CN117362027A - High-strength high-toughness nano zirconia ceramic material and preparation method and application thereof - Google Patents
High-strength high-toughness nano zirconia ceramic material 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 247
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000465 moulding Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 23
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 230000008439 repair process Effects 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 3
- 239000010409 thin film Substances 0.000 claims 2
- 230000004071 biological effect Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000002188 osteogenic effect Effects 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 210000000963 osteoblast Anatomy 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 3
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000007569 slipcasting Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 102100024506 Bone morphogenetic protein 2 Human genes 0.000 description 2
- 108010024682 Core Binding Factor Alpha 1 Subunit Proteins 0.000 description 2
- 101000762366 Homo sapiens Bone morphogenetic protein 2 Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102100025368 Runt-related transcription factor 2 Human genes 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000021164 cell adhesion Effects 0.000 description 2
- 229910002086 ceria-stabilized zirconia Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 241000309551 Arthraxon hispidus Species 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000015775 Core Binding Factor Alpha 1 Subunit Human genes 0.000 description 1
- 101710102802 Runt-related transcription factor 2 Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000921 morphogenic effect Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6022—Injection moulding
Abstract
The invention relates to the technical field of ceramic material preparation, in particular to a high-strength high-toughness nano zirconia ceramic material, and a preparation method and application thereof. The preparation method of the nano zirconia ceramic material provided by the invention comprises the following steps: the method is characterized by taking zirconia powder particles with amorphous oxide films on the surfaces as raw materials, and performing molding and sintering treatment. According to the invention, a functional gradient film layer is constructed on the surface of zirconia powder particles by utilizing an ALD technology for the first time, and the obtained film is recrystallized in the subsequent forming and sintering processes to form oxide grains with nano and submicron sizes distributed in zirconia grains and grain boundaries, so that the purposes of reinforcing and toughening are realized; meanwhile, the obtained material has a nano-phase structure, and the biological activity of the material is obviously improved.
Description
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to a high-strength high-toughness nano zirconia ceramic material, and a preparation method and application thereof.
Background
The zirconia ceramic material is a common repairing material for dentistry and orthopaedics due to good mechanical property, attractive performance and biocompatibility, such as zirconia crown bridge, zirconia implant, zirconia joint head and the like.
However, due to the brittle nature of zirconia ceramic materials, a certain thickness and size are still required during practical use to ensure sufficient strength and toughness, so as to avoid the problems of clinical complications or limited clinical use and improve the use reliability thereof. For example, the minimum thickness of the zirconia crown needs to be greater than 0.5mm, and the area of the zirconia bridge connection portion needs to be greater than 9mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The zirconia implant itself is relatively easy to break, especially for zirconia implants with small diameters (e.g., 3.3mm diameter).
The prior researches show that the structural defects of the ceramic material can be reduced and the growth of zirconia grains can be inhibited by means of improving the sintering temperature of the ceramic, hot isostatic pressing or specific oxide doping and the like, so that the strength and the reliability of the ceramic material are improved. However, the improvement effect of the above method is not ideal for zirconia ceramic materials.
Disclosure of Invention
Aiming at the problems, the invention provides a novel zirconia ceramic material, and a preparation method and application thereof. The zirconia ceramic material is nano-scale and has high strength, toughness, bioactivity and osteogenic activity.
In a first aspect, the preparation method of the nano zirconia ceramic material provided by the invention comprises the following steps: the method is characterized by taking zirconia powder particles with amorphous oxide films on the surfaces as raw materials, and performing molding and sintering treatment.
The invention provides a preparation method of a zirconia ceramic material, which uses zirconia powder particles with an amorphous oxide film on the surface as a preparation raw material of the zirconia ceramic material, wherein the amorphous oxide film can be recrystallized in the forming and sintering processes to form oxide grains (such as alumina) with nanometer and submicron sizes distributed in zirconia grains and grain boundaries, thereby realizing the purpose of reinforcing and toughening and solving the problem of high brittleness of the existing zirconia ceramic material.
Meanwhile, due to the existence of nanometer oxide crystal grains, the obtained zirconia ceramic material has a nanometer phase structure, not only can the adhesion of osteoblasts be increased, but also the synthesis of osteoblast alkaline phosphatase can be increased, the deposition of mineral substances can be promoted, the degree and the speed of cell adhesion can be improved, and the biological activity of the zirconia ceramic material can be obviously improved.
