CN110143826A - A kind of functional cellular shape ceramics and preparation method thereof - Google Patents

A kind of functional cellular shape ceramics and preparation method thereof Download PDF

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Publication number
CN110143826A
CN110143826A CN201910428517.3A CN201910428517A CN110143826A CN 110143826 A CN110143826 A CN 110143826A CN 201910428517 A CN201910428517 A CN 201910428517A CN 110143826 A CN110143826 A CN 110143826A
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ceramics
functional cellular
ceramic
cellular shape
metal oxide
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陈照峰
王恩慧
罗发
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Suqian Southern Airlines New Materials And Equipment Manufacturing Research Institute Co Ltd
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Suqian Southern Airlines New Materials And Equipment Manufacturing Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/26—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 ferrites
    • C04B35/2666—Other ferrites containing nickel, copper or cobalt
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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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
    • 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
    • C04B2235/02—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
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
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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
    • C—CHEMISTRY; METALLURGY
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    • 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

Abstract

The present invention provides a kind of functional cellular shape ceramics and preparation method thereof, it is characterised in that the functional cellular shape ceramics are by Fe2O3‑MnO2‑Co2O3The compound system ceramics of-CuO system transition metal oxide ceramics and cordierite composition, in 8~14 μm of room temperature far infrared radiation rates up to 0.90~0.95；The functional cellular shape ceramic capillary precision is 1 μm~100 μm, and AgO solid particle is contained in micropore, has bacteriostasis property.The beneficial effect that the present invention obtains is: functional cellular shape ceramics caused by the present invention do not utilize the thermal energy of external environment or human body that can work by under additional energy source room temperature, energy saving；Bacteriostasis property is had both, the wholesomeness in its use process is improved；Honeycomb structure alleviates material self weight, and substantially increases the heat storage capacity of material；Cordierite overcomes the defect of the poor thermal shock resistance of transition metal oxide system ceramics, and prepared compound system ceramics thermal expansion coefficient is low, and thermal shock resistance is good, long service life.

