CN116609399A - Pure titanium material coating sensor for detecting nitric oxide and preparation method and application thereof - Google Patents
Pure titanium material coating sensor for detecting nitric oxide and preparation method and application thereof Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000010936 titanium Substances 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 47
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 45
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 35
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 35
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 35
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229940079864 sodium stannate Drugs 0.000 claims abstract description 34
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 abstract description 30
- 238000001514 detection method Methods 0.000 abstract description 20
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 description 16
- 238000004544 sputter deposition Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to the field of coating materials, and discloses a pure titanium material coating sensor for detecting nitric oxide, a preparation method and application thereof. The sensor comprises a pure titanium material, a micro-arc oxidation coating and an electrode; the micro-arc oxidation coating is arranged on the surface of the pure titanium material through micro-arc oxidation of electrolyte of sodium phosphate, sodium tungstate and sodium stannate, and the electrode is arranged on the micro-arc oxidation coating. The invention carries out micro-arc oxidation by the composite electrolyte of sodium phosphate, sodium tungstate and sodium stannate, and forms SnO which can be applied to low-concentration nitric oxide detection on the surface of pure titanium material 2 ‑WO 3 The coating layer, through arranging the electrode and utilizing the oxygen adsorption-desorption principle to detect, shows extremely excellent sensitivity and selectivity to nitric oxide compared with conventional gases, so that the nitric oxide can be effectively, conveniently and simply detected in real time.
Description
Technical Field
The invention relates to the field of coating materials, in particular to a pure titanium material coating sensor for detecting nitric oxide, a preparation method and application thereof.
Background
Nitric Oxide (NO) is colorless and odorless, a hazardous gas threatening human survival, mostly produced by the combustion of fossil fuels in industrial production. High concentrations (25 ppm) can impair nerve function and cause neurodegeneration and other diseases. At the same time, NO is also the simplest biologically active molecule in the body, playing a vital biological role in the cardiovascular, cerebrovascular, immune, neurological, urinary and reproductive systems. For example, the concentration of NO in oral breathing in healthy people is typically less than 25ppb, and in asthmatic or airway inflammatory patients is higher than 50ppb. So its detection in daily life is becoming more and more important. However, challenges remain in achieving effective detection of NO in breath, as in inexpensive, portable devices. Therefore, there is an urgent need for stable and effective detection of low concentrations of NO.
At present, detection methods based on electrochemistry, high performance liquid chromatography, gas chromatography, polarography, fluorescence method and the like are established by conventional methods for detecting NO. Although these methods are widely used, their large-scale application is still limited due to high cost, complex operation, and in particular, the inapplicability to real-time detection.
Disclosure of Invention
In view of the above, the present invention aims to provide a sensor for detecting a coating of pure titanium material of nitric oxide, which is capable of having a high sensitivity response to NO in a low concentration environment and excellent selectivity to other VOC gases;
it is a further object of the present invention to provide a method for manufacturing the above sensor and its use for detecting nitric oxide and for manufacturing a nitric oxide detecting product.
In order to solve the above technical problems or at least partially solve the above technical problems, the present invention provides a method for solving the above technical problems or at least partially solving the above technical problems, and as a first aspect of the present invention, a pure titanium material composite coating sensor for detecting nitric oxide is provided, including a pure titanium material, a micro-arc oxidation coating and an electrode; the micro-arc oxidation coating is arranged on the surface of the pure titanium material through micro-arc oxidation of electrolyte of sodium phosphate, sodium tungstate and sodium stannate, and the electrode is arranged on the micro-arc oxidation coating.
Optionally, the pure titanium material comprises TA1 to TA4 industrial pure titanium material.
Optionally, the electrodes are interdigital electrodes.
Optionally, the concentration of sodium phosphate in the electrolyte is 8-12 g/L, the concentration of sodium tungstate is 1-2 g/L, and the concentration of sodium stannate is 1-2 g/L.
As a second aspect of the present invention, the present invention provides the use of the sensor according to the present invention for detecting nitric oxide or for preparing a nitric oxide detecting product, based on the excellent properties of high sensitivity and selectivity exhibited by the sensor according to the present invention in detecting nitric oxide. Wherein the nitric oxide comprises 0.1-200 ppm nitric oxide.
