CN110015895A - 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法 - Google Patents

一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法 Download PDF

Info

Publication number
CN110015895A
CN110015895A CN201910256731.5A CN201910256731A CN110015895A CN 110015895 A CN110015895 A CN 110015895A CN 201910256731 A CN201910256731 A CN 201910256731A CN 110015895 A CN110015895 A CN 110015895A
Authority
CN
China
Prior art keywords
zro
nano composite
powder
ceramic powder
composite ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910256731.5A
Other languages
English (en)
Inventor
陈超
陈家荣
莫培程
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Nonferrous Metal Guilin Geology and Mining Co Ltd
Original Assignee
China Nonferrous Metal Guilin Geology and Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Nonferrous Metal Guilin Geology and Mining Co Ltd filed Critical China Nonferrous Metal Guilin Geology and Mining Co Ltd
Priority to CN201910256731.5A priority Critical patent/CN110015895A/zh
Publication of CN110015895A publication Critical patent/CN110015895A/zh
Priority to US16/835,444 priority patent/US11332408B2/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C04B35/4885—Composites with aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/6325—Organic additives based on organo-metallic compounds
    • 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
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide
    • 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
    • C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride phase
    • C04B2235/465—Ammonia
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/549—Particle size related information the particle size being expressed by crystallite size or primary particle size
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明提供了一种Al2O3‑ZrO2‑Y2O3‑TiN纳米复合陶瓷粉体及其制备方法，属于陶瓷材料领域。本发明提供的陶瓷粉体中Zr、Al、Y和Ti的摩尔比为(30～70):(10～30):(0.4～1):(5～20)。本发明提供的纳米复合陶瓷粉体分散性较好，没有发生团聚，本发明提供的纳米复合陶瓷粉体烧结后得到的陶瓷材料的力学性能较好。实施例结果表明，本发明提供的纳米复合陶瓷粉体烧结得到的陶瓷材料硬度为28～35GPa、磨耗比为4500～6000:1。