Description

A kind of functional cellular shape ceramics and preparation method thereof
Technical field
The present invention relates to a kind of ceramic honeycombs more particularly to a kind of functional cellular shape ceramics and preparation method thereof
Background technique
Infrared radiation ceramic refers to the inorganic material for having high radiant rate or characteristic radiation rate in infrared band.Radiation is one Cut the build-in attribute of object.One of transition metal oxide or several mix will form AB2O4, similar point crystalline substance The ferrite of stone structure, A and B respectively represent divalent and trivalent metal cation, and are filled in the tetrahedron and eight of spinelle respectively In the body space of face.The optical frequency of the caused lattice wave of spinel crystal lattice vibration is close with infrared frequency, when substance is by red When outside line is irradiated, infra-red radiation can resonate with crystals dipole, promote infrared absorption and transmitting.When in crystal structure When mixing impurity, especially when tetrahedron gap or octahedral interstices are occupied by different metal ions, on impurity lattice Charge imbalance is caused, while electron exchange behavior can be generated between ion, causes electronics in different transition between the energy levels, enhances red The absorption of wave section, while distortion of lattice can be caused in impurity or fault location, the symmetry of lattice vibration is reduced, dipole moment becomes Change and increase, promotes material infrared absorption.Although transition metal oxide infrared emittance is high, thermal expansion coefficient is larger, resistance to Thermal impact is poor, can only be often subject in the form of powder or coating using application range is by biggish limitation.Therefore people The substances such as itself and the lesser cordierite of thermal expansion coefficient or mullite are compound to improve its performance.Cordierite structure has excellent Radiation characteristic, ion arrangement is loose, there is biggish cavity in lattice, and thermal stability is good, heat resistance with higher and anti- Thermal impact.Cordierite is introduced in multiphase system can not only reduce thermal expansion coefficient, improve material in use Shock resistance, and the low deficiency of certain other constituent elements radiances in subband can be made up.
Chinese patent CN01128407.2 discloses a kind of infrared radiation ceramic glaze layer with bacteria resistance function and its preparation Main group of method, the glaze layer becomes potassium feldspar, SiO2、CaCO3, ZnO, talcum, ZrSiO4, clay, BaCO3, opaque it is molten Block, colorant and infrared radiation ceramic material use ceramic processing technique after mixing the various composition in above-mentioned compositing range The infrared radiation ceramic glaze layer radiance of preparation is up to 0.82~0.83, to mould bacterium bacteriostasis rate up to 91.87%~100%, But its heat storage capacity is low, heat insulation effect is poor, and the material thermal shock resistance is poor, and safety in utilization is small, limits it and answers Use range.Chinese patent CN201810983537.2 discloses a kind of preparation side of cordierite complex ferrite infrared radiation ceramic Method prepares ferrite by gel method；In proportion with cordierite and calcined kaolin ground and mixed, compressed with adhesive sintering is added Obtain cordierite complex ferrite infrared radiation ceramic.Infrared radiation ceramic prepared by the invention is with lower thermal expansion system Number, good thermal shock resistance, higher infrared radiation property.But it does not have anti-microbial property, function limitation, and material sheet Body weight is big, and heat storage capacity is not as good as cellular ceramic structural.
In conclusion there is no light weight at present, heat storage capacity is extremely strong, the good functionality for having both anti-microbial property again of thermal stability Ceramic material, therefore the object of the invention is to application and preparations in medical facilities, health care, kitchen utilities, the fields such as building Antibacterial heat radiation light ceramic material.
Summary of the invention
For the shortcoming of background technique, the present invention is implemented as follows:
A kind of functional cellular shape ceramics, are by Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramics and violet are green The compound system ceramics of stone composition, in 8~14 μm of room temperature far infrared radiation rates up to 0.90~0.95；The functional cellular Shape ceramic capillary precision is 1 μm~100 μm, and AgO solid particle is contained in micropore, has bacteriostasis property.
Further, the Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramic preparation includes following Step:
1) the pure Fe of chemistry is weighed by weight 55~65: 15~25: 5~15: 5~152O3、MnO2、Co2O3, CuO, mix Synthesize batch；
2) by above-mentioned batch through 10~16h of wet ball grinding, tablet is pressed into the pressure of 15~25MPa；
3) tablet is sintered to 1.5~2.5h in air, sintering temperature is 1050~1200 DEG C, then cools to room with the furnace The obtained transition metal oxide ceramics of temperature.
Further, the functional cellular shape ceramics preparation method the following steps are included:
1) transition metal oxide Ceramic manufacturing obtained is proportionally weighed with cordierite ceramic powder and is matched at fine powder Material, transition metal oxide ceramic powder mass ratio are 20~40%；
2) plus after plasticizer use wet ball grinding to 10 μm of particles below, granule content is 75%~85%, with 120 μm Sieve screening, except iron, press filt, pug it is aging after extrude to form green honeycomb body；
3) it by green body plastic removal, is then rapidly heated through high temperature furnace to 1150~1400 DEG C, keeps the temperature 2~6h, be fired into honeycomb Shape ceramics；
4) ceramic honeycomb is immersed in 1~2h in the silver nitrate solution that concentration is 0.15mol/L, drying；It again will be described Ceramic honeycomb is immersed in 1~2h in the sodium hydroxide solution that concentration is 0.6mol/L~5.6mol/L, makes sodium hydroxide solution Or in potassium hydroxide solution infiltration into microporous；The ceramic honeycomb is put into closed container, then is passed through to the closed container dense Degree is not less than the O of 15mg/L3Gas, the time for being passed through ozone gas is 1h~8h, and the temperature in closed container is controlled at 25 DEG C Within the scope of~55 DEG C, pressure is controlled within the scope of 0~0.1MPa.