In addition, compared with the mode of adding nano particles into zirconia ceramic powder raw materials to improve the bioactivity of the ceramic material in the prior art, the amorphous oxide film recrystallization mode can avoid the growth of grains of the nano particles in the sintering process and ensure the formation of a nano-phase structure of the ceramic material.
Further, the amorphous oxide film has the following characteristics: the thickness is 0.1nm-100nm; the material is binary, ternary or multiple; the film layer is a single layer or a functionalized gradient coating which is made of binary, ternary or multielement materials and has adjustable thickness.
The amorphous oxide film is made of materials including but not limited to titanium oxide, magnesium oxide, silicon oxide, aluminum oxide, copper oxide, tantalum oxide, zinc oxide, tin oxide, lanthanum oxide, zirconium oxide and the like.
Research shows that the combination and thickness control of different film materials can improve the bonding strength of the film, further avoid the occurrence of falling off, cracks and the like in the subsequent molding and sintering, and improve the quality of oxide grains, thereby improving the strength and toughness of the zirconia ceramic material; meanwhile, through time-series release of different element components, different biological effects can be exerted, and the biological activity of the zirconia ceramic material is further provided.
For example, taking an alumina precursor as an example, zirconia powder and zirconia ceramic materials with different thicknesses and different strengths are obtained through 5 times, 10 times, 20 times, 30 times, 40 times and 50 times of circulation, and under the condition that the thicknesses are the same, as shown in fig. 5, 9 and 10, the strength of the zirconia ceramic material prepared by the method is improved by more than 30 percent compared with that of the zirconia material (3T-TZP) used in clinic at present, the toughness is improved by 1.5 times, and the thickness can be greatly reduced when the zirconia ceramic material is applied to the preparation of dental crowns.
Furthermore, the operation conditions of the forming and sintering process can be adjusted according to the film material and thickness of the amorphous oxide film so as to regulate and control the crystallinity of the amorphous oxide film, thereby realizing the time sequence of different nano film components and the exertion of biological effects accurately controlled, solving the problem that the current direct atomic layer deposition technology only focuses on deposition and ignores the biological effects, and further obtaining the ceramic functional preparation technology with strong practicability, high strength, high toughness and better biological activity.
The molding is dry press molding, wet molding or additive manufacturing molding. Preferably, the pressure of the dry press molding is 130-200MPa; the wet molding includes slip casting, injection molding, and the like.
The sintering temperature is 1200-1550 ℃.
Oxide crystal grains (such as alumina) with nanometer and submicron sizes are formed in the crystal grains and at the crystal boundary by reasonably controlling the forming and sintering conditions, and the formed oxide crystal grains (such as alumina) are crystalline or nanocrystalline, so that the strength, toughness, bioactivity and osteogenic activity of the ceramic material are obviously improved.
Further, based on the different amorphous oxide films, the corresponding molding and sintering process conditions are also different, and the formed oxide grains also exhibit different strength, toughness and bioactivity.
As one of the specific embodiments of the present invention, zirconia powder particles having an amorphous alumina film on the surface thereof are used as a raw material for molding and sintering; the molding and sintering treatment conditions are as follows: dry-pressing to form at 160-200MPa, heating to 1300-1550 deg.C at 10-30 deg.C/min, and sintering for 2 hr.
Further, the amorphous oxide film is formed on the surface of zirconia powder particles by an atomic layer deposition technique. And the material and thickness of each film layer in the functional gradient coating can be regulated and controlled by adjusting the types, the deposition sequence and the circulation times of the precursors.
As one of the specific embodiments of the present invention, a method for preparing a nano zirconia ceramic material by ALD technology is provided, taking alumina as an example, the reaction principle of which is shown in fig. 1, and the method comprises the following steps:
(1) Carrying out first surface reaction on reaction sites of precursor A trimethylaluminum and zirconia powder particles;
the operation conditions are as follows: placing the dried zirconia powder material into a cavity of an atomic layer deposition device filled with inert gas, raising the temperature, keeping the temperature of the reaction cavity between 200 and 350 ℃, and vacuumizing the reaction cavity after the temperature is reached to 1 -10 s；
Introducing trimethylaluminum into the cavity with nitrogen as carrier, and controlling reaction time to 0.1 -10 s；
(2) Introducing inert gas into the cavity for purging, and removing unreacted precursor A and volatile byproducts hydrogen chloride in the reaction cavity;
(3) Carrying out a second surface reaction on the water of the precursor B and the sites subjected to the surface reaction in the step (1), and converting the surfaces of the zirconia powder particles back to the initial surfaces with the same reaction sites;
the operation conditions are as follows: introducing H into the cavity by taking nitrogen as a carrier 2 O, reaction time was controlled to 0.01 -20 s；
(4) Purging with inert gas again to obtain a layer of amorphous alumina film, and completing a circulation process;
(5) Repeating the steps (1) - (4) until the thickness of the amorphous alumina film reaches the target thickness;
(6) Forming and sintering the zirconia powder particles with the amorphous alumina film obtained in the step (5);
the conditions of the molding and sintering treatment are as follows: the molding conditions may be dry press molding: the pressure is 160-200MPa, or wet forming (such as slip casting), or additive manufacturing forming, etc., and the final sintering temperature is 1450-1550 ℃.