As a third aspect of the present invention, there is provided a method for manufacturing the sensor, comprising:
step 1, polishing, degreasing and cleaning pretreatment of a pure titanium material;
step 2, performing micro-arc oxidation on the pretreated pure titanium material in sodium phosphate, sodium tungstate and sodium stannate electrolyte to form a micro-arc oxidation coating;
and step 3, setting an electrode on the micro-arc oxidation coating to obtain the sensor.
As a fourth aspect of the invention there is provided a product for detecting nitric oxide comprising a device for recording a change in resistance and a sensor according to the invention, the device and the electrodes on the sensor being connected by wires.
Optionally, the device for recording the change in resistance value includes a multimeter and a data processor.
As a fifth aspect of the present invention, there is provided a method for detecting nitric oxide, comprising placing the sensor of the present invention in nitric oxide standards of different concentrations, and establishing a standard curve of resistance change data and nitric oxide concentration by means of a device for recording resistance value changes; and then placing the sensor in an environment to be detected, obtaining resistance value change data, and obtaining the concentration of nitric oxide in the environment to be detected through a standard curve.
The invention uses sodium phosphate and tungstic acidMicro-arc oxidation is carried out on the composite electrolyte of sodium and sodium stannate, and SnO which can be applied to low-concentration nitric oxide detection is formed on the surface of a pure titanium material 2 -WO 3 The coating layer, through arranging the electrode and utilizing the oxygen adsorption-desorption principle to detect, shows extremely excellent sensitivity and selectivity to nitric oxide compared with conventional gases, so that the nitric oxide can be effectively, conveniently and simply detected in real time.
Description of the drawings:
FIG. 1 is an SEM image of a sensor coating of the present invention;
FIG. 2 is an EDS diagram of a sensor coating of the present invention;
FIG. 3 is a schematic diagram showing the components of the detection system;
FIG. 4 shows the results of the nitric oxide response of the sensor pairs (0.1-200 ppm) prepared in the electrolyte sets (1) - (4) of example 1; wherein, the legend is respectively represented by numbers 1-4 in the electrolyte groups (1) - (4), and the scatter diagrams are corresponding results of the electrolyte groups (4), (3), (2) and (1) from top to bottom in sequence;
FIG. 5 shows the results of the nitric oxide response of the sensor pairs (0.1-200 ppm) prepared in the electrolyte sets (1) - (4) of example 2; wherein, the numbers 1-4 respectively represent the electrolyte groups (1) - (4), and the scatter diagrams are the corresponding results of the electrolyte groups (2), (4), (3) and (1) from top to bottom;
FIG. 6 shows the results of the sensor pair (0.1-200 ppm) nitric oxide response prepared for electrolyte sets (5) - (8) of example 2; wherein, the numbers 1-4 respectively represent the electrolyte groups (5) - (8), and the scatter diagrams are the corresponding results of the electrolyte groups (3), (2), (4) and (1) from top to bottom;
FIG. 7 shows the results of the sensor pair (0.1-200 ppm) nitric oxide response prepared for electrolyte sets (1) - (2) of example 3; wherein, the numbers 1-2 respectively represent the electrolyte groups (1) - (2), and the scatter diagrams are the corresponding results of the electrolyte groups (2) - (1) from top to bottom;
FIG. 8 shows the results of the nitric oxide response of the sensor pairs (0.1-200 ppm) prepared in the electrolyte sets (1) - (4) of example 4; wherein, the numbers 1-4 respectively represent the electrolyte groups (1) - (4), and the scatter diagrams are the corresponding results of the electrolyte groups (4), (3), (1), (2) from top to bottom;
FIG. 9 is a bar graph showing Ra/Rg values for various detected gases (gas selectivity test results);
FIG. 10 is a graph showing a fit of a sensor of the present invention for detecting different concentrations of nitric oxide;
FIG. 11 shows the optimum operating temperature profile of the sensor of the present invention.
