WO2024051651A1 - High-strength high-toughness nano zirconium oxide ceramic material, preparation method therefor, and use thereof - Google Patents

High-strength high-toughness nano zirconium oxide ceramic material, preparation method therefor, and use thereof Download PDF

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WO2024051651A1
WO2024051651A1 PCT/CN2023/116763 CN2023116763W WO2024051651A1 WO 2024051651 A1 WO2024051651 A1 WO 2024051651A1 CN 2023116763 W CN2023116763 W CN 2023116763W WO 2024051651 A1 WO2024051651 A1 WO 2024051651A1
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zirconia
grains
zirconia ceramic
nano
ceramic materials
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韩建民
郭现伟
李楠
郭传瑸
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北京大学口腔医学院
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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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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

Definitions

  • the invention relates to the technical field of ceramic material preparation, and specifically relates to a high-strength and high-toughness nano-zirconia ceramic material and its preparation method and application.
  • zirconia ceramic materials are commonly used restorative materials in today's dentistry and orthopedics, such as zirconia crowns and bridges, zirconia implants, zirconia joint heads, etc.
  • zirconia ceramic materials due to the brittleness of zirconia ceramic materials, a certain thickness and size are still required to ensure sufficient strength and toughness during actual use to avoid clinical complications or limited clinical use and improve its use. reliability.
  • the minimum thickness of zirconia crowns needs to be greater than 0.5mm, and the connecting area of zirconia bridges needs to be greater than 9mm 2 ; and zirconia implants themselves are more prone to breakage, especially small-diameter zirconia implants (such as diameter 3.3 mm).
  • the present invention provides a new zirconia ceramic material and its preparation method and application.
  • the zirconia ceramic material is nanoscale and has high strength, toughness, biological activity and osteogenic activity.
  • the present invention provides a method for preparing nano-zirconia ceramic materials, including: using zirconium oxide powder particles with an amorphous oxide film on the surface as raw materials, and performing shaping and sintering processes.
  • the present invention proposes for the first time that zirconium oxide powder particles with an amorphous oxide film on the surface are used as raw materials for preparing zirconium oxide ceramic materials.
  • the amorphous oxide film can be recrystallized during the molding and sintering processes to form particles distributed within the zirconium oxide grains and Nano- and sub-micron-sized oxide grains (such as alumina) at the grain boundaries achieve the purpose of strengthening and toughening and solve the problem of high brittleness of existing zirconia ceramic materials. question.
  • the resulting zirconia ceramic material has a nano-phase structure, which not only increases the adhesion of osteoblasts, but also increases the synthesis of osteoblast alkaline phosphatase and promotes mineral deposition. , improve the degree and speed of cell attachment, and significantly improve the biological activity of zirconia ceramic materials.
  • the present invention can avoid the crystallization of nanoparticles during the sintering process by recrystallizing the amorphous oxide film.
  • the occurrence of grain growth ensures the formation of nanophase structure of ceramic materials.
  • the amorphous oxide film has the following characteristics: thickness is 0.1nm-100nm; material is binary, ternary or multi-element; the film layer is a single layer or binary, ternary or multi-element material and the thickness is adjustable Functionalized gradient coating.
  • the materials of the amorphous oxide film include but are not limited to titanium oxide, magnesium oxide, silicon oxide, aluminum oxide, copper oxide, tantalum oxide, zinc oxide, tin oxide, lanthanum oxide, zirconium oxide, etc.
  • zirconia powder and zirconia ceramic materials with different thicknesses and strengths are obtained, as shown in Figure 5
  • the strength of the zirconia ceramic material prepared by the present invention is increased by more than 30% and the toughness is increased by 1.5 times compared with the zirconia material (3T-TZP) currently used in clinical practice.
  • the thickness can be significantly reduced when used in crown preparation.
  • the operating conditions of the molding and sintering process of the present invention can be adjusted according to the film material and thickness of the amorphous oxide film to regulate its crystallinity, thereby achieving timing and precise control of different nanofilm components.
  • Biological effects are exerted to solve the current direct atomic layer deposition The technology only focuses on the deposition itself and ignores the biological effects, thereby obtaining functionalized ceramic preparation technology with high practicality, high strength and toughness, and better biological activity.
  • the molding is dry pressing molding, wet molding or additive manufacturing molding.
  • the pressure of the dry pressing molding is 130-200MPa; the wet molding includes slip molding, injection molding, etc.
  • the sintering temperature is 1200-1550°C.
  • oxide grains such as alumina
  • the crystal form of the formed oxide grains is crystal or Nanocrystals can significantly improve the strength, toughness, biological activity and osteogenic activity of ceramic materials.
  • the corresponding molding and sintering process conditions are also different, and the formed oxide grains also show different strengths, toughness and biological activities.
  • zirconium oxide powder particles with an amorphous aluminum oxide film on the surface are used as raw materials for molding and sintering treatment; the molding and sintering treatment conditions are: dry pressing first, and the pressure is 160-200MPa , and then increase the temperature to 1300°C-1550°C for 2 hours at a speed of 10-30°C/min.
  • the amorphous oxide film is formed on the surface of the zirconium oxide powder particles through atomic layer deposition technology. Furthermore, the material and thickness of each film layer in the functionalized gradient coating can be adjusted by adjusting the type of precursor, deposition sequence and number of cycles.
  • a method for preparing nano-zirconia ceramic materials through ALD technology is provided. Taking alumina as an example, the reaction principle is shown in Figure 1, including the following steps:
  • reaction site of precursor A trimethylaluminum and zirconia powder particles undergoes the first surface reaction
  • the operating conditions are: put the dried zirconia powder material into the cavity of the atomic layer deposition equipment filled with inert gas, increase the temperature, and keep the temperature of the reaction cavity between 200-350°C. After reaching the temperature, The reaction chamber is evacuated for 1-10 s;
  • step (3) Perform a second surface reaction between the precursor B water and the sites after the surface reaction in step (1). At this time, the surface of the zirconia powder particles is converted back to the starting surface with the same reaction site;
  • the operating conditions are: nitrogen is used as the carrier, H 2 O is introduced into the cavity, and the reaction time is controlled to 0.01 -20 s;
  • the conditions for molding and sintering treatment are:
  • the molding conditions can be dry pressing molding: the pressure is 160-200MPa, or wet molding (such as slip molding), or additive manufacturing molding, etc.
  • the final sintering temperature is 1450°C-1550°C.
  • the present invention provides a nano-zirconia ceramic material, which is obtained by the above preparation method.
