CN1374519A - Prepn of oxygen-sensing sensor - Google Patents
Prepn of oxygen-sensing sensor Download PDFInfo
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- CN1374519A CN1374519A CN 02112887 CN02112887A CN1374519A CN 1374519 A CN1374519 A CN 1374519A CN 02112887 CN02112887 CN 02112887 CN 02112887 A CN02112887 A CN 02112887A CN 1374519 A CN1374519 A CN 1374519A
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Abstract
The preparation of oxygen-sensing sensor includes the steps of: preparation of titanium trichloride doped with certain amount of niobium or tantalum pentachloride as source matter; addition of hydrogen peroxide as strong oxidant and DBS surface cladding agent and stirring at 50-70 deg.c water bath for 3-5 hr to form gel; mixing obtained powder with terpineol and painting the mixture to ceramic tube with brush-type electrodes; sintering in a muffle furnace at 380-450 deg.c for 1 hr to prepare niobium or tantalum pentachloride doped TiO2 nanometer powder, addition of heating filament to prepare the thick-film oxygen-sensing element; and aging through electrical heating for 10 dyas. The present invention has low working temperature, high sensitivity, fast response and high stability.
Description
Technical field:
The present invention relates to a kind of preparation method of oxygen-sensing sensor, exactly, it is the preparation method who belongs to a kind of nano-functional material.
Background technology:
Oxygen is one of the abundantest element of the earth, and is closely related with mankind's activity, and a lot of fields relate to oxygen measurement.As in car exhaust gas purifier, by measuring the content of oxygen in the tail gas, can control and reduce harmful gas pollution in the tail gas, raise the efficiency; Coal-fired (oil) boiler is the monitoring combustion conditions, regulates wind (oil) ratio by lambda sensor is installed, and reaches purpose energy-conservation and the protection environment; Anoxic in the operating environment detects (anoxic instrument); Clinical in the medical treatment has aspects such as oxygen therapy and atmosphere environment monitoring, bioengineering, Aero-Space, petrochemical complex all to need to possess oxygen sensor, this shows that oxygen sensor has application prospect widely.
Yet, at present comparatively ripe and practicability have only ZrO
2Electrolyte oxygen sensor and the build TiO that is used to monitor vehicle exhaust
2Oxygen-sensing sensor, the former working temperature height (〉=600 ℃) costs an arm and a leg, and quality because it needs doped precious metal, easily causes poison deactivation preferably all by import, and needs reference, complex structure, shortcoming such as will regularly replace; And the quick narrow range of latter's oxygen, and can only use down at high temperature (〉=700 ℃), limited its application in other respects.At TiO
2Base oxygen-sensing sensor research aspect, low working temperature semiconductor lambda sensor is also pursued in research by the man research institution of number both at home and abroad, but they all adopt tetravalent salt of titanium is the source material, can't be under sintering temperature and low, obtain the quick phase of oxygen-rutile phase, and high temperature sintering can cause defectives such as big, the easy reunion of crystal grain, surfactivity reduction, and need at high temperature work, the minimum operating temperature that is obtained at present is 250 ℃ (Australian scholars), still can't satisfy the demand of practicability.
From searching document as can be known: application number is 94102375, the applying date is on 03 09th, 1994, name is called the method for preparing titanium dioxide-niobium oxide composite oxides oxygen-sensitive material, the way of inventor's solid phase synthesis that Peng Jun adopts, though its material and the present invention belong to semi-conductor type together, and is titania and mixes niobium oxide, but the preparation method is different with the present invention, and its working temperature higher be 720 ℃.Application number is 94107885, and the applying date is 1994.07.29, and the application people is a Nippondenso Co., Ltd., and name is called oxygen sensor, adopts solid electrolyte.