Further, the plasticizer is the one of which in styrene-acrylic emulsion, pure-acrylic emulsion or silicone acrylic emulsion.
The present invention is by above technical scheme beneficial effect obtained:
1, the present invention caused by functional cellular shape ceramics be transition metal oxide ceramics and cordierite composition answer Zoarium system ceramics, transition metal oxide ceramics realize material in 8~14 μm of room temperature far infrared radiation rates up to 0.90~0.95, no Utilize the thermal energy of external environment or human body that can work by under additional energy source room temperature, it is environmentally friendly and energy saving；
2, cordierite overcomes the defect of the poor thermal shock resistance of transition metal oxide system ceramics, and prepared is compound System ceramics thermal expansion coefficient is low, and thermal shock resistance is good, long service life.
3, honeycomb structure alleviates material self weight, and substantially increases the heat storage capacity of material；Inside its micropore AgO solid particle makes material have both bacteriostasis property, guarantees that material is multi-functional, improves the wholesomeness in its use process；
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention It is as defined in the appended claims that the modification of form falls within the application.
Embodiment 1
Prepare Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramics:
1) the pure Fe of chemistry is weighed by weight 55: 25: 10: 102O3、MnO2、Co2O3, CuO, be mixed into batch；
2) by above-mentioned batch through wet ball grinding 12h, tablet is pressed into the pressure of 20MPa；
3) tablet is sintered to 2h in air, sintering temperature is 1200 DEG C, then cools to room temperature with the furnace and transition gold is made Belong to oxide ceramics.
Prepare functional cellular shape ceramics:
1) transition metal oxide Ceramic manufacturing obtained is proportionally weighed with cordierite ceramic powder and is matched at fine powder Material, transition metal oxide ceramic powder mass ratio are 25%；
2) plus after silicone acrylic emulsion plasticizer use wet ball grinding to 10 μm of particles below, granule content 75%, with 120 μm sieve screening, except iron, press filt, pug it is aging after extrude to form green honeycomb body；
3) it by green body plastic removal, is then rapidly heated through high temperature furnace to 1150 DEG C, keeps the temperature 3h, be fired into ceramic honeycomb；
4) ceramic honeycomb is immersed in 1h in the silver nitrate solution that concentration is 0.15mol/L, drying；Again by the honeycomb Shape ceramic immersion 1h in the sodium hydroxide solution that concentration is 1.4mol/L penetrates into sodium hydroxide solution or potassium hydroxide solution In micropore；The ceramic honeycomb is put into closed container, then is passed through the O that concentration is not less than 15mg/L to the closed container3 Gas, the time for being passed through ozone gas is 5h, and at 35 DEG C, pressure is controlled in 0~0.1MPa model the temperature control in closed container In enclosing.
Obtained functional cellular shape ceramics are by Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramics and The compound system ceramics of cordierite composition, in 8~14 μm of room temperature far infrared radiation rates up to 0.93；Ceramic capillary precision is 80 μm, Contain AgO solid particle in micropore, there is bacteriostasis property.
Embodiment 2
Prepare Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramics:
1) the pure Fe of chemistry is weighed by weight 60: 23: 7: 102O3、MnO2、Co2O3, CuO, be mixed into batch；
2) by above-mentioned batch through wet ball grinding 15h, tablet is pressed into the pressure of 22MPa；
3) tablet is sintered to 2.5h in air, sintering temperature is 1150 DEG C, then cools to room temperature with the furnace and transition is made Metal oxide ceramic.
Prepare functional cellular shape ceramics:
1) transition metal oxide Ceramic manufacturing obtained is proportionally weighed with cordierite ceramic powder and is matched at fine powder Material, transition metal oxide ceramic powder mass ratio are 30%；
2) plus after silicone acrylic emulsion plasticizer use wet ball grinding to 10 μm of particles below, granule content 80%, with 120 μm sieve screening, except iron, press filt, pug it is aging after extrude to form green honeycomb body；
3) it by green body plastic removal, is then rapidly heated through high temperature furnace to 1250 DEG C, keeps the temperature 3.5h, be fired into ceramic honeycomb；
4) ceramic honeycomb is immersed in 1.5h in the silver nitrate solution that concentration is 0.15mol/L, drying；Again by the bee Nest shape ceramic immersion 1h in the sodium hydroxide solution that concentration is 3.8mol/L seeps sodium hydroxide solution or potassium hydroxide solution Enter in micropore；The ceramic honeycomb is put into closed container, then is passed through concentration not less than 15mg/L's to the closed container O3Gas, the time for being passed through ozone gas is 6h, and at 35 DEG C, pressure is controlled in 0~0.1MPa the temperature control in closed container In range.
Obtained functional cellular shape ceramics are by Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramics and The compound system ceramics of cordierite composition, in 8~14 μm of room temperature far infrared radiation rates up to 0.92；Ceramic capillary precision is 70 μm, Contain AgO solid particle in micropore, there is bacteriostasis property.
It above are only two specific embodiments of the invention, but the design concept of the present invention is not limited to this, all benefits It is made a non-material change to the present invention with this design, should belong to the behavior for invading the scope of protection of the invention.But it is all Without departing from the content of technical solution of the present invention, according to the technical essence of the invention any type of letter to the above embodiments Single modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.