  • the nano-zirconia ceramic material includes zirconia grains and oxide grains distributed in the zirconia grains and at grain boundaries; the average particle diameter of the zirconia grains is ⁇ 1 ⁇ m; the oxide grains The average particle size is ⁇ 500nm; and as the oxide grain content increases, the average grain size of the zirconia grains decreases; oxide grains with an average grain size ⁇ 200nm exist in the zirconia grains; oxide grains The crystal form of grains is crystal or nanocrystal.
  • the nano zirconia ceramic materials obtained by the present invention have higher strength, toughness and better biological activity.
  • the present invention provides a ceramic repair material, which contains the above-mentioned nano-zirconia ceramic material.
  • the ceramic repair material of the present invention has better strength and toughness, good aesthetic properties and biocompatibility.
  • the present invention proposes for the first time the application of atomic layer deposition technology to the preparation technology of zirconia ceramic materials.
  • amorphous oxide films By plating amorphous oxide films layer by layer on the surface of zirconia powder particles in the form of single-atom films, they are recrystallized in the subsequent molding and sintering processes to form distribution in the zirconia grains.
  • Nano-sized oxide grains (such as alumina) at the internal and grain boundaries are crystals or nanocrystals, thereby achieving the purpose of strengthening and toughening and solving the brittleness of existing zirconia ceramic materials. Big question.
  • the zirconia ceramic material obtained by the present invention has a nano-phase structure, which not only increases the attachment of osteoblasts, but also increases the synthesis of osteoblast alkaline phosphatase and promotes the deposition of minerals, improving the degree and speed of cell attachment. , significantly improving the biological activity of zirconia ceramic materials.
  • the present invention controls the atomic composition and thickness of each layer in the amorphous oxide film by adjusting the precursor type, deposition sequence and cycle number in the atomic layer deposition process, so that each film layer works synergistically and improves the bonding strength of each film layer. , thereby avoiding the occurrence of shedding, cracks, etc. during subsequent molding and sintering, improving the quality of oxide grains, thereby improving the strength and toughness of zirconia ceramic materials; at the same time, through the sequential release of different elemental components, it can exert Different biological effects further provide the biological activity of zirconia ceramic materials.
  • the preparation method of the present invention has the advantages of relatively simple process, easy control, and is suitable for large-scale industrial production.
  • Figure 1 is a reaction principle diagram of the preparation process of nano-zirconia ceramic materials described in Example 1.
  • Figure 2 shows the TEM results of zirconia powder particles obtained with different cycle times; where control is untreated zirconia powder; 10cycles is 10 cycles (10nm); 30cycles is 30 cycles (10nm); 50cycles is 50 cycles ( 10nm).
  • Figure 3 shows the results of Fourier transform (FFT) crystal analysis of the zirconia powder particles and the surface deposited coating after 50 cycles.
  • FFT Fourier transform
  • Figure 4 shows the XRD results of zirconia powder particles and nano-zirconia ceramic materials obtained by different cycle times; among them, (a) is zirconia powder particles; (b) is the nano-zirconia ceramic material obtained by pressing and sintering.
  • Figure 5 shows the electron microscope and surface distribution diagram of nano-zirconia ceramic materials containing alumina grains with different cycles;
  • (a) is 5 cycles (1 ⁇ m), and the right picture shows the distribution of aluminum elements in zirconia grains;
  • (b) is 10 cycles (400nm);
  • (c) is 20 cycles (400nm);
  • (d) is 30 cycles (400nm);
  • (e) is 40 cycles (400nm);
  • (f) is 50 cycles (400nm);
  • (g) is the untreated group (400nm);
  • (h) is the measurement and analysis results of the zirconia grain size of each group.
  • Figure 6 is an electron microscope image of a nano-zirconia ceramic material containing alumina grains after 30 cycles; arrows with different grayscales indicate different distribution forms of doped alumina particles.
  • Figure 7 shows the TEM observation results after 50 cycles of FIB slicing of nano-zirconia ceramic materials containing alumina grains; (a) is a picture of nano-zirconia particles contained in alumina particles; (b) is a picture of zirconium oxide particles Contains a diagram of nano-alumina particles.
  • Figure 8 shows the results of aperture selected diffraction of alumina particles in TEM.
  • Figure 9 shows the strength comparison of different zirconia ceramic materials.
  • Figure 10 shows the toughness comparison of different zirconia ceramic materials.
  • Figure 11 shows the comparison of osteogenic properties of different zirconia ceramic materials.
  • Figure 12 shows the comparison of osteogenesis-related gene expression results of different zirconia ceramic materials; among them, Runx2 is Runt-related transcription factor-2; BMP2 is bone morphogenetic protein-2.
  • This embodiment provides a method for preparing nano-zirconia ceramic materials.
  • ALD alumina as an example, the reaction process and principle are shown in Figure 1, and the overall reaction equation is as follows: 2Al(CH 3 ) 3 (g)+3H 2 O(g) ⁇ Al 2 O 3 +6CH 4 (g) ⁇
  • Step two Zr-O-Al(CH 3 ) 2 (s)+2H-OH(g) ⁇ Zr-O-Al(OH) 2 (s)+2CH 4 (g) ⁇
  • the operation is as follows: put the dried cathode material into the cavity of the atomic layer deposition equipment filled with inert gas, increase the temperature, and keep the temperature of the reaction chamber at 180°C. After reaching the temperature, the reaction chamber is evacuated for 10 seconds;
  • trimethylaluminum is introduced into the cavity, and the reaction time is controlled to 1 s;
  • the operating conditions are: nitrogen is used as the carrier, H 2 O is introduced into the cavity, and the reaction time is controlled to 0.5s;
  • Molding methods and operating conditions dry pressing molding with a pressure of 160-200MPa; or wet molding (such as grouting molding); or additive manufacturing molding, etc.;
  • the sintering temperature is 1450-1550°C.
  • the alumina grains after sintering have different distribution forms in zirconia. Some are distributed at the junctions of zirconia grains and are surrounded by 4 to 5 zirconia grains; Distributed on the intersection line of two zirconia grains; part of it is completely wrapped by zirconia grains;

Abstract

The present invention relates to the technical field of ceramic material preparation, and in particular to a high-strength high-toughness nano zirconium oxide ceramic material, a preparation method therefor, and a use thereof. The preparation method for the nano zirconium oxide ceramic material provided by the present invention comprises: using zirconium oxide powder particles of which the surfaces are provided with an amorphous oxide thin film as a raw material, and carrying out forming and sintering treatment. The present invention first puts forward constructing a functionalized gradient film layer on the surfaces of the zirconium oxide powder particles by utilizing an ALD technique, and recrystallizing the prepared thin film in the subsequent forming and sintering process to form nano-sized and submicron-sized oxide crystal grains distributed in zirconium oxide crystal grains and grain boundaries, so as to achieve the objective of strengthening and toughening; moreover, the prepared material has a nano-phase structure, and the biological activity of the material is remarkably improved.