Description

一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其 制备方法
技术领域
本发明涉及陶瓷材料领域，尤其涉及一种纳米复合陶瓷粉体及其制备方法。
背景技术
氧化锆增韧氧化铝陶瓷(zirconia-toughenedalumina，ZTA)材料具有良好的力学性能，ZTA材料的强度和韧性值可以通过改变Y203的添加量来调节，但是最终得到的陶瓷材料的力学性能仍然无法满足人们的需求。
为了提高ZTA材料的硬度和耐磨性，人们选取TiN作为添加相制作氧化物和非氧化物复相陶瓷。将TiN引入ZTA材料后，一方面利用TiN的高熔点、高硬度，能够提高ZTA材料的耐磨性能和硬度；另一方面利用TiN的高导电性，能够采用电火花加工技术将ZTA材料加工成复杂形状的器件。
但是，目前常规的复合方法是用ZTA粉料与TiN粉料机械混合，成型后烧结。这种方法常常造成添加相TiN的团聚，或导致局部组分偏聚，使最终制备得到的复相陶瓷材料的力学性能无法满足人们的需求。
发明内容
本发明提供了一种Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体及其制备方法，本发明提供的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体分散性较好，没有团聚，有效提高了制备得到的陶瓷材料的力学性能。
本发明提供了一种Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，所述陶瓷粉体中Zr元素、Al元素、Y元素和Ti元素的摩尔比为(30～70):(10～30):(0.4～1):(5～20)。
优选的，所述陶瓷粉体中Al2O3、ZrO2、Y2O3和TiN形成固溶体。
优选的，所述陶瓷粉体的一次颗粒的粒径为10～100nm。
本发明还提供了上述技术方案所述Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体的制备方法，包括以下步骤：
(1)将铝盐、锆盐、钇盐和钛盐的有机盐在有机溶剂中混合，加入氨水进行水解反应，得到水解反应产物；
(2)将所述步骤(1)得到的水解反应产物进行固液分离后，固体进行烘干处理，得到中间产物粉体；
(3)将所述步骤(2)得到的中间产物粉体进行梯度煅烧处理，得到Al2O3-ZrO2-Y2O3-Ti2O的固溶体；
(4)将所述步骤(3)得到的固溶体在氨气下进行选择性氮化反应，得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体；所述选择性氮化反应的温度为900～1200℃。
优选的，所述步骤(1)中水解反应的温度为60～90℃，时间为20～40h。
优选的，所述步骤(1)中有机溶剂包括异丙醇和丙三醇中的一种或两种。
优选的，所述步骤(1)中铝盐包括异丙醇铝和正丙醇铝中的一种或两种；所述锆盐包括正丙醇锆、锆酸酯和丙三醇锆中的一种或多种；所述钇盐包括异丙醇钇和正丙醇钇中的一种或两种；所述钛盐包括钛酸异丙酯和钛酸酯中的一种或两种。
优选的，所述步骤(1)中氨水的质量浓度为5％～30％。
优选的，所述步骤(3)中梯度煅烧处理包括顺次进行的一级煅烧和二级煅烧；所述一级煅烧的温度为700～800℃，时间为8～12h；所述二级煅烧的温度为900～1000℃，时间为2～5h。
优选的，所述步骤(3)中梯度煅烧处理在空气气氛中进行。
本发明提供了一种Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，所述陶瓷粉体中Zr元素、Al元素、Y元素和Ti元素的摩尔比为(30～70):(10～30):(0.4～1):(5～20)。本发明提供的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体分散性较好，没有发生团聚，有效提高了制备得到的陶瓷材料的力学性能。实施例结果表明，本发明提供的Al203-Zr02-Y203-TiN纳米复合陶瓷粉体烧结得到的陶瓷材料具有较好的硬度和耐磨性，硬度为28～35GPa、磨耗比为4500～6000:1。
附图说明
图1为本发明实施例1制备得到的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体的XRD图。
具体实施方式
本发明提供了一种Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，所述陶瓷粉体中Zr元素、Al元素、Y元素和Ti元素的摩尔比为(30～70):(10～30):(0.4～1):(5～20)，优选为(40～60):(15～25):(0.5～0.9):(10～15)，进一步优选为60:25:0.76:15。
在本发明中，所述陶瓷粉体中Al2O3、ZrO2、Y2O3和TiN形成固溶体。
在本发明中，所述陶瓷粉体的一次颗粒的粒径优选为10～100nm，进一步优选为10～90nm，更优选为20～60nm。
本发明还提供了上述技术方案所述Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体的制备方法，包括以下步骤：
(1)将铝盐、锆盐、钇盐和钛盐的有机盐在有机溶剂中混合，加入氨水进行水解反应，得到水解反应产物；
(2)将所述步骤(1)得到的水解反应产物进行固液分离后，固体进行烘干处理，得到中间产物粉体；
(3)将所述步骤(2)得到的中间产物粉体进行梯度煅烧处理，得到Al2O3-ZrO2-Y2O3-Ti2O的固溶体；
(4)将所述步骤(3)得到的固溶体在氨气下进行选择性氮化反应，得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体；所述选择性氮化反应的温度为900～1200℃。
本发明将铝盐、锆盐、钇盐和钛盐在有机溶剂中混合，加入氨水进行水解反应，得到水解反应产物。
在本发明中，所述铝盐优选包括异丙醇铝和正丙醇铝中的一种或两种；所述锆盐优选包括正丙醇锆、锆酸酯和丙三醇锆中的一种或多种；所述钇盐优选包括异丙醇钇和正丙醇钇中的一种或两种；所述钛盐优选包括钛酸异丙酯和钛酸酯中的一种或两种。在本发明中，所述有机溶剂优选包括异丙醇和丙三醇中的一种或两种。本发明对铝盐、锆盐、钇盐和钛盐在有机溶剂中的混合方式没有特别要求，采用本领域技术人员所熟知的方式即可。