In a second aspect, the invention provides a nano zirconia ceramic material, which is obtained by the preparation method.
The nano zirconia ceramic material comprises zirconia grains and oxide grains distributed in the zirconia grains and at grain boundaries; the average grain diameter of the zirconia grains is less than or equal to 1 mu m; the average grain diameter of the oxide crystal grains is less than or equal to 500nm; and as the content of oxide grains increases, the average grains of the zirconia grains decrease; oxide grains with average grain diameter less than or equal to 200nm exist in the zirconia grains; the crystal form of the oxide crystal grain is crystal or nanocrystalline. Compared with the conventional zirconia ceramic material, the nano zirconia ceramic material obtained by the invention has higher strength, toughness and better bioactivity.
In a third aspect, the present invention provides a ceramic repair material comprising the above nano zirconia ceramic material.
Compared with the conventional zirconia ceramic material, the ceramic repair material provided by the invention has better strength and toughness, good aesthetic property and biocompatibility.
The technical scheme of the invention has the following beneficial effects:
(1) The invention provides the atomic layer deposition technology applied to the preparation technology of the zirconia ceramic material for the first time. The amorphous oxide film is plated on the surface of zirconia powder particles layer by layer in a single-atom film mode, so that the amorphous oxide film is recrystallized in the subsequent forming and sintering process to form oxide crystal grains (such as alumina) with nanometer size, wherein the oxide crystal grains are distributed in zirconia crystal grains and grain boundaries, and the crystal forms of the oxide crystal grains are crystals or nanocrystalline, thereby realizing the purpose of reinforcing and toughening, and solving the problem of high brittleness of the traditional zirconia ceramic material.
(2) The zirconia ceramic material obtained by the invention has a nano-phase structure, not only increases the adhesion of osteoblasts, but also increases the synthesis of osteoblast alkaline phosphatase and promotes the deposition of mineral substances, thereby improving the degree and speed of cell adhesion and obviously improving the biological activity of the zirconia ceramic material.
(3) The invention controls the atomic composition and the thickness of each layer of amorphous oxide film by adjusting the precursor type, the deposition sequence and the circulation times in the atomic layer deposition process, so that each film layer has a synergistic effect, the bonding strength of each film layer is improved, the occurrence of the conditions of falling, cracking and the like in the subsequent forming and sintering is further avoided, the quality of oxide crystal grains is improved, and the strength and the toughness of the zirconia ceramic material are improved; meanwhile, through time-series release of different element components, different biological effects can be exerted, and the biological activity of the zirconia ceramic material is further provided.
(4) The preparation method has the advantages of relatively simple process, easy control and suitability for large-scale industrial production.
Drawings
FIG. 1 is a schematic reaction diagram of the process for preparing nano zirconia ceramic material according to example 1.
FIG. 2 shows TEM results of zirconia powder particles obtained for different cycle times; wherein control is untreated zirconia powder; 10cycles is 10cycles (10 nm); 30cycles is 30cycles (10 nm); 50cycles was 50cycles (10 nm).
Fig. 3 is a fourier transform (FFT) analysis result of the particle body and the surface deposited coating layer of the 50-cycle zirconia powder, respectively.
FIG. 4 shows XRD results for zirconia powder particles and nano zirconia ceramic materials obtained for different cycle numbers; wherein (a) is zirconia powder particles; (b) The nano zirconia ceramic material is obtained by pressing and sintering.
FIG. 5 is an electron microscope and surface distribution diagram of a nano zirconia ceramic material containing alumina grains with different cycle numbers; wherein (a) is 5 cycles (1 μm), and the right graph shows the distribution of aluminum element in zirconia grains; (b) 10cycles (400 nm); (c) 20 cycles (400 nm); (d) 30cycles (400 nm); (e) 40 cycles (400 nm); (f) 50cycles (400 nm); (g) is the no treatment group (400 nm); (h) The results of the analysis were measured for each group of zirconia grain sizes.
