CN103880410B - Method of synthesizing ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by molten-salt growth method - Google Patents

Method of synthesizing ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by molten-salt growth method Download PDF

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CN103880410B
CN103880410B CN201410050251.0A CN201410050251A CN103880410B CN 103880410 B CN103880410 B CN 103880410B CN 201410050251 A CN201410050251 A CN 201410050251A CN 103880410 B CN103880410 B CN 103880410B
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CN103880410A (en
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王旭
佟志芳
廖春发
焦芸芬
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Jiangxi University of Science and Technology
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Abstract

The invention relates to a method of synthesizing ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by a molten-salt growth method. The method comprises the following steps: (1) preparing materials; (2) pre-synthesizing (main parameters: a temperature of 700 DEG C-850 DEG C and synthesis time of 2hours-4hours); (3) final synthesizing (main parameters: a temperature of 900 DEG C-1000 DEG C and synthesis time of 1 hour-2hours; and (4) product separating and collecting. The method disclosed by the invention is low in cost for preparing materials, short in process flow, simple in equipment, free of emission of solids, liquid and gases, free of secondary pollution and capable of directly synthesizing the ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by ZnO, Cr2O3 and Fe2O3 oxide powder with lower cost.

Description

Molten-salt growth method synthesis ZnO-Cr 2o 3-Fe 2o 3it is humiceram agglomerated powder body method
Technical field
The present invention relates to molten-salt growth method synthesizing ceramic body technique, specifically a kind of molten-salt growth method synthesis ZnO-Cr 2o 3-Fe 2o 3it is humiceram agglomerated powder body method.
Background technology
ZnO-Cr 2o 3-Fe 2o 3based semiconductor composite oxides are spinel type humicerams more common at present, should be used as humidity sensor very extensive, as fields such as household electrical appliances, automobile, medical treatment.And increasingly extensive application proposes various requirement to such material, as stability, consistence, interchangeability is good, precision is high; Use wet district wide, sensitivity is suitable.For meeting these requirements, then require to propose effective synthetic method and preparation method more.At present, ZnO-Cr is similar to 2o 3-Fe 2o 3the production process of the composite oxides class modern functions Modern Ceramic Material and products thereof of system generally comprises the unit operation such as Feedstock treating and processing, batching and abrasive material batch mixing, shaping, sintering, product performance detection.Normally will through the powder raw material such as many oxide of processing by necessarily preparing burden, therefore, the quality of the powder raw material needed in scientific research and plant produced composite oxides is then most important.Current, the powder fineness adopting mechanical processing method (as ball milling, vibration mill and comminution by gas stream etc.) to prepare in industrial production is limited.And superfine-material often adopts chemical process to prepare, can make that material particular diameter is little, even, good fluidity, active large, formability and coking property be better.Open up that one has that synthesis temperature is low, the reaction times is short, product purity that is easy and simple to handle, synthesis is high, the feature such as the crystal formation of powder granule and morphology controllable, the preparation new way meeting the requirement of modern times " green " metallurgical technology then has practical significance.
Molten-salt synthesis is a kind of inorganic materials synthetic method that RECENT DEVELOPMENTS is got up, and compares with other synthetic method, and operating process is simple, does not need other specific equipment.Main process is at high temperature dissolved in the melt of low melting point by oxide crystal, then by slow cooling or other method, forms supersaturated solution, and oxide crystal is reset by being diffused in fused salt, forming core thus new oxide crystal is separated out mutually.First BaFe has been synthesized by molten-salt growth method from Arendt in 1973 12o 19and SrFe 12o 19since, the method obtains and studies widely in synthesizing ceramic powder.In recent years, along with deepening continuously of research, the advantage of molten-salt synthesis shows gradually, and range of application is also more and more extensive, has prepared many oxide powder, as: ZnTiO 3, CaBi 2nb 2o 9, SrBi 2ta 2o 9deng.
Summary of the invention
The present invention seeks to for existing making ZnO-Cr 2o 3-Fe 2o 3be the weak point of humiceram precursor powder (sintering powder) technique, provide a kind of by ZnO, Cr 2o 3, Fe 2o 3oxide compound direct molten-salt growth method synthesis ZnO-Cr 2o 3-Fe 2o 3it is humiceram agglomerated powder body method.
Technical solution of the present invention: a kind of molten-salt growth method synthesis ZnO-Cr 2o 3-Fe 2o 3be humiceram agglomerated powder body method, comprise the following steps:
(1) proportioning starting material:
By KCl, NaCl, CaCl not containing crystal water 2villaumite is the medium of building-up reactions, granularity 200-300 object ZnO, Cr 2o 3, Fe 2o 3oxide powder is primitive reaction material;
Ratio requirement:
Pre-synthesis system: ZnO, Cr 2o 3it is 20 ~ 40% that mixture accounts for pre-synthesis reaction system material molar content, wherein ZnO:Cr 2o 3mol ratio=1:1; All the other are KCl, NaCl, CaCl 2any two kinds of mixing salts in salt, blending ratio is mol ratio 1:1;
Whole synthetic system: Fe 2o 3account for ZnO, Cr 2o 3, Fe 2o 3the molar content of material total amount is 2 ~ 6% add pre-synthesis system;
(2) pre-synthesis:
