CN104150912A - 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 - Google Patents

一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 Download PDF

Info

Publication number
CN104150912A
CN104150912A CN201410392587.5A CN201410392587A CN104150912A CN 104150912 A CN104150912 A CN 104150912A CN 201410392587 A CN201410392587 A CN 201410392587A CN 104150912 A CN104150912 A CN 104150912A
Authority
CN
China
Prior art keywords
powder
metal
raw material
oxide
gas
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.)
Granted
Application number
CN201410392587.5A
Other languages
English (en)
Other versions
CN104150912B (zh
Inventor
张建峰
吴玉萍
郭文敏
洪晟
李改叶
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.)
Hohai University HHU
Original Assignee
Hohai University HHU
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 Hohai University HHU filed Critical Hohai University HHU
Priority to CN201410392587.5A priority Critical patent/CN104150912B/zh
Publication of CN104150912A publication Critical patent/CN104150912A/zh
Priority to PCT/CN2015/082892 priority patent/WO2016023405A1/zh
Priority to SG11201700921PA priority patent/SG11201700921PA/en
Priority to AU2015303706A priority patent/AU2015303706B2/en
Priority to GB1700878.0A priority patent/GB2542321B8/en
Priority to US15/328,094 priority patent/US10112874B2/en
Priority to DE112015003242.8T priority patent/DE112015003242B4/de
Application granted granted Critical
Publication of CN104150912B publication Critical patent/CN104150912B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5188—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal organic
    • 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
    • C04B35/62892—Coating the powders or the macroscopic reinforcing agents with a coating layer consisting of particles
    • 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
    • C04B35/62802—Powder coating materials
    • C04B35/62842—Metals
    • 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
    • C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • 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
    • C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/053—Fine 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
    • 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
    • C04B35/10—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 aluminium oxide
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/111—Fine 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
    • 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
    • C04B35/14—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 silica
    • 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
    • C04B35/46—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 titanium oxides or titanates
    • 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
    • C04B35/01—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
    • 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
    • C04B35/6261—Milling
    • 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
    • C04B35/6261—Milling
    • C04B35/62615—High energy or reactive ball milling
    • 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
    • C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
    • 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
    • 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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/405—Iron group metals
    • 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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/407—Copper
    • 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
    • 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
    • C04B2235/652—Reduction 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
    • C04B2235/658—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
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • 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
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/781—Nanograined materials, i.e. having grain sizes 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

本发明公开了一种在氧化物陶瓷粉体表面均匀包覆无碳杂质的金属纳米粒子的方法，包括将金属有机原料和氧化物陶瓷粉末研磨混合后放入旋转反应室中，然后在旋转加热的条件通入氧化性气体将金属有机原料氧化为金属氧化物，最后通入还原性气体，将金属氧化物还原为金属态纳米粒子，实现了金属态纳米粒子的均匀包覆，避免高温下长时间包覆反应所导致的纳米粒子粗化和长大的问题。本发明方法简单，制备周期短，制备出的金属纳米粒子分散均匀，作为催化材料、导电陶瓷等在多个领域具有广阔的应用前景。

