding a dispersant, an adhesive, a plasticizer and a lubricant into the sieved mixed powder for later use, carrying out ball milling, defoaming and then carrying out tape casting to obtain a green body, placing the green body at 1500-1600 ℃ for high-temperature sintering, and naturally cooling the green body to room temperature along with the furnace after the sintering is finished to obtain the alumina ceramic substrate.
8. The method for producing an alumina substrate according to claim 7, wherein in the step (1), the mixing dispersion is performed by sand-milling dispersion.
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