Description

一种高强度高韧性纳米氧化锆陶瓷材料及其制备方法与应用A high-strength and high-toughness nano-zirconia ceramic material and its preparation method and application 技术领域Technical field
本发明涉及陶瓷材料制备技术领域，具体涉及一种高强度高韧性纳米氧化锆陶瓷材料及其制备方法与应用。The invention relates to the technical field of ceramic material preparation, and specifically relates to a high-strength and high-toughness nano-zirconia ceramic material and its preparation method and application.
背景技术Background technique
氧化锆陶瓷材料由于良好机械性能、美观性能和生物相容性，是当今牙科和骨科的常用修复材料，如氧化锆冠桥、氧化锆种植体、氧化锆关节头等。Due to its good mechanical properties, aesthetic properties and biocompatibility, zirconia ceramic materials are commonly used restorative materials in today's dentistry and orthopedics, such as zirconia crowns and bridges, zirconia implants, zirconia joint heads, etc.
然而，由于氧化锆陶瓷材料的脆性特点，在实际的使用过程中仍然需要一定的厚度和大小以保证足够的强度和韧性，以避免临床并发症的发生或临床使用受限的问题，提高其使用可靠性。例如，氧化锆牙冠最小厚度需要大于0.5mm，氧化锆桥体连接部分面积需要大于9mm2；而氧化锆种植体本身就较为容易发生折断，尤其是小直径的氧化锆种植体(如直径3.3mm)。However, due to the brittleness of zirconia ceramic materials, a certain thickness and size are still required to ensure sufficient strength and toughness during actual use to avoid clinical complications or limited clinical use and improve its use. reliability. For example, the minimum thickness of zirconia crowns needs to be greater than 0.5mm, and the connecting area of zirconia bridges needs to be greater than 9mm 2 ; and zirconia implants themselves are more prone to breakage, especially small-diameter zirconia implants (such as diameter 3.3 mm).
现有研究表明，可通过提高陶瓷烧结温度、热等静压或特定氧化物掺杂等手段减少陶瓷材料的结构缺陷、抑制氧化锆晶粒生长，从而增加陶瓷材料的强度和可靠性。但对于氧化锆陶瓷材料，上述方法改善效果并不理想。Existing research shows that the structural defects of ceramic materials can be reduced and the growth of zirconium oxide grains can be inhibited by means such as increasing the ceramic sintering temperature, hot isostatic pressing, or doping with specific oxides, thereby increasing the strength and reliability of ceramic materials. However, for zirconia ceramic materials, the improvement effect of the above method is not ideal.
发明内容Contents of the invention
针对上述问题，本发明提供一种新的氧化锆陶瓷材料及其制备方法与应用。所述氧化锆陶瓷材料为纳米级，具有较高的强度、韧性、生物活性及成骨活性。In view of the above problems, the present invention provides a new zirconia ceramic material and its preparation method and application. The zirconia ceramic material is nanoscale and has high strength, toughness, biological activity and osteogenic activity.
第一方面，本发明提供的纳米氧化锆陶瓷材料的制备方法，包括：以表面具有无定型氧化物薄膜的氧化锆粉末颗粒为原料，进行成型和烧结处理。In a first aspect, the present invention provides a method for preparing nano-zirconia ceramic materials, including: using zirconium oxide powder particles with an amorphous oxide film on the surface as raw materials, and performing shaping and sintering processes.
本发明首次提出以表面具有无定型氧化物薄膜的氧化锆粉末颗粒为氧化锆陶瓷材料的制备原料，无定型氧化物薄膜可在成型和烧结过程中再结晶，形成分布于氧化锆晶粒内和晶界的具有纳米和亚微米大小的氧化物晶粒(如氧化铝)，从而实现了增强增韧的目的，解决了现有氧化锆陶瓷材料脆性大的 问题。The present invention proposes for the first time that zirconium oxide powder particles with an amorphous oxide film on the surface are used as raw materials for preparing zirconium oxide ceramic materials. The amorphous oxide film can be recrystallized during the molding and sintering processes to form particles distributed within the zirconium oxide grains and Nano- and sub-micron-sized oxide grains (such as alumina) at the grain boundaries achieve the purpose of strengthening and toughening and solve the problem of high brittleness of existing zirconia ceramic materials. question.
同时，由于纳米尺寸的氧化物晶粒的存在，所得氧化锆陶瓷材料具有纳米相结构，不仅增加了成骨细胞的附着，还可增加成骨细胞碱性磷酸酶的合成并促进矿物质的沉积，提高细胞附着的程度和速度，使氧化锆陶瓷材料的生物活性得到显著提升。At the same time, due to the existence of nano-sized oxide grains, the resulting zirconia ceramic material has a nano-phase structure, which not only increases the adhesion of osteoblasts, but also increases the synthesis of osteoblast alkaline phosphatase and promotes mineral deposition. , improve the degree and speed of cell attachment, and significantly improve the biological activity of zirconia ceramic materials.
此外，相比于现有技术通过向氧化锆陶瓷粉末原料中添加纳米颗粒以提高陶瓷材料生物活性的方式，本发明通过无定型氧化物薄膜再结晶的方式，能够避免纳米颗粒在烧结过程中晶粒长大现象的发生，确保陶瓷材料纳米相结构的形成。In addition, compared with the existing method of adding nanoparticles to zirconia ceramic powder raw materials to improve the biological activity of ceramic materials, the present invention can avoid the crystallization of nanoparticles during the sintering process by recrystallizing the amorphous oxide film. The occurrence of grain growth ensures the formation of nanophase structure of ceramic materials.
进一步地，所述无定型氧化物薄膜具有如下特点：厚度为0.1nm-100nm；材质为二元、三元或多元；膜层为单层或者为二元、三元或多元材质且厚度可调的功能化梯度涂层。Further, the amorphous oxide film has the following characteristics: thickness is 0.1nm-100nm; material is binary, ternary or multi-element; the film layer is a single layer or binary, ternary or multi-element material and the thickness is adjustable Functionalized gradient coating.
所述无定型氧化物薄膜的材质包括但不局限于氧化钛、氧化镁、氧化硅、氧化铝、氧化铜、氧化钽、氧化锌、氧化锡、氧化镧和氧化锆等。The materials of the amorphous oxide film include but are not limited to titanium oxide, magnesium oxide, silicon oxide, aluminum oxide, copper oxide, tantalum oxide, zinc oxide, tin oxide, lanthanum oxide, zirconium oxide, etc.