The specific embodiment is as follows:
the invention discloses a pure titanium material coating sensor for detecting nitric oxide, a preparation method and application thereof, and a person skilled in the art can properly improve process parameters by referring to the content of the sensor. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the sensor and its methods of manufacture and use have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the sensor and its methods of manufacture and use described herein can be modified or adapted and combined to practice and use the technology of the invention without departing from the spirit and scope of the invention.
In a first aspect of the invention, there is provided a pure titanium material composite coating sensor for detecting nitric oxide, comprising a pure titanium material, a micro-arc oxidation coating and an electrode; the micro-arc oxidation coating is arranged on the surface of the pure titanium material through micro-arc oxidation of electrolyte of sodium phosphate, sodium tungstate and sodium stannate, the electrode is arranged on the micro-arc oxidation coating, an SEM (scanning electron microscope) diagram of the sensor coating is shown in FIG. 1, and an EDS (electron beam ionization) diagram is shown in FIG. 2.
In certain embodiments of the invention, the pure titanium material comprises TA 1-TA 4 industrial pure titanium material, wherein Ti in the pure titanium material is more than or equal to 99%; in other embodiments of the present invention, the pure titanium material comprises a TA1 pure titanium material, more specifically, the TA1 pure titanium material comprises the following elemental components (mass fraction): fe:0.2%, C:0.08%, N:0.03%, H:0.015%, O:0.18%, others: 0.4% and the balance Ti.
In certain embodiments of the invention, the electrodes are interdigitated electrodes.
In some embodiments of the invention, the electrolyte has a sodium phosphate concentration of 8-12 g/L, a sodium tungstate concentration of 1-2 g/L, and a sodium stannate concentration of 1-2 g/L. In still other embodiments of the invention, the electrolyte has a sodium phosphate concentration of 8g/L, 10g/L, or 12g/L, a sodium tungstate concentration of 1g/L, or 2g/L, and a sodium stannate concentration of 1g/L, or 2g/L.
The sensor for detecting the nitric oxide gas is based on the resistance change of metal oxide formed by micro-arc oxidation and coating on the surface, which is exposed to air and nitric oxide gas, and is based on the principle of oxygen adsorption-desorption of the metal oxide. When the pure titanium coating material is exposed to air, oxygen can extract electrons from a conduction band of the surface coating of the pure titanium material, so that the resistance is increased; when NO is exposed to a pure titanium material surface coating, NO will undergo an oxidation-reduction reaction with adsorbed oxygen on the metal oxide coating surface, releasing trapped electrons, and the electrical resistance will decrease, as follows:
NO(gas)+O - →NO 2 (gas)+e -
in the comparison of different electrolytes, the prepared pure titanium material is used for detecting the responsiveness of nitric oxide, and the result shows that the electrolyte prepared from sodium phosphate, sodium tungstate and sodium stannate has excellent performance in the aspect of NO detection under the condition of low concentration and has high sensitivity.
Compared with common VOC gases such as triethylamine, ethanol, acetone, formaldehyde and the like, the pure titanium material provided by the invention is used for detecting the responsivity of each gas, and the result shows that the resistance specific sensitivity (K=Ra/Rg) of the pure titanium material to nitric oxide is far higher than that of other gases, so that the tungsten and tin doped coating on the surface of the pure titanium material provided by the invention has high sensitivity to low-concentration nitric oxide, better selectivity and interference reduction. In view of the above-mentioned beneficial effects of the sensor of the present invention and the excellent performance in practical detection processes, in a second aspect of the present invention, there is provided the use of the sensor for detecting nitric oxide or for preparing a nitric oxide detecting product. Wherein the nitric oxide comprises 0.1-200 ppm nitric oxide.
In a third aspect of the present invention, there is also provided a method for manufacturing the sensor, comprising:
step 1, polishing, degreasing and cleaning pretreatment of a pure titanium material;
step 2, performing micro-arc oxidation on the pretreated pure titanium material in sodium phosphate, sodium tungstate and sodium stannate electrolyte to form a micro-arc oxidation coating;
and step 3, setting an electrode on the micro-arc oxidation coating to obtain the sensor.