Description

一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
技术领域
本发明具体涉及一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法，属于材料加工工程领域。
背景技术
在陶瓷粉体，特别是氧化铝(Al2O3)、氧化锆(ZrO2)、氧化硅(SiO2)、四氧化三铁(Fe3O4)等氧化物粉体表面包覆一层一种或几种异相金属纳米粒子，可以同时具备金属包覆壳和陶瓷核的性能，降低粉体团聚效应及各物相(特别是金属和陶瓷)之间的偏聚，赋予氧化物粉体新的性能，如催化性能、电磁性能等，或者有效改变粉体的表面性能，如电化学性能和烧结过程中的扩散能力。因此包覆技术的开发及在结构与功能陶瓷等多领域的应用受到了广泛关注。
目前金属包覆陶瓷型粉体的制备方法主要有机械混合法、溶胶凝胶法、化学镀法和化学气相沉积法等。其中机械混合法最为简单，但对密度性质差别较大的粉体通常难以混合均匀。溶胶凝胶法是将原料分散在溶剂中，通过水解形成溶胶及凝胶，经过干燥和热处理获得所需纳米粒子材料的方法。Rodeghiero等人就曾采用溶胶凝胶法在获得了Ni-Al2O3粉体。他们将溶胶凝胶处理后的粉体在H2气氛中热处理1小时，将Ni盐还原为Ni，后将粉体在1350～1400℃的温度条件下热压烧结2～4小时，获得了致密的Al2O3-Ni复合材料(Materials Science andEngineering A,1995,195,pp151～161)。虽然与固相反应相比，溶胶凝胶法中的化学反应更容易进行，且合成温度较低，但后续的高温热处理(煅烧晶化及还原得到金属相)往往温度较高，易引起粉体团聚及金属相的微烧结。
化学镀通过无外加电场的电化学过程对粉体进行包覆，具有设备简单、镀层性能可设计等优点，是应用较为广泛的一种方法。曹晓国等人采用化学镀法，以甲醛为还原剂，在水/乙醇介质中将银包覆在Fe3O4粉体表面。测试结果表明，在Fe3O4粉体表面包覆的均匀、完整的银层有效提高了Fe3O4粉体的体剂电导率。(材料工程，2007，4，pp57～60)。Mehmet Uysal等人采用电镀法获得了Ni包覆的Al2O3粉体。他们首先是在SnCl2溶液中对Al2O3粉体进行预处理以提高Al2O3粉体的表面活性，然后以NiCl2为Ni源，通过控制溶液的PH值，NiCl2浓度等工艺参数，在Al2O3粉体表面包覆了均匀分布的Ni纳米粒子(CeramicsInternational，2013，39，pp5485-5493)。但粉体化学镀具有一定的特殊性。要实现表面改性层的均匀沉积，粉体表面应具有良好的催化活性，对于陶瓷等不具有表面催化活性的粉体，应进行必要的预处理使之活化；同时，为使粉体能在镀液中均匀分散，镀液应具有一定的稳定性以免自发分解。因此，其应用范围受到一定的限制。
化学气相沉积法通过原料气体在颗粒表面聚集反应而形成固态沉积物，从而达到对粉体颗粒的包覆效果。蒋永等采用化学气相沉积法在粒径为200nm的LiFePO4粉体表面包覆了碳层(硅酸盐学报，2008，36，pp1295～1299)。Zhang等人采用化学气相沉积法，以金属有机物为原料，先将原料加热挥发，以Ar气带入到高温反应室中，通过高温分解在氧化铝表面包覆了Ni纳米粒子。但在较高的包覆温度下，纳米粒子容易团聚和长大，从而导致粉体烧结后的硬度和强度降低(Journal of the European Ceramic Society,2014,34,pp435-441)。
发明内容
本发明的目的在于提供一种在氧化物陶瓷粉体表面均匀包覆金属纳米粒子的方法，通过事先将金属有机原料和包覆粉体混合，在反应室加热的过程中实现金属纳米粒子的均匀包覆，降低包覆温度，提高分散的均匀性。
为实现上述技术目的，本发明采取如下技术方案：一种在氧化物陶瓷表面包覆金属纳米粒子的方法，包括如下步骤：
(1)将氧化物陶瓷粉体与金属有机原料按照重量比(1:1)～(10:1)进行配料，研磨混合1～3h得到混合粉体，将研磨后的混合粉体放置于旋转式反应器中，启动旋转反应器使其旋转；
(2)向旋转反应器内通入氧气和氩气的混合气体，以5～10℃/min的速率升温至400～500℃后，保温0.5～2h，使金属有机原料氧化为金属氧化物，然后关闭氧气和氩气的气体进气阀门；
(3)向旋转式反应器中通入还原性气体将步骤(2)中的金属氧化物还原为金属态纳米粒子，同时以5～10℃/min的速率降温，降至室温后，关闭还原性气体的进气阀门，停止旋转式反应器的旋转，打开仪器，取出粉体，过筛，收集粉体。
