CN117602931A - Metal oxide modified multilayer oxide ceramic and preparation method and application thereof - Google Patents
Metal oxide modified multilayer oxide ceramic and preparation method and application thereof Download PDFInfo
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- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 112
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 112
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 126
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 66
- 238000004040 coloring Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 26
- 230000000052 comparative effect Effects 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 14
- 238000007792 addition Methods 0.000 claims description 11
- 150000002601 lanthanoid compounds Chemical class 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims 7
- 239000002184 metal Substances 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 206010017472 Fumbling Diseases 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 104
- 239000000919 ceramic Substances 0.000 description 36
- 230000008569 process Effects 0.000 description 15
- 238000005452 bending Methods 0.000 description 14
- 229910052747 lanthanoid Inorganic materials 0.000 description 12
- 150000002602 lanthanoids Chemical class 0.000 description 12
- 239000004014 plasticizer Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000002457 bidirectional effect Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000588731 Hafnia Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 210000004195 gingiva Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- -1 zirconium ions Chemical class 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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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
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Abstract
The invention relates to a metal oxide modified multilayer oxide ceramic, a preparation method and application thereof, which are based on Y in oxide powder of raw materials of each layer 2 O 3 The total weight proportion of the lanthanide oxide and other coloring element oxides is that at least one layer of oxide powder is selected to be added with Al 2 O 3 Mixing uniformly to obtain the selected nth layer and Y in two adjacent layers 2 O 3 The layer with the smallest weight proportion is a contrast layer, and is expressed by the formula m (Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 ) +b.DELTA.m (La) -c.DELTA.m (O), a of 0.01 to 0.05, b of 0.02 to 0.1, cThe addition amount of the alumina in each layer of powder can be rapidly determined and added according to the calculation result, the prepared multilayer oxide ceramic is not easy to deform after being presintered, and experimental fumbling time and cost are greatly saved.
Description
Technical Field
The invention relates to the technical field of multilayer oxide ceramic bodies, in particular to metal oxide modified multilayer oxide ceramic, a preparation method and application thereof.
Background
The preparation of oxide ceramics for dental restorations generally involves compression molding of oxide powders and high temperature presintering, the presintered oxide ceramics being machined by CAD/CAM processes to obtain the desired shape of the dental restoration, and secondary sintering to obtain the dental restoration. In which zirconia based on Tetragonal Zirconia Polycrystalline (TZP) form is a common raw material for preparing oxide ceramics, however pure zirconia undergoes tetragonal phase to monoclinic phase transformation at a temperature below 950 ℃ with a considerable volume increase, in order to suppress the tetragonal phase to monoclinic phase transformation, it is generally necessary to use a stabilizer such as Y 2 O 3 、CeO 2 MgO or CaO, which inhibit the transformation of zirconia from tetragonal to monoclinic phase, so that the zirconia maintains its tetragonal form, either completely or partially, and forms metastable states. Among them, yttria-stabilized zirconia powder is currently the most favored dental restorative material by virtue of its good biocompatibility, excellent corrosion resistance and wear resistance, stable chemical properties and other biomechanical properties.
As consumers better pursue the same graded-appearance aesthetic effect as their teeth, multi-layered oxide ceramics have been developed and widely studied and used. The multilayer oxide ceramic is prepared by using multiple layers containing stabilizers such as Y with different mass fractions 2 O 3 The gradual change of the transparency of the zirconia powder is controlled, the color of the zirconia powder is controlled by adopting metal ion oxides such as Fe, mn, co and the like or oxides of lanthanoids such as Ce, pr, er and the like, and the performances such as the transparency, the color and the like are combined through experimental debugging so as to achieve the aesthetic effect of gradual change of the transparency and the color and the like as those of natural teeth. A dental zirconia restorative material, a method for preparing the same and use thereof, as in patent CN114671684A, wherein a multi-layered zirconia material is prepared by using different raw materials and colorants for the gingival and dental parts, respectively, wherein the raw materials for the gingival part comprise Er 2 O 3 Stabilized zirconia powder and Y 2 O 3 Stabilized zirconia powder with Er 2 O 3 The stabilized zirconia powder is mainly used, and the raw material for dental portion comprises Y 2 O 3 Stabilized zirconia powder and Er 2 O 3 Stabilizing zirconia powder with Y 2 O 3 The stable zirconia powder is mainly used for solving the problems that the existing part of gingiva is missing, can not be well matched and is not attractive as a whole, but has high selection requirement on raw materials and is difficult to be universally applicable, and the multi-layer zirconia ceramic material has different performance requirements on transparency, color and the like of each layer, so that Y in each layer of powder 2 O 3 The weight ratio of the oxide of the lanthanide and the weight ratio of the oxide of other coloring elements are different, so that the multilayer oxide ceramic after sintering is easy to bend and deform due to inconsistent thermal compact sintering shrinkage performance of each layer, and the yield of finished products is lower.
