CN1079088C - Oxygen sensitive film with stable high temperature property and its preparing method - Google Patents
Oxygen sensitive film with stable high temperature property and its preparing method Download PDFInfo
- Publication number
- CN1079088C CN1079088C CN 99104596 CN99104596A CN1079088C CN 1079088 C CN1079088 C CN 1079088C CN 99104596 CN99104596 CN 99104596 CN 99104596 A CN99104596 A CN 99104596A CN 1079088 C CN1079088 C CN 1079088C
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- Prior art keywords
- film
- oxygen sensitive
- sensitive film
- oxygen
- solution
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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
- 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
- C04B41/5025—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 with ceramic materials
- C04B41/5027—Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The present invention discloses an oxygen sensitive film with stable high temperature performance and a preparing method thereof. The oxygen sensitive film uses a ceramic sheet of alpha <=-Al2O3 as a substrate, and a chemical composition formed on the substrate comprises a chemical compound La<1-x>Sr<x>Ni<1-y>Co<y>O<3>, wherein 0<= x <=0.2, and 0<= y <=0.3. The oxygen sensitive film is prepared in an ISG method, namely, the method mainly comprises the steps of preparing a salt solution, compounding the solution into solation, coating a film on the substrate, performing heat treatment for the film and sintering. The oxygen sensitive film has the advantages of stable performance and high sensitivity under high temperature. The oxygen sensitive film can be widely used as a gas sensitive element on sensors for detecting automobile tail gas and kiln discharged fume.
Description
The present invention relates to the preparation method of the stable oxygen sensitive film of a kind of high-performance.It belongs to the inorganic oxygen sensitive film technology of preparing that is used on the high temperature oxygen transmitter.
The high temperature oxygen transmitter can be used for the electronic automatic control system of vehicle exhaust and Industrial Stoves discharging flue gas, and mostly existing oxygen-sensitive material that uses is to adopt ZrO on it
2And TiO
2Based semiconductor ceramics sintering block, this block materials temperature stability is poor, for improving stability, needs the complicated temperature-compensated system of preparation.In addition, material is also relatively poor to oxygen sensitivity, for improving its susceptibility, need modify with the platinum one class precious metal of costliness.Above-mentioned compensation and modification way have increased difficulty and cost all for the manufacturing oxygen sensor.
Purpose of the present invention is to provide a kind of preparation method of the oxygen sensitive film that has stable high-temperature performance.Prepared film, stable performance at high temperature, the susceptibility height to oxygen is specially adapted to make various oxygen sensors; This oxygen sensitive film preparation technology is simple, with low cost.
In order to achieve the above object, the present invention is realized by following technical proposals.Said oxygen sensitive film is at a kind of α-Al
2O
3On the ceramic sheet, the formation chemical constitution is La
1-xSr
xNi
1-yCo
yO
3, to the uhligite polycrystalline phase compound of oxygen sensitive, wherein 0≤X≤0.2,0≤Y≤0.3.This film adopts inorganic salt sol-gel methodes (JSG method) to be prepared from.Its technological process mainly comprises successively: the complexing solation of the preparation of salts solution, solution, at α-Al
2O
3Dip-coating on the substrate, spin coating or spraying system sol gel film and film thermal treatment sintering step.It is characterized in that: a, with La (NO
3)
36H
2O, Sr (NO
3)
2, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O is a raw material, is solvent with deionized water, ethanol or their mixing solutions, and being mixed with concentration is 0.2～0.8mol/L, and the pH value is 2～6 salts solution; B, in above-mentioned solution, the citric acid that adds 0.2～0.8mol/L is a complexing agent, the ethylene glycol that adds 0.05～0.1mol/L is linking agent, 40～60 ℃ of stirrings produce stable in vitreosol; C. to be coated after on-chip sol gel film drying, after handling 10～40min under 500～600 ℃ of excess oxygens, in oxygen-enriched atmosphere, obtain oxygen sensitive film again at 800～1000 ℃ of following sintering.
Below main points of the present invention are described in detail.Preparation process of the present invention is the key point that directly influences oxygen sensitive film performance quality.Good concentration of GPRS and pH value in the process of the preparation of salts solution, the concentration height directly influence the viscosity size of colloidal sol, so strength of solution is moderate, grasp at 0.2～0.8mol/L, the size of pH value and solution have deny precipitate separate out relevant.The pH value that the present invention controls salts solution is 2～6, can effectively stop solution that precipitation takes place like this and separate out.Citric acid is adopted in the solation of solution to be complexing agent and to be linking agent with ethylene glycol, they help forming stable sols on the one hand, under air-proof condition, help prolonging prepared colloidal sol preservation period in addition again, the colloidal sol that the present invention produced can be preserved under air-proof condition more than two months, and having is that they have cheap advantage again; Film-forming process should be noted that substrate α-Al especially
2O
3Polish and purifying treatment, the system film can adopt dip-coating, spin coating, spraying,, which kind of carries out no matter but adopting is coated with the equal repeated multiple times of method, coating finishes treat the film drying after, the film thermal treatment of carrying out in 500～600 ℃ of oxygen-enriched atmospheres is also grasped the time, and overlong time can take place that film crystal grain is excessive, sensitivity decline phenomenon.Be at last at oxygen-enriched atmosphere behind 800～1000 ℃ of sintering, finally can obtain the oxygen sensitive film that has stable high-temperature performance of the present invention.
The present invention is further described with embodiment more below.