其中，所述的氧化物陶瓷粉体为Al2O3、ZrO2、SiO2、MgO和TiO2中的任意一种，粒径为100nm～100μm，纯度大于95％。
所述金属有机源为烷基或者芳香基的烃基与金属原子结合形成的稳定有机金属化合物，其种类根据需要包覆的金属纳米粒子的种类进行选择，如当需要在氧化陶瓷粉体表面包覆镍纳米粒子时，所述的金属有机源为二茂镍(NiCp2)、四羟基镍(Ni(CO)4)和醋酸镍(Ni(CH3COO)2·4H2O)中的任意一种。
当需要在氧化陶瓷粉体表面包覆铜纳米粒子时，选用的金属有机源可以为Cu(DPM)2。
当需要在氧化陶瓷粉体表面包覆钴纳米粒子时，选用的金属有机源为二茂钴或羟基钴。
当需要在氧化陶瓷粉体表面包覆铁纳米粒子时，选用的金属有机源为二茂铁。
具体地，步骤(2)中，通入的氧气和氩气的混合气体总压力为200～1000Pa，其中氧气的分压为50～200Pa，升温速度为2～10℃min，旋转反应器的旋转速率为15～60r/min。
步骤(3)中，所述的还原性气体为氢气、一氧化碳和甲烷中的任意一种，所述还原性气体的分压为100～400Pa。
优选地，步骤(3)中，所述的粉体过50～200目筛三次。
有益效果：本发明提供了一种能够在不同氧化物陶瓷粉体表面包覆均匀分布的金属纳米粒子的新方法。通过控制工艺条件和选择合适的金属有机原料，在不同氧化物陶瓷粉体表面包覆金属纳米粒子层，从而对粉体的表面形貌、导电性等进行调控，使材料的利用率、产品的可靠性得到大大提高，制备周期短、能耗低、环境友好，生产成本显著降低，从而具有良好的产业前景。通过将氧化物陶瓷粉体与金属有机原料预先混合，提高了金属纳米粒子包覆的均匀性；另外在加热过程中，同时进行金属纳米粒子的氧化分解，降低了在高温下反应时间，避免了金属纳米粒子的粗化和长大。
附图说明
图1实施例1中Al2O3粉体包覆Ni纳米粒子的X射线衍射图谱：(a)包覆前，(b)包覆后；
图2实施例1中Al2O3粉体包覆Ni纳米粒子的透射电镜照片；
图3实施例3中ZrO2粉体包覆Ni纳米粒子后的X射线衍射图谱；
图4实施例3中ZrO2粉体包覆Ni纳米粒子的透射电镜照片。
具体实施方式
以下为本发明的优选实施方式，仅用于解释本发明，而非用于限制本发明，且由该说明所作出的改进都属于本发明所附权利要求所保护的范围。
实施例1 Al2O3粉体表面包覆Ni纳米粒子。
首先将普通商用5g Al2O3粉体(粒径为500nm)和0.5g Ni(CO)4混合后，放入旋转反应器中，将反应器旋转，旋转速率为45r/min。通入氧气和Ar的混合气体，混合气体的总压力为1000Pa，其中氧气的分压为100Pa。升温速率为8℃/min，升温至温度为450℃后保温45min，使Ni(CO)4氧化为氧化镍，然后关闭氧气供应阀门，通入一氧化碳将金属氧化物氧化镍还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为45min，然后开始降温，降温速率为8℃/min。降至室温后，关闭气体阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过100目筛三次，收集粉体。对收集的粉体进行表征，结果如图1和图2所示。其中，图1为Al2O3粉体包覆Ni纳米粒子的X射线衍射图谱，a为包覆前，b为包覆后，证明了Al2O3粉体成功包覆上了Ni纳米粒子。图2为Al2O3粉体包覆Ni纳米粒子的透射电镜照片，从图中可以看出，Ni纳米粒子均匀地包覆在Al2O3粉体表面。
实施例2 Al2O3粉体表面包覆Cu纳米粒子。
首先将普通商用5g Al2O3粉体(粒径为100nm)和2g Cu(DPM)2(copperdipivaloylmethanate)混合后，放入旋转反应器中，关闭旋转反应器的入料口阀门，启动旋转反应器旋转，旋转速率调节为60r/min。然后通入氧气和氩气的混合气体，混合气体的总压力为800Pa，其中氧气的分压为50Pa。升温速率设置为5℃/min，升温至400℃后保温60min，使Cu(DPM)2氧化为氧化铜，然后关闭氧气供应阀门，通入甲烷将金属氧化物CuO还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为60min，然后开始降温，降温速率为5℃/min。降至室温后，关闭一氧化碳进气阀门和氩气进气阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过200目筛三次，收集粉体。