At present, in order to solve the problem of deformation of the multilayer oxide ceramic after sintering, sintering modifiers such as La are usually added into different layers of powder 2 O 3 、Er 2 O 3 However, it is often time-consuming and laborious to determine the appropriate amount of sintering modifier to be added based on experience or extensive experimentation. Although CN 109937140A has a uniform sintering behavior, it is a multilayer oxide ceramic body with a colorant and a dopant La 2 O 3 Treating the zirconia powder to cause at least one of the layers to contain La 2 O 3 And at least two ofAt its La are different layers 2 O 3 The content varies and La in each layer is disclosed 2 O 3 The weight ratio calculation formula of (2):
m(La 2 O 3 )＝m min (La 2 O 3 )+(m max (Y 2 O 3 )-m(Y 2 O 3 ))*f；
however, the patent does not consider the influence of lanthanide compounds and other coloring element oxides in the raw materials, and the adding types and adding amounts of the stabilizers in zirconia powder of different manufacturers or models are different, even very different. However, it is not clear yet that other sintering modifier additions and Y in the raw materials 2 O 3 The relation between the two components still needs a great deal of experiments to find out the proper adding amount, which is time-consuming and labor-consuming.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a metal oxide modified multi-layer oxide ceramic, a preparation method and application thereof, and aims to select at least one layer of powder to be added with metal oxide for sintering modification so as to select Y in the two adjacent layers of powder 2 O 3 The layer with the smallest weight proportion is a comparison layer, and the following relation is found: m (Al) 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 ) +b.DELTA.m (La) -c.DELTA.m (O), wherein a has a value of 0.01 to 0.05, b has a value of 0.02 to 0.1, and c has a value of 0.01 to 0.04, and Al is added as a result of the calculation 2 O 3 The compact sintering of each layer can keep more consistent shrinkage performance, and the deformation of the multi-layer oxide ceramic after pre-sintering is avoided, so that the technical problems that the adding amount of the metal oxide of the existing sintering modifier needs a large amount of experimental groping and determination, and time and labor are wasted are solved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a metal oxide modified multi-layered oxide ceramic, comprising the steps of:
(1) Determination of Y in the raw oxide powder of each layer 2 O 3 Oxide of lanthanoid elementAnd the total weight proportion of other coloring element oxides;
at least one layer of oxide powder is selected to be added with Al 2 O 3 Mixing uniformly to obtain the selected nth layer and Y in two adjacent layers 2 O 3 The layer with the smallest weight proportion is a contrast layer, n is a positive integer and n is more than 1; the Al is 2 O 3 The addition amount in the selected nth layer powder is calculated according to the following formula:
m(Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 )+b*Δm(La)-c*Δm(O)；
wherein: the value of a is 0.01-0.05, the value of b is 0.02-0.1, and the value of c is 0.01-0.04;
m min (Al 2 O 3 ) Is selected from the powder of the layer and the contrast layer of Al 2 O 3 Is a minimum weight ratio of (2);
Δm(Y 2 O 3 ) Is selected from Y in the powder of the layer and the contrast layer 2 O 3 Difference in weight ratio;
Δm (La) is the difference between the total weight ratio of lanthanide compounds in the selected layer and comparative layer powders;
Δm (O) is the difference between the total weight ratio of the selected layer and the oxides of other coloring elements in the powder of the contrast layer;
(2) Sequentially spreading oxide powder in a die according to a hierarchical sequence to form an oxide ceramic powder layer, compressing and molding to obtain a green body, and presintering the green body to obtain the multilayer oxide ceramic body.
Preferably, the metal oxide modified multilayer oxide ceramic has a value of a ranging from 0.02 to 0.04, b ranging from 0.02 to 0.06, and c ranging from 0.01 to 0.03.
Preferably, the metal oxide modified multilayer oxide ceramic is prepared by a value range of 0.03-0.04, b value range of 0.04-0.05 and c value range of 0.015-0.025.
Preferably, the method for preparing the metal oxide modified multi-layer oxide ceramicThe Al of 2 O 3 When being partially or completely replaced by MgO, according to MgO and Al 2 O 3 Is replaced and added in a weight ratio of 2:1.
Preferably, the method for preparing the metal oxide modified multi-layer oxide ceramic, wherein in the step (2), the compression molding comprises one or more of dry press molding and cold isostatic molding; wherein the dry-pressing forming pressure is 20-150MPa, the dwell time is 30-120 seconds, the cold isostatic pressing pressure is 150-350MPa, and the dwell time is 30-300 seconds.
Preferably, the preparation method of the metal oxide modified multilayer oxide ceramic has the pre-sintering temperature of 950-1150 ℃ and the heat preservation time of more than or equal to 1h.
Preferably, the preparation method of the metal oxide modified multilayer oxide ceramic comprises the steps that the raw material oxide powder is selected from Y 2 O 3 Oxide powder with doping amount of 0-26%, preferably Y 2 O 3 The doping amount of (2) is 5-11%.
According to another aspect of the present invention, there is also provided a metal oxide modified multi-layered oxide ceramic body prepared according to the preparation method of the present invention.
Preferably, the metal oxide modified multilayer oxide ceramic body, the multilayer oxide ceramic body thereof, comprises at least two different layers, at least one of which is doped with Al 2 O 3 And/or MgO; and Al in at least two layers 2 O 3 Or a different MgO content, wherein at least one layer contains 0 to 10% by weight of Al 2 O 3 。
According to another aspect of the present invention there is also provided the use of a metal oxide modified multi-layer oxide ceramic body according to the present invention for the preparation of a dental restoration.