Abundant dewatered raw material, with ZnO, Cr of above-mentioned content 2o 3kCl, NaCl, CaCl of mixed oxide and mol ratio 1:1 2in salt, any two kinds of mixing salts fully mix, and load reactor, require to react 2-4h at temperature 700 ~ 850 DEG C;
(3) synthesis eventually:
System to pre-synthesis adds the Fe of above-mentioned content 2o 3, at temperature 900 ~ 1000 DEG C reaction 1-2h;
(4) collection of product:
After distilled water cleaning reaction thing, its insoluble solid particle drying and obtain end product.
Containing KCl, NaCl, CaCl of crystal water 2it is the 48h that dewaters at 300 DEG C of temperature in atmosphere that villaumite removes crystal water condition; Granularity 200-300 object ZnO, Cr 2o 3, Fe 2o 3oxide powder is dry 24h at 150 DEG C of temperature in atmosphere.
Major control condition and foundation:
1, Reactive Synthesis temperature will make the substance system of set proportioning fully melt and reach suitable activity, the volatilization of fused salt
Amount is 3-5%, and OK range is 700 ~ 1000 DEG C.
2, the Reactive Synthesis time is wanted fully, and OK range is 1 ~ 4h.
Raw materials cost of the present invention and existing technics comparing low by about 30%, technical process shortens nearly 50%, and equipment is simple, can with lower cost directly by ZnO, Cr 2o 3, Fe 2o 3oxide powder making ZnO-Cr 2o 3-Fe 2o 3be humiceram precursor powder, product particle size is little and even, and economical efficiency significantly improves.
Embodiment
Embodiment 1: by atmosphere 300 DEG C dehydration 48h after KCl, NaCl and 150 DEG C of dry 24h after granularity be 200 object ZnO, Cr 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=40:40:10:10 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 700 DEG C, and constant temperature pre-synthesis reacts 2h; After 150 DEG C of dry 24h, granularity is 200 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=49:49:2 weighs, by the Fe weighed 2o 3after powder is warming up to 900 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 1h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 3%, and the recovery rate of powder is 95%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 2um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
Embodiment 2: by atmosphere 300 DEG C dehydration 48h after KCl, NaCl and 150 DEG C of dry 24h after granularity be 300 object ZnO, Cr 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=30:30:20:20 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 850 DEG C, and constant temperature pre-synthesis reacts 4h; After 150 DEG C of dry 24h, granularity is 300 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=47:47:6 weighs, by the Fe weighed 2o 3after powder is warming up to 1000 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 2h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 5%, and the recovery rate of powder is 96%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 5um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
Embodiment 3: by atmosphere 300 DEG C dehydration 48h after CaCl 2, granularity is 200 object ZnO, Cr after NaCl and 150 DEG C dry 24h 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=40:40:10:10 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 700 DEG C, and constant temperature pre-synthesis reacts 2h; After 150 DEG C of dry 24h, granularity is 200 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=49:49:2 weighs, by the Fe weighed 2o 3after powder is warming up to 900 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 1h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 3%, and the recovery rate of powder is 95%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 2um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
Embodiment 4: by atmosphere 300 DEG C dehydration 48h after CaCl 2, granularity is 300 object ZnO, Cr after NaCl and 150 DEG C dry 24h 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=30:30:20:20 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 850 DEG C, and constant temperature pre-synthesis reacts 4h; After 150 DEG C of dry 24h, granularity is 300 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=47:47:6 weighs, by the Fe weighed 2o 3after powder is warming up to 1000 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 2h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 5%, and the recovery rate of powder is 96%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 5um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
Embodiment 5: by atmosphere 300 DEG C dehydration 48h after CaCl 2, granularity is 200 object ZnO, Cr after KCl and 150 DEG C dry 24h 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=40:40:10:10 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 700 DEG C, and constant temperature pre-synthesis reacts 2h; After 150 DEG C of dry 24h, granularity is 200 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=49:49:2 weighs, by the Fe weighed 2o 3after powder is warming up to 900 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 1h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 3%, and the recovery rate of powder is 95%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 2um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
Embodiment 6: by atmosphere 300 DEG C dehydration 48h after CaCl 2, granularity is 300 object ZnO, Cr after KCl and 150 DEG C dry 24h 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=30:30:20:20 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 850 DEG C, and constant temperature pre-synthesis reacts 4h; After 150 DEG C of dry 24h, granularity is 300 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=47:47:6 weighs, by the Fe weighed 2o 3after powder is warming up to 1000 DEG C after adding pre-synthesis system, constant temperature carries out whole building-up reactions 2h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product.Fused salt volatilization quality is 5%, and the recovery rate of powder is 96%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 5um, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.