混合完成后，本发明向上述混合物中加入氨水，进行水解反应。在本发明中，所述氨水的质量浓度优选为5％～30％，进一步优选为10％～25％，所述氨水的加入量优选为过量。在本发明中，所述水解反应的温度优选为60～90℃，进一步优选为70～80℃，更优选为78℃；时间优选为20～40h，进一步优选为20～30h，更优选为24h。本发明通过水解反应，生成了氢氧化铝、氢氧化锆、氢氧化钇和氢氧化钛。
水解反应完成后，本发明将水解反应产物进行固液分离后，固体进行烘干处理，得到中间产物粉体。在本发明中，所述固液分离的方式优选为离心；所述烘干的温度优选为100～140℃，进一步优选为120℃，时间优选为8～10h。本发明通过烘干处理，得到中间产物粉体，能够避免中间产物在后续煅烧过程中发生团聚，有利于提高最终制备得到的陶瓷粉体的均匀性。
得到中间产物粉体后，本发明将中间产物粉体进行梯度煅烧处理，得到Al2O3-ZrO2-Y2O3-Ti2O的固溶体。
在本发明中，所述梯度煅烧处理优选包括顺次进行的一级煅烧和二级煅烧；所述一级煅烧的温度优选为700～800℃，进一步优选为750℃，时间优选为8～12h，进一步优选为10～11h；所述二级煅烧的温度优选为900～1000℃，进一步优选为950℃，时间优选为2～5h，进一步优选为3～4h。在本发明中，所述梯度煅烧处理优选在空气气氛中进行。
得到固溶体后，本发明将所述固溶体在氨气下进行选择性氮化反应，得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体；所述选择性氮化反应的温度为900～1200℃，优选为1000～1100℃。在本发明中，所述选择性氮化反应的时间优选为3～7h，进一步优选为5h。在本发明中，所述选择性氮化反应的具体实施方式优选为：用99％的氧化铝瓷舟将Al2O3-ZrO2-Y2O3-TiO2固溶体放入真空管式高温电炉中，通入流动的氨气，在900～1200℃条件下，反应3～7h。
在本发明中，Al2O3、ZrO2、Y2O3与氨气的反应温度较高，均在1300℃以上，本发明将选择性氮化反应的温度控制在900～1200℃，使得只有TiO2能够与氨气发生氮化反应，生成TiN。在本发明中，所述氨气优选为高纯氨气；所述氨气的流速优选为2～6m/s。本发明优选将氨气流速控制在上述范围内，使氧化钛能够充分被氮化。
本发明通过原位合成氧化钛，然后将氧化钛氮化成氮化钛的方法，有效降低了复相材料的不均匀性，改善TiN相与基体的物理化学相容性。本发明通过原位合成的方法制备得到的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体分散性较好，没有团聚，有效提高了陶瓷材料的力学性能。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。
实施例1
以异丙醇铝(C9H21AlO3)、正丙醇锆(C12H28O4Zr)、异丙醇钇(C9H21O3Y)和钛酸异丙酯(C12H28O4Ti)为原料，按照摩尔比ZrO2:Y2O3＝98.5:1.5、ZrO2:Al2O3:TiO2＝60:25:15称量原料，正丙醇锆19.65克，异丙醇铝10.2克，钛酸异丙酯4.26克，异丙醇钇0.486克。在异丙醇中溶解，放置两小时，加氨水作沉淀剂，接下来在78℃的温度下进行回流24小时，从而得到水解产物。将所述水解产物进行离心，得到的固体用热水清洗。然后将水洗后的固体在120℃真空中烘干，从而得到中间产物(粉末)。
将所得到的中间产物(粉末)在700℃空气中煅烧9h，再以900℃的高温空气煅烧3小时，从而得到结晶Al203-Zr02-Y203-Ti02固溶体超细粉料。超细粉体的一次颗粒的尺寸在10～25nm。
用99％的氧化铝瓷舟直接将Al203-Zr02-Y203-Ti02固溶体超细粉放入真空管式高温电炉中，通入流动的高纯氨气，在900℃下进行选择性氮化反应，反应时间为5h，即可得到Al203-Zr02-Y203-TiN纳米复合陶瓷粉体。
对实施例1制备得到的Al203-Zr02-Y203-TiN纳米复合陶瓷粉体进行XRD测试，测试结果如图1所示，由图1可知，氧化铝、氧化钇、氧化锆已经形成相容的固溶体。
对比例1
以异丙醇铝(C9H21AlO3)、正丙醇锆(C12H28O4Zr)和异丙醇钇(C9H21O3Y)为原料，按照摩尔比ZrO2:Y2O3＝98.5:1.5、ZrO2:Al2O3＝60:25称量原料，正丙醇锆19.65克，异丙醇铝10.2克，异丙醇钇0.486克。在异丙醇中溶解，放置两小时，加氨水作沉淀剂，接下来在78℃的温度下进行回流24小时，从而得到水解产物。这个水解产物被离心，得到的固体用热水清洗。然后将水洗后的固体在120℃真空中烘干，从而得到中间产物粉末。
将所得到的中间产物粉末与TiN粉料机械混合，其中中间产物粉末中Zr元素和TiN粉料中Ti元素的摩尔比为25:15，TiN粉料0.928克，在700℃空气中煅烧9h，再以900℃的高温空气煅烧3小时，从而得到结晶Al2O3-ZrO2-Y2O3-TiN陶瓷粉料。
实施例2
以异丙醇铝(C9H21AlO3)、正丙醇锆(C12H28O4Zr)、异丙醇钇(C9H21O3Y)和钛酸异丙酯(C12H28O4Ti)为原料，按照摩尔比ZrO2:Y2O3＝98.5:1.5、ZrO2:Al2O3:TiO2＝80:15:5称量原料，正丙醇锆26克，异丙醇铝6克，钛酸异丙酯1.4克，异丙醇钇0.646克。在异丙醇中溶解，放置两小时，加氨水作沉淀剂，接下来在78℃的温度下进行回流24小时，从而得到水解产物。将水解产物离心，得到的固体用热水清洗。然后将水洗后的固体在120℃真空中烘干，从而得到中间产物(粉末)。
将所得到的中间产物(粉末)在700℃空气中煅烧9h，再以900℃的高温空气煅烧3小时，从而得到结晶Al2O3-ZrO2-Y2O3-TiO2固溶体超细粉料。超细粉体的一次颗粒的尺寸在10～25nm。