实施例3 ZrO2粉体表面包覆Ni纳米粒子。
首先将普通商用5g ZrO2粉体(粒径为10μm)和5g NiCp2(nickelocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为15r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为200Pa。升温速率为7℃/min，升温至温度为450℃后保温30min，从而将NiCp2氧化为NiO，然后关闭氧气供应阀门，通入氢气将金属氧化物NiO还原为金属态纳米粒子。氢气的分压为400Pa，还原反应时间为30min，然后开始降温，降温速率为7℃/min。降至室温后，关闭气体阀门，停止仪器旋转和反应器的加热，打开仪器，取出粉体，过100目筛三次，收集粉体。对收集的粉体进行表征，结果如图3和图4所示。其中，图3为ZrO2粉体包覆Ni纳米粒子的X射线衍射图谱，证明了ZrO2粉体成功包覆上了Ni纳米粒子。图4为ZrO2粉体包覆Ni纳米粒子的透射电镜照片，从图中可以看出，Ni纳米粒子均匀地包覆在ZrO2粉体表面。
实施例4 TiO2粉体表面包覆Co纳米粒子。
以在TiO2粉体表面包覆Co纳米粒子为例，首先将普通商用5g TiO2粉体(粒径为50μm)和2g CoCp2(Cobaltocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为200Pa，其中氧气的分压为50Pa。升温速率为10℃/min，升温至温度为400℃后保温15min，从而将CoCp2转化为氧化钴，然后关闭氧气供应阀门，通入甲烷将金属氧化物氧化钴还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为15in，然后开始降温，降温速率为10℃/min。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例5 SiO2粉体表面包覆Fe纳米粒子。
以在SiO2粉体表面包覆Fe纳米粒子为例，首先将普通商用5g SiO2粉体(粒径为100μm)和1g FeCp2(ferrocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为10Pa。升温速率为8℃/min，最终反应温度为500℃，保温时间为30min，从而将FeCp2氧化为氧化铁，然后关闭氧气供应阀门，通入一氧化碳将氧化铁还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为30min，然后以8℃/min的速率降温。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例6 MgO粉体表面包覆Co纳米粒子。
以在MgO粉体表面包覆Co纳米粒子为例，首先将普通商用6g MgO粉体(粒径为50μm)和2g CoCp2(Cobaltocene)混合后，放入旋转反应器中，将反应器旋转，旋转速率为60r/min。通入氧气和Ar的混合气体，混合气体的总压力为600Pa，其中氧气的分压为150Pa。升温速率为6℃/min，升温至温度为400℃后保温20min，从而CoCp2被氧化为氧化钴，然后关闭氧气供应阀门，通入甲烷将金属氧化物Co2O3还原为金属态纳米粒子。甲烷的分压为100Pa，还原反应时间为15in，然后开始降温，降温速率为10℃/min。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。
实施例7 SiO2粉体表面包覆Ni纳米粒子。
以在SiO2粉体表面包覆Ni纳米粒子为例，首先将普通商用5g SiO2粉体(粒径为100μm)和3g Ni(CH3COO)2·4H2O混合后，放入旋转反应器中，将反应器旋转，旋转速率为50r/min。通入氧气和Ar的混合气体，混合气体的总压力为800Pa，其中氧气的分压为15Pa。升温速率为8℃/min，最终反应温度为500℃，保温时间为30min，从而Ni(CH3COO)2·4H2O被氧化为氧化镍，然后关闭氧气供应阀门，通入一氧化碳将氧化镍还原为金属态纳米粒子。一氧化碳的分压为200Pa，还原反应时间为30min，然后以8℃/min的速率降温。降至室温后，关闭气体阀门，停止仪器旋转，打开仪器，取出粉体，过50目筛三次，收集粉体。

