CN100366575C - Stannic dioxide- zinc lithium vanadate composite rod-shape crystal granule humidity-sensitive ceramic material and its preparation method - Google Patents
Stannic dioxide- zinc lithium vanadate composite rod-shape crystal granule humidity-sensitive ceramic material and its preparation method Download PDFInfo
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- CN100366575C CN100366575C CNB2005100370673A CN200510037067A CN100366575C CN 100366575 C CN100366575 C CN 100366575C CN B2005100370673 A CNB2005100370673 A CN B2005100370673A CN 200510037067 A CN200510037067 A CN 200510037067A CN 100366575 C CN100366575 C CN 100366575C
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Abstract
The present invention relates to a Sno 2-LiZn Vo4 composite rod-shaped crystal granule humidity-sensitive ceramic material. As for the humidity-sensitive material, tin tetrachloride (one portion) and zinc chloride (0.12 to 0.35 portion) are prepared into water solution to be mixed according to the net molar (portion) ratio; then, ammonium is added into the water solution, and the pH value of the solution is adjusted to 5; the solution is repeatedly washed with distilled water and deionized water or the deionized water to remove chlorine ions in the solution. Then, lithium vanadate and potassium nitrate are added into a deposition; after the lithium vanadate, the potassium nitrate and the deposition are uniformly mixed, drying, grinding, heat treatment at the temperature of 550 DEG C to 700 DEG C, regrind and drying are carried out. At last, a powder body mold which is pressed into the shape of a sheet is sintered for two hours at the temperature of 750 DEG C to 850 DEG C, and the humidity-sensitive material is obtained when the powder body mold is cooled with a furnace. The Sno 2-LiZn Vo4 composite rod-shaped crystal granule humidity-sensitive ceramic material of the present invention has a rod-shaped crystal granule structure. A tubular passage and large numbers of communicated air holes are easy to form on the rod-shaped crystal granule structure, which is favorable for the adsorption and the desorption of water molecules. A thick film humidity-sensitive resistor which is manufactured by using the present invention has the advantages of small resistance, high sensitivity, good humidity sensing linearity, high response speed and good stability.
Description
Invention field
The present invention relates to by means of the chemistry of measuring material or physical properties is tested or the technical field of analysis of material, specifically relate to a kind of materials of electronic components, particularly relate to a kind of tindioxide-vanadic acid zinc lithium (SnO2-LiZn VO4) compound humidity-sensitive ceramic material and preparation method.
Technical background
At present, the preparation material of the wet quick electronic component of widespread use both at home and abroad mainly contains macromolecular material and stupalith two big classes.The humidity sensitive resistor element that adopts macromolecular material to make, response is fast, the high advantage of precision though have, and the life-span is short, especially can not and have under the environment of pollution at high temperature, high humidity and work.State Intellectual Property Office disclosed " a kind of organic polymer---inorganic nano combined resistance type thin film humidity-sensitive element " on December 3rd, 2003, and (publication number is: 1459876), the disclosed humidity-sensitive element of this patent document is that employing organic polymer material and inorganic nano material are compounded, though the resistance to elevated temperatures of existing similar technology makes moderate progress, but exist inorganic nano-particle in organic polymer solution, to be difficult to really mix, the conforming obvious deficiency when influence is produced in batches.The metal oxide humidity-sensitive ceramic material has thermostability preferably, the characteristics of antipollution and long service life, and particularly having can be in the advantage than testing humidity under the mal-condition (as hot environment)." Journal of Inorganic Materials " 1999 14 phases the 6th volume 995-999 page or leaf has been delivered one piece and has been entitled as: the article of " nanostructure of LiCl/SiO2-Al2O3 film and wet quick characteristic " discloses the method and the nanometer LiC1/SiO2-Al2O3 properties of materials that use nanometer LiC1/SiO2-Al2O3 material to make humidity sensitive resistor element in this article.According to the description in the literary composition, humidity sensitive resistor element with this nanometer LiCl/SiO2-Al2O3 material making, though possess advantage with plain metal oxide compound humidity-sensitive ceramic material made humidity sensitive resistor element, but remain in following deficiency: 1, the impedance of element-humidity relation curve linear lag is bad, particularly during high humidity; 2, the resistance of element is big, adjusts resistance by LiCl and can make element high humidity degradation.Delivered " the K that is entitled as that the inventor and co-worker write on the 16th～18 page of " electronic component and material " 2004 the 7th phase
+Doping is to SnO
2-LiZnVO
4Be the humiceram Effect on Performance " article, disclosed tindioxide-vanadic acid zinc lithium (SnO in the literary composition
2-LiZnVO
4) matrix material and this preparation methods.In follow-up research, we test and study the electric property of the humidity sensitive resistor element that adopts the ceramic humidity-sensitive material described in the literary composition and make, find that its wet quick linear lag is bad, and stability is not very good yet.Thereafter we observe the microtexture of the ceramic humidity-sensitive material described in the literary composition with scanning electronic microscope again, find that its crystal grain is spheric, and crystal grain is not of uniform size, the porous ceramics that causes being produced contains a large amount of sealed porositys, these sealed porositys have limited the suction of water molecules and have deviate from, thereby restricted the further lifting of further improvement, especially the sensitivity K value of its gas-sensitive property.