Claims (4)

1. a kind of functional cellular shape ceramics, it is characterised in that the functional cellular shape ceramics are by Fe2O3-MnO2- Co2O3The compound system ceramics of-CuO system transition metal oxide ceramics and cordierite composition, in 8~14 μm of room temperature far infrareds Radiance is up to 0.90~0.95；The functional cellular shape ceramic capillary precision is 1 μm~100 μm, solid containing AgO in micropore Body particle has bacteriostasis property.
2. a kind of functional cellular shape ceramics according to claim 1, it is characterised in that the Fe2O3-MnO2-Co2O3- CuO system transition metal oxide ceramic preparation the following steps are included:
1) the pure Fe of chemistry is weighed by weight 55~65: 15~25: 5~15: 5~152O3、MnO2、Co2O3, CuO, be mixed into Batch；
2) by above-mentioned batch through 10~16h of wet ball grinding, tablet is pressed into the pressure of 15~25MPa；
3) tablet is sintered to 1.5~2.5h in air, sintering temperature is 1050~1200 DEG C, then cools to room temperature system with the furnace Obtain transition metal oxide ceramics.
3. a kind of preparation method of functional cellular shape ceramics, it is characterised in that the following steps are included:
1) by transition metal oxide Ceramic manufacturing obtained at fine powder, ingredient, mistake are proportionally weighed with cordierite ceramic powder Crossing metal oxide ceramic mass ratio is 20~40%；
2) plus after plasticizer use wet ball grinding to 10 μm of particles below, granule content is 75%~85%, is sieved with 120 μm of sieves Point, except iron, press filt, pug it is aging after extrude to form green honeycomb body；
3) it by green body plastic removal, is then rapidly heated through high temperature furnace to 1150~1400 DEG C, keeps the temperature 2~6h, be fired into honeycomb pottery Porcelain.
4) ceramic honeycomb is immersed in 1~2h in the silver nitrate solution that concentration is 0.15mol/L, drying；Again by the honeycomb Shape ceramic immersion 1~2h in the sodium hydroxide solution that concentration is 0.6~5.6mol/L, makes sodium hydroxide solution or potassium hydroxide In solution infiltration into microporous；The ceramic honeycomb is put into closed container, then is passed through concentration to the closed container and is not less than The O of 15mg/L3Gas, the time for being passed through ozone gas is 1~8h, and the temperature in closed container is controlled in 25~55 DEG C of ranges Interior, pressure controls within the scope of 0~0.1MPa.
4. a kind of preparation method of functional cellular shape ceramics according to claim 3, it is characterised in that the plasticising Agent is the one of which in styrene-acrylic emulsion, pure-acrylic emulsion or silicone acrylic emulsion.
CN201910428517.3A 2019-05-16 2019-05-16 A kind of functional cellular shape ceramics and preparation method thereof Pending CN110143826A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111187098A (en) * 2020-02-20 2020-05-22 郑州普利飞尔环保科技有限公司 Antibacterial silver-loaded ceramic and preparation method thereof
CN115385573A (en) * 2022-08-29 2022-11-25 陕西科技大学 Far infrared emitting ceramic powder for daily ceramic and preparation method thereof
CN115926551A (en) * 2022-11-02 2023-04-07 杭州明敏涂料有限公司 Cordierite infrared reflection heat insulation coating and preparation process thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042092A (en) * 1988-10-26 1990-05-16 中国科学院生态环境研究中心 A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof
CN102643106A (en) * 2012-04-12 2012-08-22 耿良玲 Antibacterial microporous ceramic and manufacturing method thereof
CN102910898A (en) * 2012-11-09 2013-02-06 苏州赛格瑞新材料有限公司 Ferrite-based high-temperature infrared radiation material and preparation method thereof
CN107793141A (en) * 2017-11-28 2018-03-13 陕西启源科技发展有限责任公司 The preparation method of infrared radiant material
CN108975896A (en) * 2018-08-27 2018-12-11 芜湖市元奎新材料科技有限公司 A kind of method that opoka prepares cordierite honeycomb ceramic

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042092A (en) * 1988-10-26 1990-05-16 中国科学院生态环境研究中心 A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof
CN102643106A (en) * 2012-04-12 2012-08-22 耿良玲 Antibacterial microporous ceramic and manufacturing method thereof
CN102910898A (en) * 2012-11-09 2013-02-06 苏州赛格瑞新材料有限公司 Ferrite-based high-temperature infrared radiation material and preparation method thereof
CN107793141A (en) * 2017-11-28 2018-03-13 陕西启源科技发展有限责任公司 The preparation method of infrared radiant material
CN108975896A (en) * 2018-08-27 2018-12-11 芜湖市元奎新材料科技有限公司 A kind of method that opoka prepares cordierite honeycomb ceramic

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111187098A (en) * 2020-02-20 2020-05-22 郑州普利飞尔环保科技有限公司 Antibacterial silver-loaded ceramic and preparation method thereof
CN115385573A (en) * 2022-08-29 2022-11-25 陕西科技大学 Far infrared emitting ceramic powder for daily ceramic and preparation method thereof
CN115385573B (en) * 2022-08-29 2023-08-18 陕西科技大学 Far infrared emission ceramic powder for domestic ceramics and preparation method thereof
CN115926551A (en) * 2022-11-02 2023-04-07 杭州明敏涂料有限公司 Cordierite infrared reflection heat insulation coating and preparation process thereof

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