Claims (9)

1.一种在氧化物陶瓷表面包覆金属纳米粒子的方法，其特征在于，包括如下步骤：
(1)将氧化物陶瓷粉体与金属有机原料按照重量比(1:1)～(10:1)进行配料，研磨混合1～3h得到混合粉体，将研磨后的混合粉体放置于旋转式反应器中，启动旋转反应器使其旋转；
(2)向旋转反应器内通入氧气和氩气的混合气体，以5～10℃/min的速率升温至400～500℃后，保温0.5～2h，使金属有机原料氧化为金属氧化物，然后关闭氧气和氩气的气体进气阀门；
(3)向旋转式反应器中通入还原性气体将步骤(2)中的金属氧化物还原为金属态纳米粒子，同时以5～10℃/min的速率降温，降至室温后，关闭还原性气体的进气阀门，停止旋转式反应器的旋转，打开仪器，取出粉体，过筛，收集粉体。
2.根据权利要求1所述的方法，其特征在于，所述的氧化物陶瓷粉体为Al2O3、ZrO2、SiO2、MgO和TiO2中的任意一种，粒径为100nm～100μm，纯度大于95％。
3.根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂镍、四羟基镍和醋酸镍中的任意一种。
4.根据权利要求1所述的方法，其特征在于，所述的金属有机原料为Cu(DPM)2。
5.根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂钴或羟基钴。
6.根据权利要求1所述的方法，其特征在于，所述的金属有机原料为二茂铁。
7.根据权利要求1所述的方法，其特征在于，步骤(2)中，通入的氧气和氩气的混合气体总压力为200～1000Pa，其中氧气的分压为50～200Pa，升温速度为2～10℃min，旋转反应器的旋转速率为15～60r/min。
8.根据权利要求1所述的方法，其特征在于，步骤(3)中，所述的还原性气体为氢气、一氧化碳和甲烷中的任意一种，所述还原性气体的分压为100～400Pa。
9.根据权利要求1所述的方法，其特征在于，步骤(3)中，所述的粉体过50～200目筛三次。
CN201410392587.5A 2014-08-11 2014-08-11 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法 Expired - Fee Related CN104150912B (zh)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201410392587.5A CN104150912B (zh) 2014-08-11 2014-08-11 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
PCT/CN2015/082892 WO2016023405A1 (zh) 2014-08-11 2015-06-30 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
SG11201700921PA SG11201700921PA (en) 2014-08-11 2015-06-30 Method for coating metal nanoparticles on oxide ceramic powder surface
AU2015303706A AU2015303706B2 (en) 2014-08-11 2015-06-30 Method for coating metal nanoparticles on surface of oxide ceramic powder
GB1700878.0A GB2542321B8 (en) 2014-08-11 2015-06-30 Method for coating metal nanoparticles on surface of oxide ceramic powder
US15/328,094 US10112874B2 (en) 2014-08-11 2015-06-30 Method for coating metal nanoparticles on oxide ceramic powder surface
DE112015003242.8T DE112015003242B4 (de) 2014-08-11 2015-06-30 Verfahren zum Beschichten der Oberfläche der oxidkeramischen Pulver mit den Metallnanopartikeln