FIG. 6 is an electron micrograph of a 30cycle alumina grain containing nano zirconia ceramic material; arrows of different grey scale indicate different distribution forms of the doped alumina particles.
FIG. 7 is a TEM observation of 50cycles of FIB slicing of a nano zirconia ceramic material containing alumina grains; wherein, (a) is a graph of alumina particles containing nano zirconia particles; (b) Is a graph of zirconia particles containing nano alumina particles.
Fig. 8 is a plot of the results of diaphragm selective diffraction of alumina particles in a TEM.
Fig. 9 is a comparison of the strength of different zirconia ceramic materials.
FIG. 10 is a comparison of toughness of different zirconia ceramic materials.
FIG. 11 is a graph showing the comparison of the osteogenic properties of different zirconia ceramic materials.
FIG. 12 is a comparison of results of osteogenic related gene expression for different zirconia ceramic materials; wherein Runx2 is Runt-related transcription factor-2; BMP2 is bone morphogenic protein-2.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a nano zirconia ceramic material, taking ALD alumina as an example, the reaction process and the principle are shown in figure 1, and the total reaction equation is as follows:
2Al(CH 3 ) 3 (g)+3H 2 O(g)→Al 2 O 3 +6CH 4 (g)↑
the first step:
Al(CH 3 ) 3 (g)+Zr(OH)(s)→Zr-O-Al(CH 3 ) 2 (s)+CH 4 (g)↑
and a second step of:
Zr-O-Al(CH 3 ) 2 (s)+2H-OH(g)→Zr-O-Al(OH) 2 (s)+2CH 4 (g)↑
the method comprises the following specific steps:
s1, formation of amorphous alumina film
(1) Introducing precursor A trimethylaluminum into a reaction bottle to react with reaction sites on zirconia powder particles;
the operation is as follows: placing the dried positive electrode material into a cavity of an atomic layer deposition device filled with inert gas, raising the temperature, keeping the temperature of a reaction chamber at 180 ℃, and vacuumizing the reaction cavity for 10s after the temperature is reached;
introducing trimethylaluminum into the cavity by taking nitrogen as a carrier, and controlling the reaction time to be 1s;
(2) Purging with inert gas to remove unreacted precursor and volatile byproduct hydrogen chloride in the reaction chamber;
(3) Introducing the precursor B water into the reaction cavity to perform a second reaction, and converting the surfaces of the zirconia powder particles back to the initial surfaces with the same reaction sites;
the operation conditions are as follows: introducing H into the cavity by taking nitrogen as a carrier 2 O, the reaction time is controlled to be 0.5s;
(4) Purging with inert gas again to obtain a layer of amorphous alumina film, and completing a circulation process;
(5) Repeating the steps (1) - (4) until the thickness of the amorphous alumina film reaches the target thickness;
s2, molding and sintering:
(6) Forming and sintering the zirconia powder particles with the amorphous alumina film obtained in the step (5);
the molding mode and the operation condition are as follows: dry-pressing to form at 160-200MPa; or wet forming (e.g., slip casting); or additive manufacturing molding, etc.;
sintering treatment conditions: the sintering temperature is 1450-1550 ℃.
The results show that:
(1) As shown in fig. 2, in the result of the powder Transmission Electron Microscope (TEM), the powder particles with different numbers of ALD cycles were uniformly coated with the coating layers with different thicknesses, and the coating layers increased in thickness with the increase of the number of cycles.
(2) As shown in fig. 3, the powder particle body and the surface coating were subjected to a selected area fourier transform (FFT) analysis, and the result showed that the zirconia particle body was crystalline and the surface coating was amorphous.