In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:
the invention provides a preparation method of a multilayer oxide ceramic, which uses Y in an nth layer and two adjacent layers thereof 2 O 3 The layer with the smallest weight proportion is a contrast layer and can be based on Y in the powder of the selection layer and the contrast layer 2 O 3 The total weight ratio of lanthanide oxide and other coloring element oxide is calculated according to the formula m (Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 ) +b.DELTA.m (La) -c.DELTA.m (O), wherein a has a value of 0.01 to 0.05, b has a value of 0.02 to 0.1, and c has a value of 0.01 to 0.04, the addition amount of alumina in the selected layer powder is calculated and determined, and alumina is added according to the calculation result, the prepared multilayer oxide ceramic is not easy to deform after being presintered, and the strength and the color stability of the multilayer oxide ceramic can be improved.
The multilayer oxide ceramic prepared by the preparation method provided by the invention is mechanically processed by using a CAD/CAM process to obtain the shape required by the dental restoration, is not easy to deform after secondary sintering, and can be applied to preparation of the dental restoration.
Drawings
FIG. 1 is a schematic view of the multilayer oxide ceramic after pre-sintering in example 1, wherein A is an overview of the multilayer oxide ceramic after pre-sintering, B is a detailed view of the multilayer oxide ceramic after pre-sintering, and C is a detailed view of the multilayer oxide ceramic after secondary sintering;
FIG. 2 is a schematic view of the multilayer oxide ceramic after pre-sintering in comparative example 1, wherein A is an overview of the multilayer oxide ceramic after pre-sintering, and B is a detailed view of the multilayer oxide ceramic after pre-sintering;
FIG. 3 is a schematic view of the pre-sintered multilayer oxide ceramic of example 2, wherein A is an overview of the pre-sintered multilayer oxide ceramic, and B is a detailed view of the pre-sintered multilayer oxide ceramic;
FIG. 4 is a schematic view of the pre-sintered multilayer oxide ceramic of comparative example 2, wherein A is an overview of the pre-sintered multilayer oxide ceramic, and B is a detailed view of the pre-sintered multilayer oxide ceramic;
FIG. 5 is a schematic view of the pre-sintered multilayer oxide ceramic in example 3, wherein A is an overview of the pre-sintered multilayer oxide ceramic, and B is a detailed view of the pre-sintered multilayer oxide ceramic;
FIG. 6 is a schematic view of the pre-sintered multilayer oxide ceramic of comparative example 3, wherein A is an overview of the pre-sintered multilayer oxide ceramic, and B is a detailed view of the pre-sintered multilayer oxide ceramic.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific implementation, structure, characteristics and effects according to the present invention with reference to the accompanying drawings and preferred embodiments.
The invention considers the influence of lanthanide compounds and other coloring element oxides in oxide ceramic raw material powder on the bending deformation of a sintered multilayer oxide ceramic block, and uses Y 2 O 3 The stable zirconia powder was used as a raw material, and found through extensive experiments that when the selected layer was the nth layer (n>1) Y in the two adjacent layers of the selection layer 2 O 3 The layer with the smallest weight proportion is a contrast layer, and the powder of the selected layer is Al 2 O 3 The weight ratio of the added amount to the yttrium oxide, the lanthanide and other coloring element oxides in the raw material powder in the layer and the contrast layer satisfies the following relation:
m(Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 ) +b Δm (La) -c Δm (O); wherein Δm (Y) 2 O 3 ) Is selected from Y in the layer and the contrast layer 2 O 3 Difference in weight ratio; Δm (La) is the difference in the total weight ratio of lanthanide compounds in the selected layer to that in the control layer; Δm (O) is the difference in the total weight ratio of the selected layer to the other coloring element oxides in the comparative layer.
Through the summary analysis of a large number of experimental results, the value range of a is found to be 0.10-0.05, the value range of b is found to be 0.02-0.1, and Al is calculated according to the formula 2 O 3 The addition of the amount of the ceramic powder can ensure that compact sintering of each layer keeps consistent shrinkage performance and avoids deformation of the multilayer oxide ceramic after presintering; in particular, the value of a is 0.02-0.04, the value of b is 0.02-0.06, and the oxide ceramic is sinteredThe shrinkage of different layers in the process is most matched, the obtained multi-layer oxide ceramic has good sintering behavior consistency, and the pre-sintering and even secondary sintering do not deform.
Further, it was found that MgO was used instead of Al 2 O 3 When according to the invention Al 2 O 3 Calculation of the addition amount of MgO and Al 2 O 3 Completely or partially replacing Al with a weight ratio of 2:1 2 O 3 The obtained multilayer oxide ceramic has good sintering behavior consistency and does not deform after presintering.
Based on this, the present invention provides a method for preparing a metal oxide modified multi-layered oxide ceramic, comprising the steps of:
(1) Determination of Y in the raw oxide powder of each layer 2 O 3 Weight ratio, lanthanide oxide weight ratio, and other coloring element oxide weight ratio; the lanthanide oxides include oxides of one or more lanthanides as in Ce, pr, nd, er, tb, la, sm, eu, tm, yb, the weight ratio of which refers to the total weight ratio of all lanthanide compounds in the layer of powder;
the other coloring element oxides are coloring element oxides except zirconium oxide, hafnium oxide, yttrium oxide, aluminum oxide and lanthanide element oxides in the corresponding powder layer, and comprise one or more coloring element oxides of Fe, mn and Co, wherein the weight proportion of the coloring element oxides refers to the total weight proportion of all the other coloring element oxides in the powder layer;
at least one layer of oxide powder is selected to be added with Al 2 O 3 Mixing uniformly, and making Al in at least two different layers 2 O 3 Is different in content;
(2) Sequentially spreading oxide powder in a die according to a hierarchical sequence to form an oxide ceramic powder layer, compressing and forming to obtain a green body, and presintering the green body to obtain a presintered multilayer oxide ceramic body.