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410392587.5A CN104150912B (zh) 2014-08-11 2014-08-11 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法

Publications (2)

Publication Number Publication Date
CN104150912A true CN104150912A (zh) 2014-11-19
CN104150912B CN104150912B (zh) 2015-10-21

Family

ID=51876577

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410392587.5A Expired - Fee Related CN104150912B (zh) 2014-08-11 2014-08-11 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法

Country Status (7)

Country Link
US (1) US10112874B2 (zh)
CN (1) CN104150912B (zh)
AU (1) AU2015303706B2 (zh)
DE (1) DE112015003242B4 (zh)
GB (1) GB2542321B8 (zh)
SG (1) SG11201700921PA (zh)
WO (1) WO2016023405A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023405A1 (zh) * 2014-08-11 2016-02-18 河海大学 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
CN108610059A (zh) * 2016-12-09 2018-10-02 财团法人工业技术研究院 表面改质陶瓷粉体及其应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111517757B (zh) * 2019-02-01 2022-05-27 河北勇龙邦大新材料有限公司 一种空心陶瓷微珠的烧结方法与装置
CN113233882A (zh) * 2021-05-17 2021-08-10 中南大学 一种体导电石英的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5271969A (en) * 1985-10-29 1993-12-21 Atsushi Ogura Method of manufacturing metal oxide ceramic composite powder
JPH0987039A (ja) * 1995-09-29 1997-03-31 Taiyo Yuden Co Ltd セラミック材料粉末の製造方法
CN102660261A (zh) * 2012-04-19 2012-09-12 中国科学技术大学 一种硅氧氮化物荧光粉的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2825296B1 (fr) 2001-05-30 2003-09-12 Toulouse Inst Nat Polytech Procede de fabrication de nanoparticules metalliques supportees en lit fluidise
CN1159259C (zh) * 2002-04-05 2004-07-28 北京化工大学 一种纳米金属粒子/炭复合材料的制备方法
CN101259532A (zh) * 2008-01-02 2008-09-10 中南大学 纳米Fe或Fe2O3包覆Si3N4颗粒的复合粉末及其制备方法
US8481115B2 (en) * 2008-03-27 2013-07-09 Hitachi Metals, Ltd. Coated, fine metal particles comprising titanium oxide and silicon oxide coating, and their production method
CN101314545A (zh) * 2008-07-02 2008-12-03 广东风华高新科技股份有限公司 一种制备电介质陶瓷粉体的喷雾包覆方法及所得的产品
CN101439973A (zh) * 2008-12-23 2009-05-27 四川大学 一种铜包覆碳化硅复合材料及其制备
CN104583129B (zh) 2012-08-30 2016-09-07 国立大学法人东京工业大学 导电性钙铝石型化合物粉末的制造方法
CN104150912B (zh) * 2014-08-11 2015-10-21 河海大学 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5271969A (en) * 1985-10-29 1993-12-21 Atsushi Ogura Method of manufacturing metal oxide ceramic composite powder
JPH0987039A (ja) * 1995-09-29 1997-03-31 Taiyo Yuden Co Ltd セラミック材料粉末の製造方法
CN102660261A (zh) * 2012-04-19 2012-09-12 中国科学技术大学 一种硅氧氮化物荧光粉的制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023405A1 (zh) * 2014-08-11 2016-02-18 河海大学 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
GB2542321A (en) * 2014-08-11 2017-03-15 Univ Hohai Method for coating metal nanoparticles on surface of oxide ceramic powder
GB2542321B (en) * 2014-08-11 2018-05-02 Univ Hohai Method for coating metal nanoparticles on surface of oxide ceramic powder
US10112874B2 (en) 2014-08-11 2018-10-30 Hohai University Method for coating metal nanoparticles on oxide ceramic powder surface
CN108610059A (zh) * 2016-12-09 2018-10-02 财团法人工业技术研究院 表面改质陶瓷粉体及其应用
US10894288B2 (en) 2016-12-09 2021-01-19 Industrial Technology Research Institute Surface-treated ceramic powder and applications thereof
CN108610059B (zh) * 2016-12-09 2021-10-22 财团法人工业技术研究院 表面改质陶瓷粉体及其应用