用99％的氧化铝瓷舟直接将Al2O3-ZrO2-Y2O3-TiO2固溶体超细粉放入真空管式高温电炉中，通入流动的高纯氨气，在900℃下进行选择性氮化反应，反应时间为5h，即可得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体。
实施例3
以异丙醇铝(C9H21AlO3)、正丙醇锆(C12H28O4Zr)、异丙醇钇(C9H21O3Y)和钛酸异丙酯(C12H28O4Ti)为原料，按照摩尔比ZrO2:Y2O3＝98.5:1.5、ZrO2:Al2O3:TiO2＝60:25:15称量原料，正丙醇锆19.65克，异丙醇铝10.2克，钛酸异丙酯4.26克，异丙醇钇0.486克。在异丙醇中溶解，放置两小时，加氨水作沉淀剂，接下来在78℃的温度下进行回流24小时，从而得到水解产物。将水解产物离心，得到的固体用热水清洗。然后将水洗后的固体在120℃真空中烘干，从而得到中间产物(粉末)。
将所得到的中间产物(粉末)在700℃空气中煅烧9h，再以950℃的高温空气煅烧3小时，从而得到结晶Al2O3-ZrO2-Y2O3-TiO2固溶体超细粉料。超细粉体的一次颗粒的尺寸在10～100nm。
用99％的氧化铝瓷舟直接将Al2O3-ZrO2-Y2O3-TiO2固溶体超细粉放入真空管式高温电炉中，通入流动的高纯氨气，在1000℃下进行选择性氮化反应，反应时间为5h，即可得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体。
采用热压烧结的方法，将实施例1～3制备得到的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体以及对比例1制备得到的Al2O3-ZrO2-Y2O3-TiN陶瓷粉料制备成陶瓷材料，对实施例1～3以及对比例1制备得到的陶瓷材料的硬度和耐磨性进行测试，测试结果如表1所示：
表1实施例1～3和对比例1制备得到的陶瓷材料的硬度和耐磨性
实施例1 实施例2 实施例3 对比例1
硬度 28GPa 32GPa 35GPa 20GPa
磨耗比 4500:1 5300:1 6000:1 3000:1
由表1可知，由于本发明提供的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体分散性较好，使得本发明提供的纳米复合陶瓷粉体烧结得到的陶瓷材料具有较好的硬度和耐磨性，硬度为28～35GPa、磨耗比为4500～6000:1。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，其特征在于，所述陶瓷粉体中Zr元素、Al元素、Y元素和Ti元素的摩尔比为(30～70):(10～30):(0.4～1):(5～20)。
2.根据权利要求1所述的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，其特征在于，所述陶瓷粉体中Al2O3、ZrO2、Y2O3和TiN形成固溶体。
3.根据权利要求1或2所述的Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体，其特征在于，所述陶瓷粉体的一次颗粒的粒径为10～100nm。
4.权利要求1～3任一项所述Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体的制备方法，包括以下步骤：
(1)将铝盐、锆盐、钇盐和钛盐的有机盐在有机溶剂中混合，加入氨水进行水解反应，得到水解反应产物；
(2)将所述步骤(1)得到的水解反应产物进行固液分离后，固体进行烘干处理，得到中间产物粉体；
(3)将所述步骤(2)得到的中间产物粉体进行梯度煅烧处理，得到Al203-Zr02-Y203-Ti2O的固溶体；
(4)将所述步骤(3)得到的固溶体在氨气下进行选择性氮化反应，得到Al2O3-ZrO2-Y2O3-TiN纳米复合陶瓷粉体；所述选择性氮化反应的温度为900～1200℃。
5.根据权利要求4所述的制备方法，其特征在于，所述步骤(1)中水解反应的温度为60～90℃，时间为20～40h。
6.根据权利要求4或5所述的制备方法，其特征在于，所述步骤(1)中有机溶剂包括异丙醇和丙三醇中的一种或两种。
7.根据权利要求4或5所述的制备方法，其特征在于，所述步骤(1)中铝盐包括异丙醇铝和正丙醇铝中的一种或两种；所述锆盐包括正丙醇锆、锆酸酯和丙三醇锆中的一种或多种；所述钇盐包括异丙醇钇和正丙醇钇中的一种或两种；所述钛盐包括钛酸异丙酯和钛酸酯中的一种或两种。
8.根据权利要求4或5所述的制备方法，其特征在于，所述步骤(1)中氨水的质量浓度为5％～30％。
9.根据权利要求4所述的制备方法，其特征在于，所述步骤(3)中梯度煅烧处理包括顺次进行的一级煅烧和二级煅烧；所述一级煅烧的温度为700～800℃，时间为8～12h；所述二级煅烧的温度为900～1000℃，时间为2～5h。
10.根据权利要求4或9所述的制备方法，其特征在于，所述步骤(3)中梯度煅烧处理在空气气氛中进行。
CN201910256731.5A 2019-04-01 2019-04-01 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法 Pending CN110015895A (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201910256731.5A CN110015895A (zh) 2019-04-01 2019-04-01 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法
US16/835,444 US11332408B2 (en) 2019-04-01 2020-03-31 Al2O3—ZrO2—Y2O3—TiN nanocomposite ceramic powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910256731.5A CN110015895A (zh) 2019-04-01 2019-04-01 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法