" the Improvement of the oxygen gassensitivity in doped TiO of work such as document Rajnish K.Sharma
2Think films " " improvement of the base and doped thick-film type oxygen-sensing sensor of titania sensitivity " (Sensors and Actuators B 56 (1999) 215-219) write:
Utilize solid phase synthesis technique to prepare TiO
2Nb mixes respectively
5+, Cr
3+The solid phase powder, on the aluminium substrate, utilize screen printing technique to be made into thick-film type oxygen photosensitive elements again, 1300 ℃ of sintering are 5 hours in air, obtained the quick phase of rutile phase-oxygen, and material carries out structure and characteristic present with XRD (X-ray powder diffraction) and SEM (scanning electron microscope); Obtained optimum doping amount and optimum working temperature is respectively by the quick feature measurement of oxygen: Nb (0.2wt%), 550 ℃ in the 1200ppm partial pressure of oxygen; Cr (0.4wt%), 700 ℃ in the 1000ppm partial pressure of oxygen.With unadulterated TiO
2Oxygen photosensitive elements characteristic relatively shows that mainly sensitivity and response time all increase.
Summary of the invention:
The present invention seeks to invent that a kind of working temperature is low, highly sensitive, response is fast, good stability, practicality semi-conductor type nanometer oxygen sensor that cost is low.
Task of the present invention is: the preparation method who makes a kind of oxygen-sensing sensor the steps include:
(1) utilizes the columbium pentachloride of titanium trichloride and doping 7-15% mole, 1-8% mole tantalic chloride to be the source material, under 50 ℃ of-70 ℃ of water-baths, fully stir;
(2) adopt sol-gel process, that is: the ultimate principle of sol-gel process is that metal alkoxide or inorganic salts are directly formed colloidal sol or form colloidal sol with fixed attention through separating through hydrolysis, make the solute polymeric gelization then, again gel drying, sintering are removed the process that organic principle obtains inorganic material at last.
Add hydrogen peroxide strong oxidizer and DBS surface covering, 50 ℃ of-70 ℃ of water-baths are stirred until forming gel down, continue insulation 3-5 hour;
(3) modulate above nano-powder with terpinol, evenly spread upon on the porcelain tube with brush electrode;
(4) it is placed muffle furnace, after 380 ℃ of-450 ℃ of following 1-5 hour sintering, prepared TiO
2Base and doped certain proportion columbium pentachloride, tantalic chloride nano-powder are enclosed heater strip and are made thick film gas sensing element, aging 10 days of electrical heating.
Between step 2-3, insert (1) and gel is formed on vacuum drying chamber 70-90 ℃, dry 4-24 hour; (2) ground 2 hours, make nano-powder, at 350 ℃, pre-burning 1 hour to remove relevant organism, forms the thick-film type semiconductor element.
The present invention adopts new method, new technology, preparation titanium dioxide base nano to mix the thick model oxygen-sensing sensor of Nano semiconductor of niobium, tantalum, with realize low working temperature, highly sensitive, response is fast, the oxygen sensitive characteristic of high stability, has application prospect extensively.The present invention is different with the structure of quick powder of existing oxygen and gas sensor, and material is different with existing invention.
Description of drawings:
The present invention will be further described below with reference to accompanying drawing:
Fig. 1 thick-film type semiconductor oxygen-sensing sensor element synoptic diagram
Fig. 2 gas-sensitive property proving installation figure
In the drawings: 1 be the double-deck Stainless Steel net of 100 orders, 2 for the noble metal electrode lead-in wire, 3 for the sensitive element tube core, 4 for heater coil, 5 for the resin material base, 6 for the nickel-clad copper hoop, 7 for the nickel pin, 8 for vacuum pump, 9 for vacuum meter, 10 for sealing vacuum test chamber, 11 for gas sensor, 12 be the air-sensitive tester.
Its step 3 of preparation method of a kind of oxygen-sensing sensor is described with more than the terpinol modulation Nano-powder evenly spreads upon on the porcelain tube with brush electrode, that is to say with terpinol and transfers Make above nano-powder, evenly spread upon on the sensing element tube core 3 among Fig. 1.