Also Published As

Publication number Publication date
WO2016023405A1 (zh) 2016-02-18
DE112015003242T5 (de) 2017-04-13
GB201700878D0 (en) 2017-03-01
CN104150912B (zh) 2015-10-21
AU2015303706A1 (en) 2017-02-09
GB2542321B (en) 2018-05-02
GB2542321B8 (en) 2018-07-11
US20170217840A1 (en) 2017-08-03
US10112874B2 (en) 2018-10-30
AU2015303706B2 (en) 2017-07-20
GB2542321A (en) 2017-03-15
SG11201700921PA (en) 2017-03-30
DE112015003242B4 (de) 2023-01-05

Similar Documents

Publication Publication Date Title
Zhang et al. Recent advances in 1D electrospun nanocatalysts for electrochemical water splitting
CN100534675C (zh) 一种球形纳米银粉的制备方法
Kong et al. Construction of metal-organic framework derived Co/ZnO/Ti3C2Tx composites for excellent microwave absorption
CN104150912B (zh) 一种在氧化物陶瓷粉体表面包覆金属纳米粒子的方法
CN110038614B (zh) 一种氮化钴负载的氮掺杂碳材料及其制备方法
CN109201068B (zh) 一种减少副产物碳层的碳纳米线圈合成用催化剂的制备方法及其应用
CN110148760B (zh) 一种多孔碳-碳纳米管复合材料及其制备方法和应用
Wang et al. Synthesis of multishelled SnOx/Co3O4 amorphous/crystalline heterophase with galvanic replacement reaction for superior HCHO sensing
CN113477270B (zh) 一种铜铁双金属限域氮掺杂碳纳米管复合材料的制备方法
CN110975914B (zh) 磷掺杂氧化镍铁氮掺杂碳纳米纤维复合材料及其制备方法与应用
CN103072987B (zh) 一种制备金属碳化物或碳包覆金属碳化物的方法
CN114042468B (zh) 一种核壳结构Fe2P@C-Fe3C电催化剂及其制备方法和应用
CN112705235B (zh) 碳包覆碳化镍的纳米复合材料及其制备方法和应用
CN104625082B (zh) 一种纳米级镍粉的制备方法
US11668016B2 (en) Ultra-thin carbon-layer composite material modified by nickel nanoclusters and vanadium carbide particles and its preparation method and application
Guo et al. Preparation and in situ reduction of Ni/SiCxOy catalysts supported on porous SiC ceramic for ethanol steam reforming
CN112938936A (zh) 一种金属原子负载的纳米复合材料及其制备方法
Yu et al. Synergistic enhancement of optical properties in Ca/Ni co-doped LaFeO3 perovskite coatings enabling high-temperature photothermal conversion
CN110451498B (zh) 一种石墨烯-氮化硼纳米片复合结构及其制备方法
Qiu et al. Enhanced catalytic activity for methane dry reforming of Ce-doped Ba0. 9Zr0. 7Y0. 2Ni0. 1O3-δ perovskite catalyst
CN112897483A (zh) TiN(B)@TiO2核-壳颗粒粉末材料及制备方法
WO2023241152A1 (zh) 一种空心氮掺杂碳包裹二氧化钛光催化剂的制备方法
Liu et al. Experimental study on the preparation of monodisperse nano-silver by hydrothermal synthesis
Zhong et al. Research progress of Co-based spinel oxide materials for direct methanol fuel cells
CN109371505B (zh) 一种生物质基螺旋状碳纤维及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151021

Termination date: 20180811