研究表明，通过不同膜层材质的组合及厚度控制，可提高膜层的结合强度，进而避免在后续成型及烧结中脱落、裂纹等情况的发生，提高了氧化物晶粒的品质，从而提高氧化锆陶瓷材料的强度及韧性；同时，通过不同元素成分的时序性释放，可发挥不同的生物学效应，进一步提供了氧化锆陶瓷材料的生物活性。Research shows that through the combination of different film layer materials and thickness control, the bonding strength of the film layer can be improved, thereby avoiding the occurrence of shedding and cracks during subsequent molding and sintering, improving the quality of oxide grains, thereby improving oxidation The strength and toughness of zirconium ceramic materials; at the same time, through the sequential release of different elemental components, different biological effects can be exerted, further providing the biological activity of zirconium oxide ceramic materials.
例如，以氧化铝前驱体为例，经循环次数5次、10次、20次、30次、40次、50次，得到厚度不同、强度不同的氧化锆粉末及氧化锆陶瓷材料，如图5、图9、图10所示，在厚度相同的情况下，本发明所制备的氧化锆陶瓷材料比目前临床中使用的氧化锆材料(3T-TZP)强度提高超过30％，韧性提高1.5倍，应用于牙冠制备时可大幅度降低厚度。For example, taking the alumina precursor as an example, after cycling 5, 10, 20, 30, 40, and 50 times, zirconia powder and zirconia ceramic materials with different thicknesses and strengths are obtained, as shown in Figure 5 As shown in Figures 9 and 10, when the thickness is the same, the strength of the zirconia ceramic material prepared by the present invention is increased by more than 30% and the toughness is increased by 1.5 times compared with the zirconia material (3T-TZP) currently used in clinical practice. The thickness can be significantly reduced when used in crown preparation.
进一步地，本发明所述的成型和烧结工艺的操作条件可根据无定型氧化物薄膜的膜层材质及厚度进行调整，以调控其结晶度，从而实现不同纳米薄膜成分的时序性和精准控制的生物学效应发挥，解决了当前直接原子层沉积 技术只关注沉积本身、而忽略生物学效应的问题，从而获得实用性强、高强高韧、生物活性更好的陶瓷功能化制备技术。Furthermore, the operating conditions of the molding and sintering process of the present invention can be adjusted according to the film material and thickness of the amorphous oxide film to regulate its crystallinity, thereby achieving timing and precise control of different nanofilm components. Biological effects are exerted to solve the current direct atomic layer deposition The technology only focuses on the deposition itself and ignores the biological effects, thereby obtaining functionalized ceramic preparation technology with high practicality, high strength and toughness, and better biological activity.
所述成型为干压成型、湿法成型或增材制造成型。优选地，所述干压成型的压力为130-200MPa；所述湿法成型包括注浆成型、注射成型等。The molding is dry pressing molding, wet molding or additive manufacturing molding. Preferably, the pressure of the dry pressing molding is 130-200MPa; the wet molding includes slip molding, injection molding, etc.
所述烧结的温度为1200-1550℃。The sintering temperature is 1200-1550°C.
通过合理控制成型及烧结条件，在晶粒内和晶界处形成具有纳米和亚微米大小的氧化物晶粒(如氧化铝)，形成的氧化物晶粒(如氧化铝)晶型为晶体或纳米晶，从而显著提高陶瓷材料的强度、韧性及生物活性、成骨活性。By reasonably controlling the molding and sintering conditions, oxide grains (such as alumina) with nanometer and submicron sizes are formed within the grains and at the grain boundaries. The crystal form of the formed oxide grains (such as alumina) is crystal or Nanocrystals can significantly improve the strength, toughness, biological activity and osteogenic activity of ceramic materials.
进一步地，基于不同的无定型氧化物薄膜，其对应的成型及烧结工艺条件也有所不同，所形成的氧化物晶粒也表现出不同的强度、韧性及生物活性。Furthermore, based on different amorphous oxide films, the corresponding molding and sintering process conditions are also different, and the formed oxide grains also show different strengths, toughness and biological activities.
作为本发明的具体实施方式之一，以表面具有无定形氧化铝薄膜的氧化锆粉末颗粒为原料进行成型及烧结处理；所述成型及烧结处理条件为：先干压成型，压力为160-200MPa，再于10-30℃/min速度升温至1300℃-1550℃烧结2h。As one of the specific embodiments of the present invention, zirconium oxide powder particles with an amorphous aluminum oxide film on the surface are used as raw materials for molding and sintering treatment; the molding and sintering treatment conditions are: dry pressing first, and the pressure is 160-200MPa , and then increase the temperature to 1300℃-1550℃ for 2 hours at a speed of 10-30℃/min.
进一步地，所述无定型氧化物薄膜是通过原子层沉积技术在氧化锆粉末颗粒表面形成的。并且，可通过调整前驱体的种类、沉积顺序和循环次数以调控所述功能化梯度涂层中各膜层的材质及厚度。Further, the amorphous oxide film is formed on the surface of the zirconium oxide powder particles through atomic layer deposition technology. Furthermore, the material and thickness of each film layer in the functionalized gradient coating can be adjusted by adjusting the type of precursor, deposition sequence and number of cycles.