Publications (1)

Publication Number Publication Date
CN110015895A true CN110015895A (zh) 2019-07-16

Family

ID=67190326

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910256731.5A Pending CN110015895A (zh) 2019-04-01 2019-04-01 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法

Country Status (2)

Country Link
US (1) US11332408B2 (zh)
CN (1) CN110015895A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939581A (zh) * 2021-02-02 2021-06-11 广东工业大学 一种氧化锆增韧氧化铝刀具及其制备方法
CN113321504A (zh) * 2021-07-06 2021-08-31 中国有色桂林矿产地质研究院有限公司 一种氧化锆增韧氧化铝陶瓷材料及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1349950A (zh) * 2001-11-30 2002-05-22 中国科学院上海硅酸盐研究所 导电性纳米氮化钛－氧化铝复合材料的制备方法
CN1420104A (zh) * 2002-12-06 2003-05-28 中国科学院上海硅酸盐研究所 原位选择氮化法合成的纳米四方氧化锆－氮化钛复合粉体
CN1709826A (zh) * 2005-05-30 2005-12-21 东北大学 一种Al2O3/ZrO2(Y2O3)纳米复合陶瓷刀具材料及其制备方法
CN1793009A (zh) * 2004-11-29 2006-06-28 京瓷株式会社 氧化铝氮化钛类烧结体及其制造方法、磁头用基板、超声波马达、动压力轴承
US20160104551A1 (en) * 2014-10-10 2016-04-14 Korea Institute Of Machinery & Materials Yttria based conductive plasma-resistant member and methods thereof
CN107673772A (zh) * 2017-10-17 2018-02-09 齐鲁工业大学 一种添加氧化锆晶须的Al2O3/Ti(C,N)纳米复合陶瓷刀具材料及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237025C (zh) * 2002-11-28 2006-01-18 中国科学院上海硅酸盐研究所 一种纳米级氮化钛－氮化硅复合材料的制备方法
CN1733634A (zh) * 2004-08-11 2006-02-15 鸿富锦精密工业（深圳）有限公司 纳米线及其制备方法
GB201503976D0 (en) * 2015-03-09 2015-04-22 Element Six Abrasives Sa Polycrystalline abrasive constructions
US20180016678A1 (en) * 2016-07-15 2018-01-18 Applied Materials, Inc. Multi-layer coating with diffusion barrier layer and erosion resistant layer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1349950A (zh) * 2001-11-30 2002-05-22 中国科学院上海硅酸盐研究所 导电性纳米氮化钛－氧化铝复合材料的制备方法
CN1420104A (zh) * 2002-12-06 2003-05-28 中国科学院上海硅酸盐研究所 原位选择氮化法合成的纳米四方氧化锆－氮化钛复合粉体
CN1793009A (zh) * 2004-11-29 2006-06-28 京瓷株式会社 氧化铝氮化钛类烧结体及其制造方法、磁头用基板、超声波马达、动压力轴承
CN1709826A (zh) * 2005-05-30 2005-12-21 东北大学 一种Al2O3/ZrO2(Y2O3)纳米复合陶瓷刀具材料及其制备方法
US20160104551A1 (en) * 2014-10-10 2016-04-14 Korea Institute Of Machinery & Materials Yttria based conductive plasma-resistant member and methods thereof
CN107673772A (zh) * 2017-10-17 2018-02-09 齐鲁工业大学 一种添加氧化锆晶须的Al2O3/Ti(C,N)纳米复合陶瓷刀具材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
韩长日 等: "《精细无机化学品制造技术》", 31 August 2008, 科学技术文献出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112939581A (zh) * 2021-02-02 2021-06-11 广东工业大学 一种氧化锆增韧氧化铝刀具及其制备方法
CN113321504A (zh) * 2021-07-06 2021-08-31 中国有色桂林矿产地质研究院有限公司 一种氧化锆增韧氧化铝陶瓷材料及其制备方法和应用