Summary of the invention:
In view of there is above-mentioned deficiency in prior art, technical problem to be solved by this invention is to improve tindioxide-vanadic acid zinc lithium (SnO
2-LiZnVO
4) crystalline-granular texture, a kind of tindioxide-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4) and preparation method thereof is provided, adopt highly sensitive, the good stability of the humidity sensitive resistor element that humidity-sensitive ceramic material of the present invention makes.
The technical solution that the present invention solves the problems of the technologies described above is:
A kind of tindioxide-composite club-shaped crystal grain the humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4), it is composed of the following components to press this humidity-sensitive material of net value mole (part) proportioning:
Tin tetrachloride (SnCl
45H
2O) 1
Zinc chloride (ZnCl
2) 0.12～0.35
Lithium vanadate (LiVO
3) 0.12～0.35
Saltpetre (KNO3) 0.003～0.025
Above-mentioned tindioxide-vanadic acid zinc lithium (SnO2-LiZn VO4) the preferable of composite club-shaped crystal grain humidity-sensitive ceramic material consists of:
Tin tetrachloride (SnCl
45H
2O) 1
Zinc chloride (ZnCl
2) 0.2～0.3
Lithium vanadate (LiVO
3) 0.2～0.3
0.02～0.025 part in saltpetre (KNO3)
The method for preparing above-mentioned tindioxide-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4) is made up of the following step:
A) with tin tetrachloride and zinc chloride difference adding distil water wiring solution-forming;
B) with steps A) the institute wiring solution-forming mixes the back and add ammonium when stirring, and the pH value of solution is transferred to 5, removes wherein chlorion with distilled water and deionized water or deionized water repetitive scrubbing earlier again, obtains nano level white creaming thing;
C) at step B) add in the throw out of gained and carry out drying, grinding, 550 ℃～700 ℃ following thermal treatment 1 hour behind lithium vanadate and saltpetre and the mixing, grind again, dry;
D) with step C) the powder molding slabbing of gained, 750 ℃～850 ℃ following sintering 2 hours, furnace cooling is promptly.
Use scanning electron microscope that tindioxide of the present invention-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4) is carried out microscopic observation, find that its microscopic appearance is obviously different than the spherical particle material, it is bar-shaped that crystal grain is, the pore shape in a tubular form, void content increases and distribution uniform (referring to accompanying drawing 1 or Fig. 2).Because bar-like grains is in contact with one another and is easy to form tubular channel, and perforation mutually, surface smoothness, the suction of favourable water molecules or deviate from, therefore the humidity sensitive resistor element that adopts the composite club-shaped crystal grain humidity-sensitive ceramic material of tindioxide of the present invention-vanadic acid zinc lithium (SnO2-LiZn VO4) to make, not only highly sensitive, impedance-humidity relation curve linear lag is good, and long term operation is stable.