作为本发明的具体实施方式之一，提供一种通过ALD技术制备纳米氧化锆陶瓷材料的方法，以氧化铝为例，其反应原理如图1所示，包括如下步骤：As one of the specific embodiments of the present invention, a method for preparing nano-zirconia ceramic materials through ALD technology is provided. Taking alumina as an example, the reaction principle is shown in Figure 1, including the following steps:
(1)前驱体A三甲基铝与氧化锆粉末颗粒的反应位点进行第一次表面反应；(1) The reaction site of precursor A trimethylaluminum and zirconia powder particles undergoes the first surface reaction;
其操作条件为：将干燥后的氧化锆粉末材料放入充满惰性气体的原子层沉积设备的腔体中，升高温度，并保持反应腔体温度在200-350℃之间，达到温度后，反应腔体抽真空1-10s；The operating conditions are: put the dried zirconia powder material into the cavity of the atomic layer deposition equipment filled with inert gas, increase the temperature, and keep the temperature of the reaction cavity between 200-350°C. After reaching the temperature, The reaction chamber is evacuated for 1-10 s;
以氮气为载体，向腔体中通入三甲基铝，反应时间控制为0.1-10s；Use nitrogen as the carrier, pass trimethylaluminum into the cavity, and control the reaction time to 0.1 -10 s;
(2)向腔体中通入惰性气体进行吹扫，去除反应腔内未反应的前驱体A和挥发性副产物氯化氢； (2) Purge the chamber with inert gas to remove unreacted precursor A and volatile by-product hydrogen chloride in the reaction chamber;
(3)将前驱体B水与步骤(1)表面反应后的位点进行第二次表面反应，此时氧化锆粉末颗粒表面转换回具有相同反应位点的起始表面；(3) Perform a second surface reaction between the precursor B water and the sites after the surface reaction in step (1). At this time, the surface of the zirconia powder particles is converted back to the starting surface with the same reaction site;
其操作条件为：以氮气为载体，向腔体通入H2O，反应时间控制为0.01-20s；The operating conditions are: nitrogen is used as the carrier, H 2 O is introduced into the cavity, and the reaction time is controlled to 0.01 -20 s;
(4)再次用惰性气体吹扫，得到一层无定形氧化铝薄膜，完成一个循环过程；(4) Purge with inert gas again to obtain a layer of amorphous aluminum oxide film, completing a cycle process;
(5)重复上述步骤(1)-(4)，直到无定形氧化铝薄膜的厚度达到目标厚度；(5) Repeat the above steps (1)-(4) until the thickness of the amorphous aluminum oxide film reaches the target thickness;
(6)对步骤(5)得到具有无定形氧化铝薄膜的氧化锆粉末颗粒进行成型及烧结处理；(6) Shaping and sintering the zirconia powder particles with amorphous alumina thin films obtained in step (5);
成型及烧结处理的条件为：成型条件可为干压成型：压力为160-200MPa，或湿法成型(如注浆成型)，或增材制造成型等，最终烧结温度为1450℃-1550℃。The conditions for molding and sintering treatment are: The molding conditions can be dry pressing molding: the pressure is 160-200MPa, or wet molding (such as slip molding), or additive manufacturing molding, etc. The final sintering temperature is 1450℃-1550℃.
第二方面，本发明提供一种纳米氧化锆陶瓷材料，其采用上述制备方法得到。In a second aspect, the present invention provides a nano-zirconia ceramic material, which is obtained by the above preparation method.
所述纳米氧化锆陶瓷材料，包括氧化锆晶粒及分布于氧化锆晶粒内和晶界的氧化物晶粒；所述氧化锆晶粒的平均粒径≤1μm；所述氧化物晶粒的平均粒径≤500nm；且随着氧化物晶粒含量的升高，氧化锆晶粒的平均晶粒随之降低；平均粒径≤200nm的氧化物晶粒存在于氧化锆晶粒内；氧化物晶粒晶型为晶体或纳米晶。相比常规氧化锆陶瓷材料，本发明所得纳米氧化锆陶瓷材料具有更高的强度、韧性及更好的生物活性。The nano-zirconia ceramic material includes zirconia grains and oxide grains distributed in the zirconia grains and at grain boundaries; the average particle diameter of the zirconia grains is ≤1 μm; the oxide grains The average particle size is ≤500nm; and as the oxide grain content increases, the average grain size of the zirconia grains decreases; oxide grains with an average grain size ≤200nm exist in the zirconia grains; oxide grains The crystal form of grains is crystal or nanocrystal. Compared with conventional zirconia ceramic materials, the nano zirconia ceramic materials obtained by the present invention have higher strength, toughness and better biological activity.
第三方面，本发明提供一种陶瓷修复材料，其含有上述纳米氧化锆陶瓷材料。In a third aspect, the present invention provides a ceramic repair material, which contains the above-mentioned nano-zirconia ceramic material.
相比与现有常规氧化锆陶瓷材料，本发明所述的陶瓷修复材料具有更好的强度及韧性，良好的美观性能和生物相容性。Compared with existing conventional zirconia ceramic materials, the ceramic repair material of the present invention has better strength and toughness, good aesthetic properties and biocompatibility.
本发明所述技术方案取得的有益效果如下：The beneficial effects achieved by the technical solution of the present invention are as follows:
(1)本发明首次提出将原子层沉积技术应用于氧化锆陶瓷材料的制备技术中。通过以单原子膜的形式将无定形氧化物薄膜一层一层的镀在氧化锆粉末颗粒表面，使其在后续成型及烧结工艺中再结晶，形成分布于氧化锆晶粒 内和晶界的具有纳米尺寸大小的氧化物晶粒(如氧化铝)，氧化物晶粒晶型为晶体或纳米晶，从而实现了增强增韧的目的，解决了现有氧化锆陶瓷材料脆性大的问题。(1) The present invention proposes for the first time the application of atomic layer deposition technology to the preparation technology of zirconia ceramic materials. By plating amorphous oxide films layer by layer on the surface of zirconia powder particles in the form of single-atom films, they are recrystallized in the subsequent molding and sintering processes to form distribution in the zirconia grains. Nano-sized oxide grains (such as alumina) at the internal and grain boundaries are crystals or nanocrystals, thereby achieving the purpose of strengthening and toughening and solving the brittleness of existing zirconia ceramic materials. Big question.
(2)本发明所得氧化锆陶瓷材料具有纳米相结构，不仅增加了成骨细胞的附着，还可增加成骨细胞碱性磷酸酶的合成并促进矿物质的沉积，提高细胞附着的程度和速度，使氧化锆陶瓷材料的生物活性得到显著提升。(2) The zirconia ceramic material obtained by the present invention has a nano-phase structure, which not only increases the attachment of osteoblasts, but also increases the synthesis of osteoblast alkaline phosphatase and promotes the deposition of minerals, improving the degree and speed of cell attachment. , significantly improving the biological activity of zirconia ceramic materials.
(3)本发明通过调整原子层沉积工艺中前驱体种类、沉积顺序及循环次数来控制无定形氧化物薄膜中各层原子组成及厚度，使各膜层协同作用，提高各膜层的结合强度，进而避免在后续成型及烧结中脱落、裂纹等情况的发生，提高了氧化物晶粒的品质，从而提高氧化锆陶瓷材料的强度及韧性；同时，通过不同元素成分的时序性释放，可发挥不同的生物学效应，进一步提供了氧化锆陶瓷材料的生物活性。(3) The present invention controls the atomic composition and thickness of each layer in the amorphous oxide film by adjusting the precursor type, deposition sequence and cycle number in the atomic layer deposition process, so that each film layer works synergistically and improves the bonding strength of each film layer. , thereby avoiding the occurrence of shedding, cracks, etc. during subsequent molding and sintering, improving the quality of oxide grains, thereby improving the strength and toughness of zirconia ceramic materials; at the same time, through the sequential release of different elemental components, it can exert Different biological effects further provide the biological activity of zirconia ceramic materials.