The Al in step (1) 2 O 3 The addition amount of the selected n-th layer (n is a positive integer and n is more than 1) is calculated according to the following formula:
m(Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 )+b*Δm(La)-c*Δm(O)；
wherein, the value range of a is 0.01 to 0.05, the value range of b is 0.02 to 0.1, and the value range of c is 0.01 to 0.04; y is Y 2 O 3 La, O respectively represent Y 2 O 3 Lanthanide compounds, other coloring element oxides.
m(Al 2 O 3 ) Is the nth layer to be added with Al 2 O 3 N is a positive integer and > 1, to select Y in the layer and two adjacent layers 2 O 3 The layer with the smallest weight proportion is a contrast layer;
m min (Al 2 O 3 ) Is selected from Al in the layer and the contrast layer 2 O 3 Is a minimum weight ratio of (2);
Δm(Y 2 O 3 ) Is selected from Y in the layer and the contrast layer 2 O 3 The difference in weight proportions, i.e. m (Y 2 O 3 ) Nth layer －m(Y 2 O 3 ) Contrast layer ；
Δm (La) is the difference in the total weight ratio of the lanthanide compounds in the selected layer to that in the comparative layer, i.e., m (La) Nth layer －m(La) Contrast layer ；
Δm (O) is the difference between the total weight ratio of the selected layer to the other coloring element oxides in the comparative layer, i.e., m (O) Nth layer －m(O) Contrast layer 。
In some implementations, the selected layer is the nth layer, n is a positive integer and n > 1, Y in two layers adjacent to the nth layer 2 O 3 The n-1 layer with smaller weight proportion is used as a comparison layer, namely, the comparison layer is calculated as follows:
m n (Al 2 O 3 )＝m n-1 (Al 2 O 3 )+a*[m n (Y 2 O 3 )-m n-1 (Y 2 O 3 )]+b*[m n (La)-m n-
1 (La)]-c*[m n (O)-m n-1 (O)]。
the lanthanide oxide refers to the total weight proportion of all lanthanide compounds in the powder layer, including oxides of lanthanoids such as Ce, pr, nd, er, tb, la, sm, eu, tm, yb.
The other coloring element oxides refer to the total weight proportion of the coloring element oxides except zirconium oxide, hafnium oxide, yttrium oxide, aluminum oxide and lanthanide element oxides in the selected layer, and include one or more coloring element oxides such as Fe, mn, co and the like.
As the content of yttrium oxide in the powder increases, the sintering activity generally decreases, and Al added in the invention 2 O 3 Because the ionic radius is smaller than that of zirconium ions (the ionic radius difference is more than 12%) and cannot be stabilized in crystal lattices, the added alumina is generally positioned at the crystal boundary of the zirconium oxide, can play a role in pinning, can inhibit abnormal growth of the zirconium oxide crystal in the sintering process, and can improve the conversion between interface energy and crystal boundary energy, thereby accelerating the sintering rate and playing a role of a sintering aid. Adding Al into the selected powder of each layer according to the calculation result of the formula 2 O 3 The shrinkage of different layers in the sintering process can be matched, so that the pre-sintered multilayer oxide ceramic is not easy to bend and deform.
Preferably, the value range of a is 0.02-0.04, the value range of b is 0.02-0.06, the value range of c is 0.01-0.03, and the shrinkage of the oxide ceramic between different layers in the sintering process can be most matched by adding according to the calculation result, so that the obtained multi-layer oxide ceramic has good sintering behavior consistency, and the pre-sintering and even secondary sintering cannot be bent and deformed.
More preferably, the value of a is in the range of 0.03-0.04, the value of b is in the range of 0.04-0.05, and the value of c is in the range of 0.015-0.025; in some embodiments a ranges from 0.035 to 0.037, b ranges from 0.043 to 0.045, and c ranges from 0.017 to 0.020.
Due to densification and grain refinement mechanism of MgO in oxide ceramic sintering and Al 2 O 3 Similarly, al is added to the oxide powder in the present invention 2 O 3 May be partially or completely replaced by MgO, preferably Al 2 O 3 Can be mixed with Al by MgO 2 O 3 Is replaced by a mass ratio of 2:1.
The oxide powder raw material in the invention has a doping amount of 0-26% (in mass percent), preferably a doping amount of 0-18%, more preferably a doping amount of 5-11%, and in some embodiments has a yttria content of 4-9.5% in yttria-stabilized zirconia powder; the powder used in each layer of the multilayer oxide ceramic can be oxide powder doped with yttrium oxide with the same content, or oxide powder doped with yttrium oxide with different contents.