Description of drawings:
Fig. 1 is for to be placed on the photo of taking under the scanning electronic microscope with following example 1 resulting humidity-sensitive ceramic material;
Fig. 2 is for to be placed on the photo of taking under the scanning electronic microscope with following example 2 resulting humidity-sensitive ceramic materials;
Fig. 3 is for to be placed on the photo of taking under the scanning electronic microscope with following example 4 resulting humidity-sensitive ceramic materials;
Fig. 4 is resistance-relative humidity curve that the thick film humidity-dependent resistor of following example 5 mades records under condition of different temperatures;
Fig. 5 is moisture absorption and the dehumidification relation curve of the thick film humidity-dependent resistor of following example 5 mades in the 42%RH atmospheric environment;
Fig. 6 is moisture absorption and the dehumidification relation curve of the thick film humidity-dependent resistor of following example 5 mades in the 65%RH atmospheric environment;
Fig. 7 uses the stability test curve of the thick film humidity-dependent resistor of the composite club-shaped crystal grain humidity-sensitive ceramic material making of tindioxide of the present invention-vanadic acid zinc lithium (SnO2-LiZn VO4).
Embodiment:
Below in conjunction with specific embodiment specific implementation method of the present invention and useful effect are further described.
Example 1:
By net value mole (part) than taking by weighing 1 part of tin tetrachloride; 0.3 part of zinc chloride; 0.3 part of lithium vanadate; 0.02 part in saltpetre, then by following step preparation:
A) with tin tetrachloride and zinc chloride difference adding distil water wiring solution-forming;
B) with steps A) solution for preparing mixes, under the electric blender vigorous stirring, splashing into concentration with the speed of 3ml/min is 25% ammoniacal liquor, when the pH value of solution stops dropping ammonia near 5 the time, leave standstill the back with distilled water and deionized water repetitive scrubbing throw out until using AgNO
3Check no Cl
-Till, obtain nano level white creaming thing;
C) dry in baking oven after interpolation lithium vanadate and saltpetre stir in above throw out, behind grinding, 550 ℃ of following thermal treatment 1h, grind again, dry;
D) powder is pressed into sheet in mould, 750 ℃ of following sintering 2 hours, furnace cooling promptly got tindioxide of the present invention-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4).
Because employed raw material itself is exactly nano level, at above-mentioned steps C) in the purpose of grinding repeatedly mainly be that throw out and lithium vanadate are mixed, so the grinding in this step can be stirred with air-flow fully and replaced.
This routine obtained tindioxide-composite club-shaped crystal grain humidity-sensitive ceramic material sem observation of vanadic acid zinc lithium (SnO2-LiZn VO4), its pattern as shown in Figure 1.
Example 2:
By net value mole (part) than taking by weighing 1 part of tin tetrachloride; 0.12 part of zinc chloride; 0.12 part of lithium vanadate; Behind 0.025 part in the saltpetre, by by the preparation of example 1 described method and step, with step C wherein) thermal treatment temp be adjusted into 700 ℃, step D) sintering temperature be adjusted into 850 ℃.
This routine prepared tindioxide-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4) is used sem observation, and its pattern as shown in Figure 2;
Example 3:
By net value mole (part) than taking by weighing 1 part of tin tetrachloride; 0.35 part of zinc chloride; 0.35 part of lithium vanadate; 0.003 part in saltpetre, then by following step preparation:
A) with tin tetrachloride and zinc chloride difference adding distil water wiring solution-forming;
B) with steps A) solution for preparing mixes, and under the electric blender vigorous stirring urea added in the mixing solutions, heat temperature raising makes the pH value of solution rise to 5 to 80-90 ℃, leave standstill the back with deionized water repetitive scrubbing throw out until using AgNO
3Check no Cl
-Till, obtain nano level white creaming thing;
C) dry in baking oven after interpolation lithium vanadate and saltpetre stir in above throw out, behind grinding, 650 ℃ of following thermal treatment 1h, grind again, dry;
D) powder is pressed into sheet in mould, 800 ℃ of following sintering 2 hours, furnace cooling promptly got tindioxide of the present invention-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4).Example 4 (comparative example):
By net value mole (part) than taking by weighing 1 part of tin tetrachloride; 0.03 part of zinc chloride; 0.03 part of lithium vanadate; 0.01 part in saltpetre adopts the step identical with example 1 and prepares the tindioxide base ceramic material in proper order.Use sem observation, its pattern as shown in Figure 3, powder crystal grain is spherical in shape substantially, with coming to the same thing described in the background technology.