Also Published As

Publication number Publication date
US11332408B2 (en) 2022-05-17
US20200308060A1 (en) 2020-10-01

Similar Documents

Publication Publication Date Title
US20240254055A1 (en) Preparation method of oxide high-entropy ceramic fiber
CN102757222B (zh) 复合稳定微晶氧化锆陶瓷混合粉体及制作工艺
CN101091914B (zh) 氧化锆基混合氧化物及其制造方法
CN110015895A (zh) 一种氧化铝-氧化锆-氧化钇-氮化钛纳米复合陶瓷粉体及其制备方法
CN102320830A (zh) 氧化锆陶瓷缸套材料及其制备方法
CN111153434A (zh) 一种用于热喷涂的锆酸镧球形粉体制备方法
CN102010185A (zh) 耐高温白色纳米远红外陶瓷粉及其制备方法
CN103936412B (zh) 一种铌锡酸铅-钪酸铋-钛酸铅三元系高温压电陶瓷材料及其制备方法
WO2019019365A1 (zh) 一种氧化铝-氧化锆复合陶瓷连续纤维的制备方法
CN100417598C (zh) 一种氧化钐掺杂稳定氧化锆纳米材料的制备方法
CN101585544A (zh) 一种制备硼酸铝纳米线的方法
CN104193307A (zh) 低成本氧化锆增韧氧化铝陶瓷造粒粉的制备方法
CN108084795A (zh) 一种陶瓷墨水用钴蓝色料及其制备方法
CN109111760A (zh) 一种黑色氧化铝陶瓷用色剂及其制备方法和应用
CN100575305C (zh) 无铅压电陶瓷铌酸锂钠钾纳米粉体的溶胶凝胶合成方法
CN109704403A (zh) 一种高韧性氧化锆基复合粉及其制备方法
CN109553413A (zh) 一种织构化压电陶瓷及其制备方法和用途
CN109704759A (zh) 一种复合稀土改性氧化锆陶瓷粉体及其制备方法
US20200308057A1 (en) Titanium nitride-reinforced zirconia toughened alumina ceramic powder and preparation method thereof
CN105801113A (zh) 一种低单斜相氧化钇部分稳定二氧化锆粉体及其制备方法
CN103626491A (zh) 一种原位合成Gd2Zr2O7/ZrO2(3Y)纳米粉体的方法
CN101687710A (zh) 复合材料制品及相关方法
CN101628733A (zh) 一种常压低温制备氧化镁部分稳定单斜氧化锆粉末的方法
CN103664218B (zh) 一种高韧高强远红外陶瓷及其制备方法
CN117902885A (zh) 一种硬度高且具有非晶-纳米晶双相结构的纳米高熵陶瓷及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Chen Chao

Inventor after: Chen Jiarong

Inventor after: Mo Peicheng

Inventor after: Xie Zhigang

Inventor after: Lin Feng

Inventor before: Chen Chao

Inventor before: Chen Jiarong

Inventor before: Mo Peicheng

CB03 Change of inventor or designer information
RJ01 Rejection of invention patent application after publication

Application publication date: 20190716

RJ01 Rejection of invention patent application after publication