Embodiment one: form (1) x=0, the y=0.3 raw material.
In the Glass Containers of 500ml, add 200ml deionized water and 29g raw material, in the following stirring and dissolving of room temperature (24～26 ℃), make and have the transparent solution of color.Add citric acid 42g then, stir and tremble dissolving 1～2 hour.Add ethylene glycol 1.2ml again, fully stir and form colloidal sol, cover room temperature preservation then completely.
Adopt α-Al
2O
3Ceramic substrate is made the substrate that film forms, and substrate surface requires smooth, concavo-convex less than 0.2 μ m.In advance with substrate in clean-out system with after the ultrasonic cleaning, fully wash with deionized water, dry again.Use the automatic lifting coating equipment, substrate is immersed in the colloidal sol, substrate is steadily promoted, form dissolved glue film on the substrate with the speed of 1～10cm/min.The dissolved glue film polymerization of dewatering gradually forms gel-film.After the drying, form xerogel in baking oven or under the infrared lamp, put into electric furnace, at 500～600 ℃ of following pre-treatment 10～40min.According to different requirements to thickness and performance, the number of times that dip-coating → drying → heat treatment cycle unit can be different repeatedly (generally repeatedly 6～10 times, film thickness is at 0.5～1 μ m).
The cold pretreatment film burns till under oxidizing condition: firing atmosphere is an air, and 800～1000 ℃ of firing temperatures are incubated 0.5～1 hour.Obtain the LaNi of composite junction crystalline phase
0.7Co
0.3O
3Film.Film room temperature surface resistivity (or the resistance of film side) 10～10
2Ω/ (according to four-probe measurement).
Embodiment two: form (2) x=0.1, the y=0.3 raw material.
Adding 200ml deionized water and 30g raw material in the glass beaker of 500ml descend stirring and dissolving in room temperature (24～26 ℃), make to have the transparent solution of color.Added citric acid 42g stirring and dissolving then 1～2 hour.Add ethylene glycol 1.2ml again, fully stir and form colloidal sol, cover room temperature preservation then completely.
At α-Al
2O
3The process of manufacturing film on the substrate is with example one.The compound crystalline phase of Huo Deing is La at last
0.9Sr
0.1Ni
0.7Co
0.3O
3Film.Film room temperature surface resistivity (or the resistance of film side) 10～10
3Ω/mouth (according to four-probe measurement).
Advantage of the present invention at first is (the NO with La3)
3·6H
2O、Sr(NO
3)
2·6H
2O and Co (NO3)
2·6H
2O etc. are raw material, and the source is wide, and price is low. The second, prepared oxygen sensitive film, it is tiny to have a rete particle, space and surface area Suitably, be conducive to absorption and the diffusion of gas. The 3rd, the crystalline phase of film is compound phase, and conducting activation energy is low, so have good Resistance-temperature stability and good sensitivity.
Oxygen sensitive film of the present invention can be used for doing gas sensor on the high temperature oxygen sensing, such as the air-fuel ratio sensor of automobile, Industrial Stoves Fume emission detecting sensor etc.
Claims (1)
1. the preparation method of an oxygen sensitive film that has stable high-temperature performance, said oxygen sensitive film is at a kind of α-Al
2O
3On the ceramic sheet, the formation chemical constitution is La
1-xSr
xNi
1-yCo
yO
3, to the uhligite polycrystalline phase compound of oxygen sensitive, wherein 0≤X≤0.2,0≤Y≤0.3; This film adopts inorganic salt sol-gel method to be prepared from, and its technological process mainly comprises successively: the complexing solation of the preparation of salts solution, solution, at α-Al
2O
3Dip-coating on the substrate, spin coating or spraying system sol gel film and film thermal treatment sintering step is characterized in that: a, and with La (NO
3)
36H
2O, Sr (NO
3)
2, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O is a raw material, is solvent with deionized water, ethanol or their mixing solutions, and being mixed with concentration is 0.2～0.8mol/L, and the pH value is 2～6 salts solution; B, in above-mentioned solution, the citric acid that adds 0.2～0.8mol/L is a complexing agent, the ethylene glycol that adds 0.05～0.1mol/L is linking agent, produces stable vitreosol 40～60 ℃ of stirrings; C, to be coated after on-chip sol gel film drying, after handling 10～40min under 500～600 ℃ of excess oxygens, again in oxygen-enriched atmosphere under 800～1000C sintering obtain oxygen sensitive film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99104596 CN1079088C (en) | 1999-05-11 | 1999-05-11 | Oxygen sensitive film with stable high temperature property and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99104596 CN1079088C (en) | 1999-05-11 | 1999-05-11 | Oxygen sensitive film with stable high temperature property and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235942A CN1235942A (en) | 1999-11-24 |
| CN1079088C true CN1079088C (en) | 2002-02-13 |
Family
ID=5271749
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99104596 Expired - Fee Related CN1079088C (en) | 1999-05-11 | 1999-05-11 | Oxygen sensitive film with stable high temperature property and its preparing method |
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|---|---|
| CN (1) | CN1079088C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427094B (en) * | 2012-05-23 | 2016-04-20 | 中国科学院物理研究所 | Oxide of perovskite structure and its production and use |
| US9287106B1 (en) | 2014-11-10 | 2016-03-15 | Corning Incorporated | Translucent alumina filaments and tape cast methods for making |
-
1999
- 1999-05-11 CN CN 99104596 patent/CN1079088C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1235942A (en) | 1999-11-24 |
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