The doped source material is titanium trichloride, columbium pentachloride, tantalic chloride, and it is strong to add the valency hydrogen peroxide Oxidant and DBS surface covering. In 50 ℃ of-70 ℃ of water-baths, utilize sol-gel process (Sol-gel method) preparation nano-powder, preparation TiO2Base and doped certain proportion columbium pentachloride, The quick powder of nanoscale oxygen of tantalic chloride. Above nanometer grade powder is through 80 ℃ of vacuum drying 12 hours, dried powder was at 350 ℃, pre-burning in 1 hour. Nano powder after the above pre-burning Body is made conditioning agent through terpinol and is evenly spread upon on the porcelain tube with electrode and heater strip process 400 ℃ of sintering form the thick-film type semiconductor gas sensor. Material property (chemistry of the present invention Composition, chemical structural formula, rational characterisitic parameter) be:
(1)TiO
2Doping columbium pentachloride, tantalic chloride nano-powder are the pure rutile phase
(2) specific surface 〉=65m of powder2/ g, granularity≤100nm, grain size≤13nm
Apparatus characteristic of the present invention is:
The present invention adopts homemade gas sensing characteristic vacuum test chamber, is measuring the quick characteristic of oxygen The time, keep gas sensor to be in all the time partial pressure of oxygen at 100ppm, utilize the heating of gas sensor Coil heats (140 ℃), the quick characteristic of the oxygen of element is by RQ-2 type Characteristics of Gas Sensors tester Measure. (referring to Figure of description 2)
In 50 ℃ of-70 ℃ of water-baths, utilize sol-gel process (Sol-gel method) preparation nano-powder, preparation TiO2The quick powder of nanoscale oxygen of base and doped certain proportion columbium pentachloride, tantalic chloride Body. Utilize titanium trichloride and be doped to the source material, under 60 ℃ of water-baths, fully stir. Add Hydrogen peroxide strong oxidizer and DBS surface covering stir under 60 ℃ of water-baths until form solidifying Glue continues insulation 3-5 hour. Above nano-powder is through 80 ℃ of vacuum drying 12 hours, Dried powder is at 350 ℃ of sintering. Nano-powder after the above pre-burning is done accent through terpinol The joint agent evenly spreads upon on the porcelain tube with electrode and heater strip, through 400 ℃ of sintering, forms The thick-film type semiconductor gas sensor.
Concrete steps of the present invention are:
(1) utilizes titanium trichloride (TiCl3) (being dissolved in content 15% in the HCl solution) and The suitable source that is doped to material fully stirs under 60 ℃ of water-baths.
(2) add an amount of hydrogen peroxide (H of valency2O
2) strong oxidizer and DBS surface covering, 60 Stir under ℃ water-bath until form gel, continue insulation 3-5 hour.
(3) gel is formed on 80 ℃ of vacuum drying chambers, dry 12 hours.At 350 ℃, pre-burning 1 hour is to remove relevant organism.
(4) ground 2 hours, make nano-powder.At 350 ℃, pre-burning 1 hour is to remove relevant organism.
(5) modulate above nano-powder with terpinol, evenly spread upon on the porcelain tube with brush electrode, form the thick-film type semiconductor element.(referring to Figure of description 1)
(6) the thick-film type element places muffle furnace, 400 ℃ of 1 hour sintering.Afterwards, enclose heater strip and make gas sensor, aging 10 days of electrical heating.
(7) on homemade air-sensitive tester, mensuration oxygen is pressed in the quick characteristic of oxygen under the 100ppm.
Embodiment one,
(1) utilizes titanium trichloride (TiCl
3) (being dissolved in content 15% in the HCl solution) and doping NbCl
5For the source material is worked as Nb: Ti=11: 89 (mol ratios) (more than be analyze pure), fully stir under 60 ℃ of water-baths.
(2) add an amount of hydrogen peroxide (H of valency
2O
2) strong oxidizer and DBS surface covering, 60 ℃ of water-baths are stirred until forming gel down, continue insulation 3-5 hour.
(3) gel is formed on 80 ℃ of vacuum drying chambers, dry 12 hours.
(4) ground 2 hours, make nano-powder.At 350 ℃, pre-burning 1 hour is to remove relevant organism.
(5) modulate above nano-powder with terpinol, evenly spread upon on the porcelain tube with brush electrode, form the thick-film type semiconductor element.