The raw material for producing the multilayer oxide ceramic body in the present invention is preferably zirconia powder, more preferably yttria-stabilized zirconia powder, and in nature, the zirconium element has a chemical property similar to that of hafnium element, and the content of hafnium in the zirconium ore is generally 2 to 3% by mass, but the zirconia raw material obtained without special purification generally contains 0.5 to 2% by mass of hafnium oxide (HfO 2 ) And extracting high purity zirconia is difficult and economical. The multilayer oxide ceramic based on zirconium oxide thus prepared in the invention is preferably prepared in the form of ZrO 2 、Y 2 O 3 And HfO 2 Zirconia powder with the total amount of 98.0 percent is taken as a raw material, wherein ZrO 2 The content of (2) is 85.0% -95.0%, Y 2 O 3 The content of (2) is 5.0% -10.0%, hfO 2 The content of (2) is 0-2.0%.
Further, the compression molding in step (2) comprises one or more of dry press molding, cold isostatic molding, and in some embodiments, dry press molding and cold isostatic molding, wherein the dry press molding pressure is 20-150MPa, the dwell time is 30-120 seconds, the cold isostatic molding pressure is 150-350MPa, and the dwell time is 30-300 seconds;
the presintering temperature is 950-1150 ℃, the heat preservation time is more than or equal to 1h, and the presintering temperature is 1000-1100 ℃ preferably.
If the prepared ceramic body is thicker, a small amount of organic plasticizer can be added into the oxide ceramic powder in the step (1), so that the powder plasticity is enhanced, the better molding in the step (2) is facilitated, and the green body with the ideal shape is obtained. The organic plasticizer is added separately after the oxide ceramic powder composition is determined. The oxide ceramic powder added with a small amount of organic plasticizer (rubber powder) can be added in a single step before presintering to remove the organic plasticizer in the green body, and a proper rubber discharging temperature is selected according to the cracking temperature corresponding to the added organic plasticizer, and in some embodiments, the rubber discharging temperature is 350-800 ℃, and the rubber discharging can also be carried out simultaneously in the presintering process.
The pre-sintered multi-layered oxide ceramic blank of the present invention is machined using CAD/CAM process to obtain the desired shape of the dental restoration such as the shape of a fixed partial denture, bridge, implant bridge, multi-unit frame, abutment, crown, partial crown, veneer, inlay, etc. to be implanted during the dental restoration process, and is subjected to secondary sintering to obtain the dental restoration.
In addition, the multilayer oxide ceramic suitable for the invention also comprises oxide ceramic types taking alumina as a main crystal phase, such as ceramic powder of alumina (ZTA) toughened by zirconia, wherein the weight proportion of lanthanoid, other coloring element oxides and yttrium oxide in the ZTA ceramic powder is determined by the deformation formula of the relational expression in the invention, and the multilayer oxide ceramic is prepared according to the preparation method and is not repeated herein.
In addition, the invention also provides a metal oxide modified multilayer oxide ceramic body, which is prepared by the preparation method.
The multilayer oxide ceramic body comprises at least two different layers, at least one of which is doped with Al 2 O 3 And Al in at least two layers 2 O 3 Is different in content.
The multilayer oxide ceramic body has at least one layer containing 0 to 10% by weight of Al 2 O 3 Preferably Al 2 O 3 The weight ratio of (C) is 0.01-1%, more preferably Al 2 O 3 The weight ratio of (2) is 0.01-0.8%; in some embodiments Al 2 O 3 The weight ratio of (2) is 0.02-0.25%.
In addition, the invention also provides application of the metal oxide modified multilayer oxide ceramic body in preparing dental restorations.
The following are examples
Y in the following examples 2 O 3 The stabilized zirconia powders were all purchased from Shandong national porcelain materials Inc.
In the examples, the Y in the raw material oxide powder of each layer is measured first 2 O 3 Total weight proportion of lanthanide oxide (abbreviated La) and other coloring element oxide (abbreviated O); at least one layer of oxide powder is selected to be added with Al 2 O 3 Uniformly mixing, namely, recording the selected layer as an nth layer, wherein n is a positive integer and is more than 1, and Y is contained in two layers adjacent to the nth layer 2 O 3 The n-1 layer is the comparison layer with smaller weight ratio.
Example 1
By doping Al 2 O 3 The double-layer green body made of zirconia ceramic powder with different yttria contents is not deformed in the sintering process, and the method concretely comprises the following steps:
two kinds of zirconia ceramic powder are adopted, alumina is added in the second layer, and the naming sequence of the powder layers is Y 2 O 3 The weight ratio is in positive order. Wherein the weight proportion of oxide powder components of each layer and Al 2 O 3 The doping amounts are listed in table 1 below.
TABLE 1 weight ratio of oxide powder components of each layer and Al 2 O 3 Doping amount
Al in the table 2 O 3 The doping amount is the weight ratio of the powder directly added into the layer, and is not counted into the powder
The weight ratio of the components is the same as the following; the lanthanide oxide refers to the total weight proportion of all lanthanide compounds in the powder, including oxides of lanthanoids such as Ce, pr, nd, er, tb, la, sm, eu, tm, yb, as follows; the other coloring element oxides are selected from the coloring element oxides other than zirconia, hafnia, yttria, alumina, lanthanoid oxides, such as one or more of Fe, mn, co, etc., in the layer, as follows.