(3) As shown in fig. 4, in the X-ray diffraction (XRD) result, no obvious alumina component is detected in the powder with different ALD cycle numbers, and after each group of zirconia powder is respectively isostatically molded and sintered, a trace amount of alumina component can be detected in the zirconia sheet, that is, it is shown that the ALD method is successful in depositing an amorphous and amorphous alumina layer on the surface of the zirconia powder particles, and the layer thickness can be calculated as sub-nanometer thickness from the cycle number;
(4) As shown in fig. 5, scanning Electron Microscope (SEM) and surface distribution (Mapping) results demonstrate that the alumina particle content increases after sintering formation as the deposition thickness increases; compared with zirconia prepared by firing untreated zirconia powder, the particle size of zirconia grains of ALD alumina on the surface of powder particles is obviously reduced, which indicates that the alumina uniformly exists among the zirconia grains and limits the growth of the zirconia grains;
(5) As shown in fig. 6, the alumina grains after sintering molding have different distribution forms in zirconia, are partially distributed at the interfaces of the zirconia grains, and are surrounded by 4-5 zirconia grains; part of the zirconium oxide crystal grains are distributed on the junction line of the two zirconium oxide crystal grains; partially completely surrounded by zirconia grains;
(6) As shown in fig. 7, a focused ion beam prepared slice was subjected to high resolution transmission electron microscopy (FIB-TEM), and it was seen that nano-sized alumina particles were packed in zirconia grains; alumina grains can also be wrapped with nano-sized zirconia particles;
(7) As shown in fig. 8, the alumina particles were subjected to selective diffraction, and the results showed that the alumina grains contained a large number of nanocrystals.
(8) As shown in the results of fig. 9, with reference to the biaxial bending strength test method for ceramic material strength in ISO 6872:2008, the flexural strength of the test specimen was calculated, and it was seen that the strength of the zirconia sheet of the ALD alumina group was increased by 30% compared to 3mol% yttria-stabilized zirconia (3Y-TZP) and 10% compared to ceria-stabilized zirconia (Ce-TZP).
(9) As shown in the results of fig. 10, with reference to the fracture toughness test method for ceramic material strength in ISO 6872:2008, the fracture toughness of the samples was calculated, and it was seen that the toughness of the zirconia sheets of the ALD alumina group increased by about 150% compared to 3mol% yttria stabilized zirconia (3Y-TZP) and 37% compared to ceria stabilized zirconia (Ce-TZP).
(10) Biological activity: as shown in the results of fig. 11, it can be seen that the nano zirconia sheets of the ALD alumina group showed increased expression level of alkaline phosphatase on osteoblasts (MC 3T3-e 1), indicating better osteogenic performance;
(11) As shown in the results of FIG. 12, compared with the 3Y-TZP, ce-TZP and nano zirconia products NANOZR, the expression of the osteogenic related gene markers RUNX2 and BMP2 in MC3T3-e1 cells cultured on the surface of the zirconia sheet of the ALD alumina group is obviously improved, which indicates that the osteogenic performance is better.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the nano zirconia ceramic material is characterized by comprising the following steps: the method is characterized by taking zirconia powder particles with amorphous oxide films on the surfaces as raw materials, and performing molding and sintering treatment.
2. The method for preparing a nano zirconia ceramic material according to claim 1, wherein the amorphous oxide thin film has the following characteristics: the thickness is 0.1nm-100nm; the material is binary, ternary or multiple; the film layer is a single layer or a functionalized gradient coating which is made of binary, ternary or multielement materials and has adjustable thickness.
3. The method for preparing a nano zirconia ceramic material according to claim 2, wherein the molding is dry press molding, wet molding or additive manufacturing molding;
preferably, the pressure of the dry press molding is 130-200MPa.
4. A method of preparing a nano zirconia ceramic material according to any one of claims 1 to 3, wherein the sintering temperature is 1200 to 1550 ℃.
5. The method for preparing nano zirconia ceramic material according to claim 4, wherein the amorphous oxide film is made of alumina, and the corresponding molding and sintering conditions are: dry-pressing at 160-200MPa, and sintering at 1300-1550 deg.C.
6. The method for preparing a nano zirconia ceramic material according to claim 5, wherein the dry press molding is followed by heating to the sintering temperature at a rate of 10-30 ℃/min.
7. The method for preparing a nano zirconia ceramic material according to claim 6, wherein the amorphous oxide thin film is formed on the surface of zirconia powder particles by atomic layer deposition technique.
8. A nano zirconia ceramic material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 7.
9. The nano-zirconia ceramic material according to claim 8, wherein the nano-zirconia ceramic material comprises zirconia grains and oxide grains distributed in the zirconia grains and at grain boundaries;
the average grain diameter of the zirconia grains is less than or equal to 1 mu m;
the average grain diameter of the oxide crystal grains is less than or equal to 500nm;
and as the content of the oxide crystal grains increases, the average grain size of the zirconia crystal grains decreases;
oxide grains with average grain diameter less than or equal to 200nm exist in the zirconia grains;
and the oxide crystal grains are crystals or nanocrystals.
10. A ceramic repair material comprising the nano zirconia ceramic material of claim 8 or 9.
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