(6) the thick-film type element places muffle furnace, 400 ℃ of 1 hour sintering.Measuring its structure with X-ray powder diffraction is the pure rutile phase, and crystallite dimension is 10 nanometers, and specific surface is 78m
2/ g.Afterwards, enclose heater strip and make gas sensor, aging 10 days of electrical heating.
(7) on homemade air-sensitive tester, mensuration oxygen is pressed in the quick characteristic of oxygen under the 100ppm.
Embodiment two,
(1) utilizes titanium trichloride (TiCl
3) (being dissolved in content 15% in the HCl solution) and doping NbCl
5For the source material is worked as Ta: Ti=4: 96 (mol ratios) (more than be analyze pure), fully stir under 60 ℃ of water-baths.
(2) add an amount of hydrogen peroxide (H of valency
2O
2) strong oxidizer and DBS surface covering, 60 ℃ of water-baths are stirred until forming gel down, continue insulation 3-5 hour.
(3) gel is formed on 80 ℃ of vacuum drying chambers, dry 12 hours.
(4) ground 2 hours, make nano-powder.At 350 ℃, pre-burning 1 hour is to remove relevant organism.
(5) modulate above nano-powder with terpinol, evenly spread upon on the porcelain tube with brush electrode, form the thick-film type semiconductor element.
(6) the thick-film type element places muffle furnace, 400 ℃ of 1 hour sintering.Measuring its structure with X-ray powder diffraction is the pure rutile phase, and crystallite dimension is 11 nanometers, and specific surface is 85m
2/ g.Afterwards, enclose heater strip and make gas sensor, aging 10 days of electrical heating.
(7) on homemade air-sensitive tester, measure the quick characteristic of the oxygen of oxygen concentration under 100ppm.The characteristics that the present invention had are:
Measure its gas-sensitive property and mechanical property under the 100ppm oxygen concentration at the air-sensitive test cabinet of self assembly, the result is as follows:
Sensitivity K=R
0/ R
x〉=3 (R
0: be the resistance value under the clean air, R
x: be the resistance value under the 100ppm oxygen)
Resistance value under the clean air: R
0≤ 10M Ω
Operating humidity range: 20～90RH
Heating work temperature: 140 ℃
The stability of gas sensor: K/K≤10% (element was through 180 days, and long-term heating back is measured under 100 ℃ of temperature air)
R
0/ R
0≤ 10% (element was through 180 days, and long-term heating back is measured under 100 ℃ of temperature air)
Response characteristic: response time t
p≤ 10 seconds
Release time t
r≤ 20 minutes
Physical strength: gas sensor is in the position of 1 meter of height, and free falling is 5 times repeatedly, and element surface is flawless.
Claims (7)
1. the preparation method of an oxygen-sensing sensor is characterized in that: the steps include:
(1) utilizes the columbium pentachloride of titanium trichloride and doping 7-15% mole, 1-8% mole tantalic chloride to be the source material, under 50 ℃ of-70 ℃ of water-baths, fully stir;
(2) adopt sol-gel process, that is: the ultimate principle of sol-gel process is that metal alkoxide or inorganic salts are directly formed colloidal sol or form colloidal sol with fixed attention through separating through hydrolysis, make the solute polymeric gelization then, again gel drying, sintering are removed the process that organic principle obtains inorganic material at last, add hydrogen peroxide strong oxidizer and DBS surface covering, 50 ℃ of-70 ℃ of water-baths are stirred down until forming gel, continue insulation 3-5 hour;
(3) modulate above nano-powder with terpinol, evenly spread upon on the porcelain tube with brush electrode;
(4) it is placed muffle furnace, after 380 ℃ of-450 ℃ of following 1-5 hour sintering, prepared TiO
2Base and doped columbium pentachloride, tantalic chloride nano-powder are enclosed heater strip and are made thick film gas sensing element, aging 10 days of electrical heating.