Wherein a is 0.036, b is 0.044, c is 0.018, al 2 O 3 The doping amount is calculated in detail by the formula:
m(Al 2 O 3 )＝0+0.036*(9.7-5.6)+0.044*(0.37-0.08)-0.018*(0.02-0.11)
＝0.162％
adding 0.162% by mass of Al to the second-layer zirconia powder 2 O 3 Fully and uniformly mixing for standby, spreading the first layer of zirconia powder in a dry pressing forming machine die for strickling, adding the second layer of zirconia powder for strickling, and forming an oxide ceramic powder layer;
maintaining the pressure for 30 seconds under the 12MPa bidirectional axial pressure of the dry-pressing forming machine, and maintaining the pressure for 40 seconds in a cold isostatic pressing machine at the 200MPa pressure to obtain a green body;
the green body is placed into a presintering degreasing furnace for presintering, and is heated to 550 ℃ at 0.3 ℃/min for 4 hours, and then heated to 1040 ℃ at 16 ℃/min for 3 hours, so as to obtain a presintering ceramic blank.
The pre-sintered ceramic blank was sawn into a slice about 2mm thick along the center, and the paper or ruler edge was placed on the lower (straight ruler end is first layer powder end, the same applies below) outer edge of the slice as a reference line, and the maximum bending height was measured, as shown in fig. 1, where a in fig. 1 is an overview view and B in fig. 1 is a detailed view.
As can be seen from fig. 1B, the pre-sintered ceramic blank did not show measurable bending, indicating that the multilayer zirconia ceramic was not deformed after pre-sintering.
Further, the pre-sintered ceramic blank is machined using a CAD/CAM process to obtain the desired shape of the dental restoration, such as the shape of a fixed partial denture, bridge, implant bridge, multi-unit frame, abutment, crown, partial crown, veneer, inlay, etc., to be implanted during the dental restoration, and is subjected to a secondary sintering at a sintering temperature of 1400-1600 ℃, in this embodiment at 1500 ℃.
The ceramic blank obtained after the secondary sintering was sawn into a cut piece of about 2mm thickness along the center, and a paper or ruler edge was placed on the lower outer edge of the cut piece as a reference line, as shown in figure 1C,
as can be seen from fig. 1C, no measurable bending was shown after secondary sintering, indicating that the multilayer zirconia ceramic was not deformed after secondary sintering.
If the prepared ceramic body is thicker, a small amount of organic plasticizer can be added into the oxide ceramic powder to enhance the powder plasticity, so that the ceramic body can be better molded in the later period and the green body with the ideal shape can be obtained. The organic plasticizer is added separately after the oxide ceramic powder composition is determined. The oxide ceramic powder added with a small amount of organic plasticizer (rubber powder) can be added in a single step before presintering to remove the organic plasticizer in the green body, and a proper rubber discharging temperature is selected according to the cracking temperature corresponding to the added organic plasticizer, and in some embodiments, the rubber discharging temperature is 350-800 ℃, and the rubber discharging can also be carried out simultaneously in the presintering process.
Comparative example 1
Two zirconia ceramic powders of example 1 were used, wherein the second layer ceramic powder was free of added Al 2 O 3 The preparation process and specific conditions are the same as in example 1, and the results are shown in FIG. 2, wherein A in FIG. 2 is an overview and B in FIG. 2 is a detailed view.
From the measurement results of B in FIG. 2, the maximum bending point of the pre-sintered blank shows a height of 0.52mm, indicating that the multilayer zirconia ceramic is significantly deformed after pre-sintering.
Example 2
Doped Al 2 O 3 The double-layer green body made of zirconia ceramic powder with different yttria contents is not deformed in the sintering process by being replaced by MgO, and the method concretely comprises the following steps:
adopts two different zirconia ceramic powders, and MgO is added into the second layer of powder to completely replace Al 2 O 3 And (5) adding. Wherein each layer of oxide powderThe weight ratios of the bulk components and the MgO doping amounts are shown in Table 2 below.
TABLE 2 weight ratio of oxide powder components and MgO doping amount of each layer
Wherein a is 0.036, b is 0.044, c is 0.018, then Al 2 O 3 The doping amount is as follows: m (Al) 2 O 3 )＝0+0.036*(9.7-7.4)+0.044*(0.37-0.12)-0.018(0.02-0.07)＝0.095％，
Al 2 O 3 The weight proportion of doping is replaced by MgO in a 2:1 ratio, so that the doping amount of MgO:
m(MgO)＝2m(Al 2 O 3 )＝0.19％
adding MgO with the mass of 0.19% into the second layer of zirconia powder, fully and uniformly mixing for standby, spreading the first layer of zirconia powder in a dry pressing forming machine die for strickling, adding the second layer of zirconia powder for strickling, and forming an oxide ceramic powder layer;
maintaining the pressure for 30 seconds under the 12MPa bidirectional axial pressure of the dry-pressing forming machine, and maintaining the pressure for 40 seconds in a cold isostatic pressing machine at the 200MPa pressure to obtain a green body;
the green body was placed in a presintering degreasing furnace for presintering under the same specific sintering conditions as in example 1 to obtain a presintered ceramic blank, and the maximum bending height was measured, as shown in fig. 3, in which a in fig. 3 is an outline view and B in fig. 3 is a detailed view.