(4)本发明所述制备方法具有工艺相对简单、易于控制，适于大规模工业化生产的优点。(4) The preparation method of the present invention has the advantages of relatively simple process, easy control, and is suitable for large-scale industrial production.
附图说明Description of the drawings
图1为实施例1所述纳米氧化锆陶瓷材料制备工艺的反应原理图。Figure 1 is a reaction principle diagram of the preparation process of nano-zirconia ceramic materials described in Example 1.
图2为不同循环次数得到的氧化锆粉末颗粒TEM结果；其中，control为未处理的氧化锆粉末；10cycles为10次循环(10nm)；30cycles为30次循环(10nm)；50cycles为50次循环(10nm)。Figure 2 shows the TEM results of zirconia powder particles obtained with different cycle times; where control is untreated zirconia powder; 10cycles is 10 cycles (10nm); 30cycles is 30 cycles (10nm); 50cycles is 50 cycles ( 10nm).
图3为对50循环的氧化锆粉末颗粒体部和表面沉积涂层分别进行傅里叶变换(FFT)晶型分析结果。Figure 3 shows the results of Fourier transform (FFT) crystal analysis of the zirconia powder particles and the surface deposited coating after 50 cycles.
图4为不同循环次数得到的氧化锆粉末颗粒及纳米氧化锆陶瓷材料的XRD结果；其中，(a)为氧化锆粉末颗粒；(b)为压制烧结得到的纳米氧化锆陶瓷材料。Figure 4 shows the XRD results of zirconia powder particles and nano-zirconia ceramic materials obtained by different cycle times; among them, (a) is zirconia powder particles; (b) is the nano-zirconia ceramic material obtained by pressing and sintering.
图5为不同循环次数的含氧化铝晶粒的纳米氧化锆陶瓷材料的电镜及面分布图；其中(a)为5次循环(1μm)，右图为氧化锆晶粒中的铝元素分布；(b)为10次循环(400nm)；(c)为20次循环(400nm)；(d)为30次循环(400nm)； (e)为40次循环(400nm)；(f)为50次循环(400nm)；(g)为无处理组(400nm)；(h)为对各组氧化锆晶粒尺寸进行测量分析结果。Figure 5 shows the electron microscope and surface distribution diagram of nano-zirconia ceramic materials containing alumina grains with different cycles; (a) is 5 cycles (1μm), and the right picture shows the distribution of aluminum elements in zirconia grains; (b) is 10 cycles (400nm); (c) is 20 cycles (400nm); (d) is 30 cycles (400nm); (e) is 40 cycles (400nm); (f) is 50 cycles (400nm); (g) is the untreated group (400nm); (h) is the measurement and analysis results of the zirconia grain size of each group.
图6为30循环的含氧化铝晶粒的纳米氧化锆陶瓷材料的电镜图；不同灰度的箭头表明掺杂的氧化铝颗粒不同的分布形式。Figure 6 is an electron microscope image of a nano-zirconia ceramic material containing alumina grains after 30 cycles; arrows with different grayscales indicate different distribution forms of doped alumina particles.
图7为对50循环对含氧化铝晶粒的纳米氧化锆陶瓷材料进行FIB切片后TEM观察结果；其中，(a)为氧化铝颗粒中包含纳米氧化锆颗粒图；(b)为氧化锆颗粒中包含纳米氧化铝颗粒图。Figure 7 shows the TEM observation results after 50 cycles of FIB slicing of nano-zirconia ceramic materials containing alumina grains; (a) is a picture of nano-zirconia particles contained in alumina particles; (b) is a picture of zirconium oxide particles Contains a diagram of nano-alumina particles.
图8为对TEM中的氧化铝颗粒进行光阑选区衍射结果。Figure 8 shows the results of aperture selected diffraction of alumina particles in TEM.
图9为不同氧化锆陶瓷材料的强度对比。Figure 9 shows the strength comparison of different zirconia ceramic materials.
图10为不同氧化锆陶瓷材料的韧性对比。Figure 10 shows the toughness comparison of different zirconia ceramic materials.
图11为不同氧化锆陶瓷材料的成骨性能对比。Figure 11 shows the comparison of osteogenic properties of different zirconia ceramic materials.
图12为不同氧化锆陶瓷材料的成骨相关基因表达结果对比；其中，Runx2为Runt-相关转录因子-2；BMP2为骨形态发生蛋白-2。Figure 12 shows the comparison of osteogenesis-related gene expression results of different zirconia ceramic materials; among them, Runx2 is Runt-related transcription factor-2; BMP2 is bone morphogenetic protein-2.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the invention but are not intended to limit the scope of the invention.