2. the preparation method of a kind of oxygen-sensing sensor according to claim 1 is characterized in that: insert (1) and gel is formed on vacuum drying chamber 70-90 ℃, dry 4-24 hour between step 2-3; (2) ground 2 hours, make nano-powder, at 350 ℃, pre-burning 1 hour to remove relevant organism, forms the thick-film type semiconductor element.
3. the preparation method of a kind of oxygen-sensing sensor according to claim 1 is characterized in that: in 50 ℃ of-70 ℃ of water-baths, utilize sol-gel process (Sol-gel method) preparation nano-powder, preparation TiO
2The quick powder of nanoscale oxygen of base and doped columbium pentachloride, tantalic chloride.
4. the preparation method of a kind of oxygen-sensing sensor according to claim 1, it is characterized in that: the nano-powder after the above pre-burning, make correctives through terpinol and evenly spread upon on the porcelain tube with electrode and heater strip,, form the thick-film type semiconductor gas sensor through 400 ℃ of sintering.
5. the preparation method of a kind of oxygen-sensing sensor according to claim 1 is characterized in that: utilize titanium trichloride and be doped to the source material, fully stir under 60 ℃ of water-baths.
6. the preparation method of a kind of oxygen-sensing sensor according to claim 1 is characterized in that: add hydrogen peroxide strong oxidizer and DBS surface covering, stir under 60 ℃ of water-baths until forming gel, continue insulation 3-5 hour.
7. the preparation method of a kind of oxygen-sensing sensor according to claim 2, it is characterized in that: above nano-powder was through 80 ℃ of vacuum drying 12 hours, and dried powder is at 350 ℃ of sintering.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368798C (en) * | 2005-05-26 | 2008-02-13 | 上海交通大学 | Method for preparing sensor for chemical oxygen demand of Nano tube array and application |
| CN101158661B (en) * | 2007-11-16 | 2011-05-11 | 华中科技大学 | Semi-conductor oxidate gas sensor preparation method |
| CN102353702A (en) * | 2011-07-22 | 2012-02-15 | 李学中 | Oxide semiconductor normal temperature oxygen sensor |
| CN103101973A (en) * | 2013-01-16 | 2013-05-15 | 曲阜师范大学 | Vanadium and palladium-codoped nanometer titania gas-sensitive material as well as preparation method and applications thereof |
| CN104422671A (en) * | 2013-08-30 | 2015-03-18 | 华中科技大学 | Method and device for improving photo-excitation gas-sensitive property of titanium dioxide |
| CN104458825A (en) * | 2014-10-22 | 2015-03-25 | 武汉工程大学 | Oxygen gas sensitive element and detection method thereof |
-
2002
- 2002-04-14 CN CNB021128871A patent/CN1195221C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368798C (en) * | 2005-05-26 | 2008-02-13 | 上海交通大学 | Method for preparing sensor for chemical oxygen demand of Nano tube array and application |
| CN101158661B (en) * | 2007-11-16 | 2011-05-11 | 华中科技大学 | Semi-conductor oxidate gas sensor preparation method |
| CN102353702A (en) * | 2011-07-22 | 2012-02-15 | 李学中 | Oxide semiconductor normal temperature oxygen sensor |
| CN103101973A (en) * | 2013-01-16 | 2013-05-15 | 曲阜师范大学 | Vanadium and palladium-codoped nanometer titania gas-sensitive material as well as preparation method and applications thereof |
| CN103101973B (en) * | 2013-01-16 | 2014-05-21 | 曲阜师范大学 | Vanadium and palladium-codoped nanometer titania gas-sensitive material as well as preparation method and applications thereof |
| CN104422671A (en) * | 2013-08-30 | 2015-03-18 | 华中科技大学 | Method and device for improving photo-excitation gas-sensitive property of titanium dioxide |
| CN104422671B (en) * | 2013-08-30 | 2017-09-29 | 华中科技大学 | It is a kind of to improve the method and device that titanium-dioxide photo excites air-sensitive performance |
| CN104458825A (en) * | 2014-10-22 | 2015-03-25 | 武汉工程大学 | Oxygen gas sensitive element and detection method thereof |
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| Publication number | Publication date |
|---|---|
| CN1195221C (en) | 2005-03-30 |
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