As can be seen from fig. 3B, the pre-sintered ceramic blank did not show measurable bending, indicating that the multilayer zirconia ceramic was not deformed after pre-sintering.
In the present invention, mgO may be used in place of Al 2 O 3 Wherein the added weight proportion of MgO is the replaced part of Al 2 O 3 Is 2 times as large as the above.
Comparative example 2
Two zirconia ceramic powders of example 2 were used, wherein the first layer was 3Y-TZP white powder and the second layer was 5Y-TZP white powder, free of addition of sintering modifier Al 2 O 3 Or MgO; the maximum bending height of the presintered blank was measured in the same manner as in example 2, and the results are shown in fig. 4a (overview) and fig. 4B (detail).
As can be measured from B in fig. 4, the maximum bending point of the pre-sintered blank shows a height of 0.35mm, indicating that significant deformation occurs after the multi-layered zirconia ceramic is pre-sintered.
Example 3
By doping Al 2 O 3 The multi-layer green body made of zirconia ceramic powder with different yttria content is not deformed in the sintering process, and the method concretely comprises the following steps:
three-layer oxide ceramic is prepared by adopting three zirconia ceramic powders, wherein the weight proportion of oxide powder components of each layer and Al 2 O 3 The doping amounts are listed in table 3 below.
TABLE 3 weight ratio of oxide powder components of each layer and Al 2 O 3 Doping amount
* Wherein a is 0.03, b is 0.04, c is 0.02,
second layer of Al 2 O 3 The doping amount is calculated in detail by the formula:
m(Al 2 O 3 )＝0+0.03*(7.61-5.6)+0.04*(0.17-0.06)-0.02(0.05-0.11)
＝0.066％
third layer Al 2 O 3 The doping amount is calculated in detail by the formula:
m(Al 2 O 3 )＝0.066+0.03*(9.62-7.61)+0.04*(0.25-0.17)-0.02(0.02-0.05)
＝0.130％
adding 0.066% of Al in mass to the second layer of zirconia powder 2 O 3 Adding 0.130% by mass of Al to the third layer zirconia powder 2 O 3 Fully and uniformly mixing for standby, and mixing the first layer of zirconia powderSpreading the powder in a dry pressing forming machine die to be scraped, adding a second layer of zirconia powder to be scraped, and then adding a third layer of zirconia powder to form an oxide ceramic powder layer;
maintaining the pressure for 30 seconds under the 15MPa bidirectional axial pressure of the dry-pressing forming machine, and then maintaining the pressure for 40 seconds in a cold isostatic pressing machine at 300MPa pressure to obtain a green body;
the green body was placed in a presintering degreasing furnace for presintering under the same specific sintering conditions as in example 1 to obtain a presintered ceramic blank, and the maximum bending height was measured, and the results are shown in fig. 5 a (overview) and fig. 5B (detail).
As can be seen from fig. 5B, the pre-sintered ceramic blank did not show measurable bending, indicating that the multilayer zirconia ceramic was not deformed after pre-sintering.
Comparative example 3
Three-layer oxide ceramics were prepared using the three zirconia ceramic powders of example 5 in which neither the second layer nor the third layer was added with Al 2 O 3 The maximum bending height of the presintered blank was measured in the same molding, presintering, and sample preparation manner as in example 3, and the results are shown in fig. 6 a (overview) and fig. 6B (detail).
As can be measured from B in fig. 6, the maximum bending point of the pre-sintered blank shows a height of 0.48mm, indicating that the multilayer zirconia ceramic undergoes significant deformation after pre-sintering.
As is clear from the test results of the above examples and comparative examples, al was added to the zirconia powder 2 O 3 Or MgO stabilizer can prevent the green compact from deformation in the compact sintering process, and the prepared multilayer oxide ceramic has good consistency.
The zirconia powder used for preparing the multilayer oxide ceramic in the above-described embodiments may be replaced with an oxide ceramic powder type having alumina as a main crystal phase, such as a ceramic powder of zirconia-toughened alumina (ZTA), which is prepared according to the above-described preparation method by determining the weight ratio of lanthanoid, other coloring element oxide, yttria content in ZTA ceramic powder by the modification formula of the relational expression in the present invention.
EXAMPLE 4 Multi-layer oxide ceramic Strength test
The multi-layered oxide ceramics obtained in examples 1 to 3 and comparative examples 1 to 3 were used as test subjects, and the three-point bending strength thereof was examined as follows:
the device comprises: TH-8201S servo computer type universal material experiment machine,
pattern size: the length is more than 15.0mm, the width is 4.0mm, the thickness is 1.2mm,
span: 16mm, loading speed: 0.5mm/min; the test results are shown in the following table.
TABLE 4 comparison of flexural Strength of different multilayered zirconia ceramics
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As can be seen from Table 4, according to the method provided by the invention, al in each layer of powder is rapidly calculated by measuring the raw materials 2 O 3 Or the addition amount of MgO can avoid fumbling of a large number of experiments, and the addition is carried out according to the calculated addition amount, so that the compact sintering of each layer can keep consistent shrinkage, the bending deformation of the sintered multilayer oxide ceramic is avoided, the sintering stress in the ceramic block is reduced, the yield of the multilayer oxide ceramic block is greatly improved, and in addition, the strength of the multilayer oxide ceramic can be obviously improved due to the refinement of crystal grains.