Claims (3)

1. a molten-salt growth method synthesis ZnO-Cr 2o 3-Fe 2o 3be humiceram agglomerated powder body method, it is characterized in that comprising the following steps:
(1) proportioning starting material:
By KCl, NaCl, CaCl not containing crystal water 2villaumite is the medium of building-up reactions, granularity 200-300 object ZnO, Cr 2o 3, Fe 2o 3oxide powder is primitive reaction material;
Ratio requirement:
Pre-synthesis system: ZnO, Cr 2o 3it is 20 ~ 40% that mixture accounts for pre-synthesis reaction system material molar content, wherein ZnO:Cr 2o 3mol ratio=1:1; All the other are KCl, NaCl, CaCl 2any two kinds of mixing salts in salt, blending ratio is mol ratio 1:1;
Whole synthetic system: Fe 2o 3account for ZnO, Cr 2o 3, Fe 2o 3the molar content of material total amount is 2 ~ 6% add pre-synthesis system;
(2) pre-synthesis:
Abundant dewatered raw material, with ZnO, Cr of above-mentioned content 2o 3kCl, the NaCl of mixed oxide and mol ratio 1:1,
CaCl 2in salt, any two kinds of mixing salts fully mix, and load reactor, require to react 2-4h at temperature 700 ~ 850 DEG C;
(3) synthesis eventually:
System to pre-synthesis adds the Fe of above-mentioned content 2o 3, at temperature 900 ~ 1000 DEG C reaction 1-2h;
(4) collection of product:
After distilled water cleaning reaction thing, its insoluble solid particle drying and obtain end product;
Described KCl, NaCl, CaCl of not containing crystal water 2villaumite is by KCl, NaCl, the CaCl containing crystal water 2the villaumite 48h that dewaters at 300 DEG C of temperature in atmosphere obtains; Granularity 200-300 object ZnO, Cr 2o 3, Fe 2o 3oxide powder is dry 24h at 150 DEG C of temperature in atmosphere.
2. a kind of molten-salt growth method synthesizes ZnO-Cr according to claim 1 2o 3-Fe 2o 3be humiceram agglomerated powder body method, it is characterized in that: pre-synthesis Reactive Synthesis temperature will make the substance system of set proportioning fully melt and reach suitable activity, the volatile quantity of fused salt is 3-5%, and OK range is 700 ~ 850 DEG C; The activity that whole building-up reactions synthesis temperature will make reactant reach suitable, OK range is 900 ~ 1000 DEG C.
3. a kind of molten-salt growth method synthesizes ZnO-Cr according to claim 1 2o 3-Fe 2o 3be humiceram agglomerated powder body method, it is characterized in that: by atmosphere 300 DEG C dehydration 48h after KCl, NaCl and 150 DEG C of dry 24h after granularity be 200 object ZnO, Cr 2o 3kCl:NaCl:ZnO:Cr in molar ratio 2o 3=40:40:10:10 weighs and fully mixing, and mixing salt is put into corundum crucible; Electrified regulation is to 700 DEG C, and constant temperature pre-synthesis reacts 2h; After 150 DEG C of dry 24h, granularity is 200 order Fe 2o 3powder is by pre-synthesis reaction ZnO, Cr 2o 3the amount of powder is with mol ratio ZnO:Cr 2o 3: Fe 2o 3=49:49:2 weighs, by the Fe weighed 2o 3powder add with synthetic system after be warming up to 900 DEG C after constant temperature carry out whole building-up reactions 1h; With after distilled water cleaning reaction thing after system air cooling, its insoluble solid particle drying and obtain end product; Fused salt volatilization quality is 3%, and the recovery rate of powder is 95%, and by material phase analysis, product is mainly ZnO-Zn (Fe, Cr) 2o 4, mean particle size is 2 μm, meets ZnO-Cr 2o 3-Fe 2o 3it is the requirement of humiceram sintering powder.
CN201410050251.0A 2014-02-14 2014-02-14 Method of synthesizing ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by molten-salt growth method Expired - Fee Related CN103880410B (en)

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