实施例1Example 1
本实施例提供一种纳米氧化锆陶瓷材料的制备方法，以ALD氧化铝为例，反应工艺及原理如图1所示，总反应方程式如下：
2Al(CH3)3(g)+3H2O(g)→Al2O3+6CH4(g)↑This embodiment provides a method for preparing nano-zirconia ceramic materials. Taking ALD alumina as an example, the reaction process and principle are shown in Figure 1, and the overall reaction equation is as follows:
2Al(CH 3 ) 3 (g)+3H 2 O(g)→Al 2 O 3 +6CH 4 (g)↑
第一步：
Al(CH3)3(g)+Zr(OH)(s)→Zr-O-Al(CH3)2(s)+CH4(g)↑first step:
Al(CH 3 ) 3 (g)+Zr(OH)(s)→Zr-O-Al(CH 3 ) 2 (s)+CH 4 (g)↑
第二步：
Zr-O-Al(CH3)2(s)+2H-OH(g)→Zr-O-Al(OH)2(s)+2CH4(g)↑Step two:
Zr-O-Al(CH 3 ) 2 (s)+2H-OH(g)→Zr-O-Al(OH) 2 (s)+2CH 4 (g)↑
具体步骤如下：Specific steps are as follows:
S1、无定形氧化铝薄膜的形成S1. Formation of amorphous aluminum oxide film
(1)将前驱体A三甲基铝引入反应瓶，与氧化锆粉末颗粒上的反应位点进行反应； (1) Introduce the precursor A, trimethylaluminum, into the reaction bottle and react with the reaction sites on the zirconia powder particles;
其操作如下：将干燥后的正极材料放入充满惰性气体的原子层沉积设备的腔体中，升高温度，并保持反应室温度在180℃，达到温度后，反应腔体抽真空10s；The operation is as follows: put the dried cathode material into the cavity of the atomic layer deposition equipment filled with inert gas, increase the temperature, and keep the temperature of the reaction chamber at 180°C. After reaching the temperature, the reaction chamber is evacuated for 10 seconds;
以氮气为载体，向腔体中通入三甲基铝，反应时间控制为1s；Using nitrogen as the carrier, trimethylaluminum is introduced into the cavity, and the reaction time is controlled to 1 s;
(2)用惰性气体吹扫，去除反应腔内未反应的前驱物和挥发性副产物氯化氢；(2) Purge with inert gas to remove unreacted precursors and volatile by-product hydrogen chloride in the reaction chamber;
(3)将前驱体B水引入反应腔进行第二次反应，此时氧化锆粉末颗粒表面转换回具有相同反应位点的起始表面；(3) Introduce the precursor B water into the reaction chamber for the second reaction. At this time, the surface of the zirconia powder particles is converted back to the starting surface with the same reaction site;
其操作条件为：以氮气为载体，向腔体通入H2O，反应时间控制为0.5s；The operating conditions are: nitrogen is used as the carrier, H 2 O is introduced into the cavity, and the reaction time is controlled to 0.5s;
(4)再次用惰性气体吹扫，得到一层无定形氧化铝薄膜，完成一个循环过程；(4) Blow with inert gas again to obtain a layer of amorphous aluminum oxide film, completing a cycle process;
(5)重复上述步骤(1)-(4)，直到无定形氧化铝薄膜的厚度达到目标厚度；(5) Repeat the above steps (1)-(4) until the thickness of the amorphous aluminum oxide film reaches the target thickness;
S2、成型及烧结处理：S2, molding and sintering treatment:
(6)对步骤(5)得到具有无定形氧化铝薄膜的氧化锆粉末颗粒进行成型及烧结处理；(6) Shaping and sintering the zirconia powder particles with amorphous alumina thin films obtained in step (5);
成型方式及操作条件：干压成型，压力为160-200MPa；或湿法成型(如注浆成型)；或增材制造成型等；Molding methods and operating conditions: dry pressing molding with a pressure of 160-200MPa; or wet molding (such as grouting molding); or additive manufacturing molding, etc.;
烧结处理条件：烧结温度为1450-1550℃。Sintering treatment conditions: The sintering temperature is 1450-1550°C.
结果显示：The results show that:
(1)如图2所示，沉积后的粉末透射电镜(TEM)结果中，ALD不同循环数的粉末颗粒表面均匀包覆不同厚度的涂层，且涂层厚度随着循环次数增加而增厚。(1) As shown in Figure 2, in the powder transmission electron microscope (TEM) results after deposition, the surface of powder particles with different ALD cycle numbers is evenly coated with coatings of different thicknesses, and the coating thickness increases as the number of cycles increases. .
(2)如图3所示，对粉末颗粒体部和表面包裹涂层进行选区傅里叶变换(FFT)分析，结果表明氧化锆颗粒体部晶型为晶体，表面涂层为非晶。(2) As shown in Figure 3, a selected Fourier transform (FFT) analysis was performed on the body of the powder particles and the surface coating. The results showed that the crystal form of the body of the zirconia particles was crystalline and the surface coating was amorphous.
(3)如图4所示，X射线衍射(XRD)结果中，ALD不同循环数的粉末中未探测出明显氧化铝成分，而各组氧化锆粉末分别等静压成型、烧结后，氧 化锆片中可探测出微量的氧化铝成分，即表明采用ALD的方法成功在氧化锆粉末颗粒表面沉积了无定型的、非晶氧化铝层，且从循环数可计算出该层厚度为亚纳米级厚度；(3) As shown in Figure 4, in the X-ray diffraction (XRD) results, no obvious alumina component was detected in the powders with different ALD cycle numbers. However, after each group of zirconia powders were isostatically pressed and sintered, the oxygen content was A trace amount of aluminum oxide can be detected in the zirconium oxide flakes, which indicates that the ALD method has successfully deposited an amorphous, amorphous aluminum oxide layer on the surface of the zirconium oxide powder particles, and the thickness of this layer can be calculated from the number of cycles. Nanoscale thickness;
(4)如图5所示，扫描电镜(SEM)及面分布(Mapping)结果证明，随沉积厚度增加，烧结成型后氧化铝颗粒含量增加；且与未处理氧化锆粉末烧制而成的氧化锆相比，在粉末颗粒表面ALD氧化铝的氧化锆晶粒粒径明显减小，表明氧化铝均匀存在于氧化锆晶粒间，限制了氧化锆晶粒的生长；(4) As shown in Figure 5, scanning electron microscopy (SEM) and surface distribution (Mapping) results prove that as the deposition thickness increases, the content of alumina particles after sintering increases; and compared with the oxide particles fired from untreated zirconia powder, Compared with zirconium, the zirconia grain size of ALD alumina on the surface of the powder particles is significantly smaller, indicating that alumina exists uniformly between zirconia grains, limiting the growth of zirconia grains;
(5)如图6所示，烧结成型后的氧化铝晶粒在氧化锆中有不同的分布形式，部分分布在氧化锆晶粒交界处，周围由4～5个氧化锆晶粒包围；部分分布于两个氧化锆晶粒的交接线上；部分被氧化锆晶粒完全包裹；(5) As shown in Figure 6, the alumina grains after sintering have different distribution forms in zirconia. Some are distributed at the junctions of zirconia grains and are surrounded by 4 to 5 zirconia grains; Distributed on the intersection line of two zirconia grains; part of it is completely wrapped by zirconia grains;
(6)如图7所示，聚焦离子束制备切片进行高分辨透射电镜观察(FIB-TEM)，可见氧化锆晶粒中包裹纳米尺寸的氧化铝颗粒；氧化铝晶粒中也会包裹纳米尺寸的氧化锆颗粒；(6) As shown in Figure 7, focused ion beam prepared slices for high-resolution transmission electron microscopy (FIB-TEM) observation. It can be seen that nano-sized alumina particles are wrapped in zirconia grains; nano-sized alumina grains are also wrapped in alumina grains. of zirconia particles;
(7)如图8所示，对氧化铝颗粒进行选区衍射，结果表明氧化铝晶粒中包含大量纳米晶。(7) As shown in Figure 8, selected area diffraction of alumina particles was performed, and the results showed that the alumina grains contained a large number of nanocrystals.