Example 5 color stability test of Multi-layered oxide ceramics
Taking the pre-sintered blanks obtained in examples 1-3 and comparative examples 1-3 as targets, selecting a second sublayer of the pre-sintered blank, respectively carrying out heat preservation at 1470 ℃ and 1530 ℃ for 2 hours, carrying out secondary sintering, and carrying out color test on a sintered sample, wherein the specific steps are as follows:
the device comprises: a Ci7800 spectrophotometer was used to determine the color of the sample,
pattern size: the thickness is 1.0mm.
The colors after the above two temperature sinters were detected, color coordinates (L, a, b) were obtained, and the distances between the color coordinates (L, a, b) measured for the two temperature sinters were used as color differences, and the results are shown in table 5 below.
TABLE 5
| Sample of | Chromatic aberration |
| Example 1 | 1.03 |
| Comparative example 1 | 2.28 |
| Example 2 | 1.24 |
| Comparative example 2 | 2.31 |
| Example 3 | 1.51 |
| Comparative example 3 | 2.75 |
As is clear from Table 5, the secondary sintered color of the multilayer oxide ceramics of examples 1 to 3 is significantly smaller than the secondary sintered color of the multilayer oxide ceramics of comparative example, and it is seen that Al is added to the zirconia powder 2 O 3 Or MgO stabilizer can not only avoid the deformation of the multilayer oxide ceramic after pre-sintering, but also obviously improve the color stability of the multilayer oxide ceramic.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A method for preparing a metal oxide modified multi-layer oxide ceramic, comprising the steps of:
(1) Determination of Y in the raw oxide powder of each layer 2 O 3 Total weight ratio of lanthanide oxide to other coloring element oxide;
at least one layer of oxide powder is selected to be added with Al 2 O 3 Mixing uniformly to obtain the selected nth layer and Y in two adjacent layers 2 O 3 The layer with the smallest weight proportion is a contrast layer, n is a positive integer and n is more than 1; the Al is 2 O 3 The addition amount in the selected nth layer powder is calculated according to the following formula:
m(Al 2 O 3 )＝m min (Al 2 O 3 )+a*Δm(Y 2 O 3 )+b*Δm(La)-c*Δm(O)；
wherein: the value of a is 0.01-0.05, the value of b is 0.02-0.1, and the value of c is 0.01-0.04;
m min (Al 2 O 3 ) Is selected from the powder of the layer and the contrast layer of Al 2 O 3 Is a minimum weight ratio of (2);
Δm(Y 2 O 3 ) Is selected from Y in the powder of the layer and the contrast layer 2 O 3 Difference in weight ratio;
Δm (La) is the difference between the total weight ratio of lanthanide compounds in the selected layer and comparative layer powders;
Δm (O) is the difference between the total weight ratio of the selected layer and the oxides of other coloring elements in the powder of the contrast layer;
(2) Sequentially spreading oxide powder in a die according to a hierarchical sequence to form an oxide ceramic powder layer, compressing and molding to obtain a green body, and presintering the green body to obtain the multilayer oxide ceramic body.
2. The method for producing a metal oxide-modified multi-layer oxide ceramic according to claim 1, wherein a has a value in the range of 0.02 to 0.04, b has a value in the range of 0.02 to 0.06, and c has a value in the range of 0.01 to 0.03.
3. The method for producing a metal oxide-modified multi-layer oxide ceramic according to claim 2, wherein a has a value in the range of 0.03 to 0.04, b has a value in the range of 0.04 to 0.05, and c has a value in the range of 0.015 to 0.025.
4. A method for producing a metal oxide-modified multi-layer oxide ceramic according to any one of claims 1 to 3, wherein said Al 2 O 3 When being partially or completely replaced by MgO, according to MgO and Al 2 O 3 Is replaced and added in a weight ratio of 2:1.
5. The method of producing a metal oxide-modified multi-layer oxide ceramic according to claim 4, wherein the compression molding in the step (2) comprises one or more of dry press molding and cold isostatic molding; wherein the dry-pressing forming pressure is 20-150MPa, the dwell time is 30-120 seconds, the cold isostatic pressing pressure is 150-350MPa, and the dwell time is 30-300 seconds.
6. The method for producing a metal oxide-modified multi-layer oxide ceramic according to claim 5, wherein the pre-sintering temperature is 950-1150 ℃ and the holding time is not less than 1h.
7. The method for producing a metal oxide-modified multi-layer oxide ceramic according to claim 1, wherein the raw material oxide powder is Y 2 O 3 Oxide powder with doping amount of 0-26%, preferably Y 2 O 3 The doping amount of (2) is 5-11%.
8. A metal oxide-modified multilayer oxide ceramic body, characterized by being prepared according to the preparation method as claimed in any one of claims 1 to 7.
9. The metal oxide modified multi-layer oxide ceramic body of claim 8, wherein the multi-layer oxide ceramic body comprises at least two different layers, at least one of which is doped with Al 2 O 3 And/or MgO; and Al in at least two layers 2 O 3 Or a different MgO content, wherein at least one layer contains 0 to 10% by weight of Al 2 O 3 。
10. Use of a metal oxide modified multi-layer oxide ceramic body according to claim 8 or 9 for the preparation of a dental restoration.
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