Example 5 (effect example):
By net value mole (part) than taking by weighing 1 part of tin tetrachloride; 0.2 part of zinc chloride; 0.2 part of lithium vanadate; Ammoniacal liquor is an amount of; 0.02 part in saltpetre adopts example 1 described method and step to prepare tindioxide of the present invention-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4), prepares the thick film hygristor by following step again:
A) in tindioxide of the present invention-composite club-shaped crystal grain humidity-sensitive ceramic material of vanadic acid zinc lithium (SnO2-LiZn VO4), add an amount of organic binder bond, be modulated into the thick film screen printing slurry based on ethyl cellulose;
B) adopt the thick film silk-screen printing technique slurry to be printed on the alumina substrate of the good gold electrode of prepared beforehand, at 750 ℃～850 ℃ sintering temperatures 2 hours, furnace cooling, welding lead promptly gets SnO then
2-LiZnVO
4Bar-like grains thick film hygristor.
With the thick film humidity-dependent resistor that aforesaid method makes, under 1kHz, the excitation of 1V voltage of alternating current, the resistance when different relative humidity and temperature condition-the relative humidity curve as shown in Figure 4.
As seen from the figure, the thick film humidity-dependent resistor has the good sense linear lag that wets, and is highly sensitive, reaches 3 more than the order of magnitude from its resistance change rate of 20-90%RH, and particularly resistance is little when low humidity, and M Ω size is only arranged, and helps simplifying follow-up metering circuit.
At 25 ℃, under 1kHz, the 1V voltage of alternating current incentive condition, adopt the computer automatic data acquisition system (ADAS), measure the thick film humidity-dependent resistor and put into 55%RH humidity cabinet and the time of response when the 42%RH atmospheric environment is put into the 32%RH humidity cabinet fast fast, as Fig. 5 from the 42%RH atmospheric environment.
The thick film humidity-dependent resistor is put into the 95%RH humidity cabinet fast from the 65%RH atmospheric environment, takes out fast from humidity cabinet then, and the time of response when putting back to the 65%RH atmospheric environment is as Fig. 6.
Example 6 (stability test example):
By example 5 described methods, select the upper and lower bound (promptly 750 ℃ and 850 ℃) of sintering range, make two SnO respectively
2-LiZnVO
4Bar-like grains thick film humidity-dependent resistor, be placed in 75%RH relative humidity and the room temperature environment then simultaneously, in 1kHz, the long-term galvanization of 1V voltage of alternating current, measure the stability of thick film humidity-dependent resistor, the time dependent trend of its resistance value is as shown in Figure 7.
More than experiment shows, the thick film humidity-dependent resistor has good long term stability, in more than 70 days energising weathering process, the resistance of resistor descends earlier and rises then, 850 ℃ of agglomerating thick film hygristors change about 1k Ω, contrast the drift of having only 1%RH with Fig. 4,750 ℃ of agglomerating thick film hygristor variations are relatively large, but also present progressively regressive trend.
Claims (3)
1. tindioxide-vanadic acid zinc lithium SnO
2-LiZnVO
4Composite club-shaped crystal grain humidity-sensitive ceramic material, it is first with tin tetrachloride and zinc chloride difference adding distil water wiring solution-forming by following component that this humidity-sensitive material is pressed net value molar part proportioning, and when stirring, institute wiring solution-forming mixing back adds ammonium, the pH value of solution is transferred to 5, with distilled water and deionized water or deionized water repetitive scrubbing removal chlorion wherein, carry out drying after adding lithium vanadate and saltpetre and mixing then, grind, 550 ℃～700 ℃ following thermal treatment 1 hour, grind again, oven dry, be molded into sheet at last, 750 ℃～850 ℃ sintering temperatures 2 hours, furnace cooling made:
Tin tetrachloride SnCl
45H
2O 1
Zinc chloride ZnCl
20.12～0.35
Lithium vanadate LiVO
30.12～0.35
Saltpetre KNO
30.003～0.025.