(8)如图9结果所示，参考ISO 6872:2008中对于陶瓷材料强度的双轴弯曲强度试验方法，计算出试样的挠曲强度，可见ALD氧化铝组的氧化锆片强度相比3mol％氧化钇稳定的氧化锆(3Y-TZP)增加30％，比氧化铈稳定的氧化锆(Ce-TZP)相比增加10％。(8) As shown in the results in Figure 9, refer to the biaxial bending strength test method for the strength of ceramic materials in ISO 6872:2008 to calculate the flexural strength of the sample. It can be seen that the strength of the zirconia sheet of the ALD alumina group is compared with 3mol % increased by 30% for yttria stabilized zirconia (3Y-TZP) and 10% compared to cerium oxide stabilized zirconia (Ce-TZP).
(9)如图10结果所示，参考ISO 6872:2008中对于陶瓷材料强度的断裂韧性试验方法，计算出试样的断裂韧性，可见ALD氧化铝组的氧化锆片韧性相比3mol％氧化钇稳定的氧化锆(3Y-TZP)增加约150％，和氧化铈稳定的氧化锆(Ce-TZP)相比增加37％。(9) As shown in the results in Figure 10, refer to the fracture toughness test method for the strength of ceramic materials in ISO 6872:2008 to calculate the fracture toughness of the sample. It can be seen that the toughness of the zirconia sheet of the ALD alumina group is compared with that of 3mol% yttrium oxide. Stabilized zirconia (3Y-TZP) increased by approximately 150% compared to cerium oxide stabilized zirconia (Ce-TZP) by 37%.
(10)生物活性：如图11结果所示，可见ALD氧化铝组的纳米氧化锆片对成骨细胞(MC3T3-e1)碱性磷酸酶表达量增加，预示更好的成骨性能；(10) Biological activity: As shown in the results in Figure 11, it can be seen that the zirconia nanosheets in the ALD alumina group increased the expression of alkaline phosphatase in osteoblasts (MC3T3-e1), indicating better osteogenic performance;
(11)如图12结果所示，和3Y-TZP、Ce-TZP及纳米氧化锆产品NANOZR相比，在ALD氧化铝组的氧化锆片表面培养的MC3T3-e1细胞中成骨相关基因 标志RUNX2和BMP2表达显著提高，表明其具有更好的成骨性能。(11) As shown in the results in Figure 12, compared with 3Y-TZP, Ce-TZP and nano-zirconia product NANOZR, osteogenesis-related genes in MC3T3-e1 cells cultured on the surface of zirconia sheets in the ALD alumina group The expression of markers RUNX2 and BMP2 was significantly increased, indicating better osteogenic properties.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。 Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims (10)

  1. 一种纳米氧化锆陶瓷材料的制备方法，其特征在于，包括：以表面具有无定型氧化物薄膜的氧化锆粉末颗粒为原料，进行成型和烧结处理。A method for preparing nano-zirconia ceramic materials, which is characterized by including: using zirconium oxide powder particles with an amorphous oxide film on the surface as raw materials, and performing shaping and sintering processes.
  2. 根据权利要求1所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述无定型氧化物薄膜具有如下特点：厚度为0.1nm-100nm；材质为二元、三元或多元；膜层为单层或者为二元、三元或多元材质且厚度可调的功能化梯度涂层。The method for preparing nano-zirconia ceramic materials according to claim 1, wherein the amorphous oxide film has the following characteristics: thickness is 0.1nm-100nm; material is binary, ternary or multi-component; film layer It is a functional gradient coating that is a single layer or a binary, ternary or multi-material material with adjustable thickness.
  3. 根据权利要求2所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述成型为干压成型、湿法成型或增材制造成型；The method for preparing nano-zirconia ceramic materials according to claim 2, wherein the forming is dry pressing forming, wet forming or additive manufacturing forming;
    优选地，所述干压成型的压力为130-200MPa。Preferably, the dry pressing pressure is 130-200MPa.
  4. 根据权利要求1-3任一项所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述烧结的温度为1200-1550℃。The method for preparing nano-zirconia ceramic materials according to any one of claims 1 to 3, characterized in that the sintering temperature is 1200-1550°C.
  5. 根据权利要求4所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述无定型氧化物薄膜的材质为氧化铝，其对应的成型及烧结条件为：于压力160-200MPa进行干压成型，再于1300℃-1550℃烧结。The method for preparing nano-zirconia ceramic materials according to claim 4, characterized in that the material of the amorphous oxide film is alumina, and the corresponding molding and sintering conditions are: dry pressing at a pressure of 160-200MPa Shaping and then sintering at 1300℃-1550℃.
  6. 根据权利要求5所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述干压成型后以10-30℃/min速度升温至烧结温度。The method for preparing nano-zirconia ceramic materials according to claim 5, characterized in that after dry pressing, the temperature is raised to the sintering temperature at a speed of 10-30°C/min.
  7. 根据权利要求6所述的纳米氧化锆陶瓷材料的制备方法，其特征在于，所述无定型氧化物薄膜是通过原子层沉积技术在氧化锆粉末颗粒表面形成的。The method for preparing nano-zirconia ceramic materials according to claim 6, wherein the amorphous oxide film is formed on the surface of zirconia powder particles through atomic layer deposition technology.
  8. 一种纳米氧化锆陶瓷材料，其特征在于，采用权利要求1-7任一项所述制备方法获得。A nanometer zirconia ceramic material, characterized in that it is obtained by using the preparation method described in any one of claims 1-7.
  9. 根据权利要求8所述的纳米氧化锆陶瓷材料，其特征在于，所述纳米氧化锆陶瓷材料包括氧化锆晶粒及分布于氧化锆晶粒内和晶界的氧化物晶粒；The nanometer zirconia ceramic material according to claim 8, characterized in that the nanometer zirconia ceramic material includes zirconia grains and oxide grains distributed within the zirconia grains and at grain boundaries;
    所述氧化锆晶粒的平均粒径≤1μm；The average particle size of the zirconium oxide grains is ≤1 μm;
    所述氧化物晶粒的平均粒径≤500nm；The average particle size of the oxide crystal grains is ≤500nm;
    且随着氧化物晶粒含量的升高，氧化锆晶粒的平均粒径随之降低；And as the oxide grain content increases, the average particle size of zirconia grains decreases;
    且平均粒径≤200nm的氧化物晶粒存在于氧化锆晶粒内； And oxide grains with an average particle size ≤200nm exist in the zirconia grains;
    且氧化物晶粒为晶体或纳米晶。And the oxide grains are crystals or nanocrystals.
  10. 一种陶瓷修复材料，其特征在于，含有权利要求8或9所述的纳米氧化锆陶瓷材料。 A ceramic repair material, characterized by containing the nano-zirconia ceramic material according to claim 8 or 9.
PCT/CN2023/116763 2022-09-05 2023-09-04 High-strength high-toughness nano zirconium oxide ceramic material, preparation method therefor, and use thereof WO2024051651A1 (en)

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