2. the described a kind of tindioxide of claim 1-vanadic acid zinc lithium SnO
2-LiZnVO
4Composite club-shaped crystal grain humidity-sensitive ceramic material, this humidity-sensitive material is made by following component by net value molar part proportioning:
Tin tetrachloride SnCl
45H
2O 1
Zinc chloride ZnCl
20.2～0.3
Lithium vanadate LiVO
30.2～0.3
Saltpetre KNO
30.02～0.025.
3. prepare claim 1 or 2 described tindioxide-vanadic acid zinc lithium SnO
2-LiZnVO
4The method of composite club-shaped crystal grain humidity-sensitive ceramic material is characterized in that this method is made up of the following step:
A) with tin tetrachloride and zinc chloride adding distil water wiring solution-forming, mixing then respectively;
B) with steps A) the institute wiring solution-forming mixes the back and add ammonium when stirring, and the pH value of solution is transferred to 5, removes wherein chlorion with distilled water and deionized water or deionized water repetitive scrubbing again;
C) at step B) add in the throw out of gained and carry out drying, grinding, 550 ℃～700 ℃ following thermal treatment 1 hour behind lithium vanadate and saltpetre and the mixing, grind again, dry;
D) with step C) the powder molding slabbing of gained, 750 ℃～850 ℃ following sintering 2 hours, furnace cooling is promptly.
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| CN100471819C (en) * | 2007-05-16 | 2009-03-25 | 中材高新材料股份有限公司 | Ceramics powder material of absorbing laser and preparation method |
| CN102140691B (en) * | 2011-02-12 | 2012-10-17 | 河北联合大学 | Method for synthesizing vanadium acid zinc micro/nanowire material by adopting hydrothermal method |
| CN102320658B (en) * | 2011-07-22 | 2013-07-10 | 河北联合大学 | Method for synthesizing alkaline earth metal vanadate micro/nano materials by adopting hydrothermal/solvothermal method |
| CN103131271B (en) * | 2013-02-28 | 2015-04-01 | 安徽工业大学 | Zinc vanadate nanorod composite paint |
| CN112830773A (en) * | 2021-01-08 | 2021-05-25 | 惠州市新泓威科技有限公司 | Humidity-sensitive porous ceramic, atomizing core and preparation method thereof |
| CN112811925A (en) * | 2021-01-08 | 2021-05-18 | 惠州市新泓威科技有限公司 | Humidity-sensitive porous ceramic, atomizing core and preparation method thereof |
| CN116283356B (en) * | 2023-02-16 | 2024-04-02 | 安徽维纳物联科技有限公司 | SnO (tin oxide) 2 Methyl hydride gas sensor and preparation method thereof |
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| JPS5848841A (en) * | 1981-09-18 | 1983-03-22 | Marcon Electronics Co Ltd | Temperature compensating circuit of ceramic moisture sensing element |
| CN85107480A (en) * | 1985-10-05 | 1987-02-25 | 华中工学院 | Ceramic moisture-sensitive element |
| CN1165125A (en) * | 1995-08-31 | 1997-11-19 | 松下电器产业株式会社 | Zinc oxide ceramics composition and its manufacture method and zinc oxide nonlinear resistance |
-
2005
- 2005-09-08 CN CNB2005100370673A patent/CN100366575C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5848841A (en) * | 1981-09-18 | 1983-03-22 | Marcon Electronics Co Ltd | Temperature compensating circuit of ceramic moisture sensing element |
| CN85107480A (en) * | 1985-10-05 | 1987-02-25 | 华中工学院 | Ceramic moisture-sensitive element |
| CN1165125A (en) * | 1995-08-31 | 1997-11-19 | 松下电器产业株式会社 | Zinc oxide ceramics composition and its manufacture method and zinc oxide nonlinear resistance |
Non-Patent Citations (1)
| Title |
|---|
| K+掺杂对SnO2-LiZnVO4系湿敏陶瓷性能的影响. 胡素梅，陈海波，傅刚.电子元件与材料，第23卷第7期. 2004 * |
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