In certain embodiments of the present invention, step 1 is:
the pure titanium material is polished step by step, ultrasonic cleaning is carried out by adopting absolute ethyl alcohol and water, and then oil removal and cleaning are carried out by adopting alkaline oil removal liquid. The silicon carbide sand paper with gradually increased marks is adopted for polishing step by step, and the polishing degree is bright, no obvious scratches exist on the surface, and the lines are consistent. The alkaline degreasing liquid is sodium hydroxide, and can be 10% sodium hydroxide solution.
In order to make the thickness of the prepared coating more uniform, the porosity of the coating is higher, and submicron holes are formed, so that the nitric oxide detection is facilitated, and in certain embodiments of the invention, the micro-arc oxidation is performed in a constant-current mode; in other embodiments of the present invention, the forward current in the constant current mode is preset to be 2-8A, and may be selected to be 4A; the negative current is preset to be 1-5A, and can be selected to be 3A; the pulse frequency is fixed to be 0.1-0.3 Hz, and can be selected to be 0.2Hz; the duty cycle is set to 70% -90%, alternatively 80%. In other embodiments of the present invention, in the constant current mode, the current rising mode is gradually increased from 0A every 0.5A until a preset value, and positive and negative directions are synchronously performed, so that the prepared micro-arc oxidation coating has better quality, and the micro-arc oxidation power supply can be protected.
In certain embodiments of the invention, pure titanium material is used as the positive electrode, other suitable metals such as stainless steel are used as the negative electrode, and the distance between the positive electrode and the negative electrode is controlled to be 10cm; the temperature of the electrolyte is controlled and maintained at 20-35 ℃ by an internal and external circulation refrigerating device.
In some embodiments of the present invention, the time of the micro-arc oxidation may be selected according to the actual situation, in some embodiments of the present invention, the time of the micro-arc oxidation is 4 to 6 minutes, and in other embodiments, the time of the micro-arc oxidation is 4 minutes, 5 minutes, or 6 minutes.
In certain embodiments of the invention, the electrode is coated on the surface coating of the pure titanium material by using a mask plate, and the interdigital electrode is prepared by an ion sputtering process. In other embodiments of the invention, the ion sputtering process employs a cyclic sputtering method, and the sputtering duration and the number of cycles are adjusted according to the shape of the desired interdigital electrode; in other embodiments of the invention, the sputtering time period is 90s and the number of cycles is 6 cycles.
In a fourth aspect of the invention, there is provided a product for detecting nitric oxide comprising a device for recording a change in resistance and a sensor according to the invention, the device and electrodes on the sensor being connected by wires.
In certain embodiments of the invention, the wire is a conductive metal wire, such as a copper wire; in other embodiments of the invention, the wires are adhered to the electrodes by conductive silver paste or other conductive material to form a connection.
In some embodiments of the invention, the device for recording changes in resistance values includes a multimeter, optionally a digital multimeter, and a data processor, optionally a computer device.
In a fifth aspect of the invention, there is provided a method of detecting nitric oxide, the sensor of the invention is placed in nitric oxide standards of different concentrations, and a standard curve of resistance change data and nitric oxide concentration is established by means of a device for recording resistance value changes; and then placing the sensor in an environment to be detected, obtaining resistance value change data, and obtaining the concentration of nitric oxide in the environment to be detected through a standard curve.
Unless specifically stated otherwise, experimental environments and parameter conditions for each group in the test of the specific examples remained consistent, except for the differences explicitly noted.
The invention provides a pure titanium material coating sensor for detecting nitric oxide, and a preparation method and application thereof.
Example 1: preparation of the sensor for nitric oxide detection of the present invention
1. Preparation method
1. Pure titanium substrate pretreatment
The pure titanium substrate is TA1 industrial pure titanium, and the element components (mass fraction) of the pure titanium substrate are as follows: fe:0.2%, C:0.08%, N:0.03%, H:0.015%, O:0.18%, others: 0.4% and the balance Ti. The method comprises the steps of dividing a pure titanium matrix into sizes of 25mm multiplied by 2mm by wire cutting, polishing with 400# silicon carbide sand paper, 800# silicon carbide sand paper, 1000# silicon carbide sand paper and 2000# silicon carbide sand paper, wherein the polishing effect is that the surface is bright, no obvious scratches and consistent in lines, respectively ultrasonically cleaning in acetone, absolute ethyl alcohol and deionized water for 10min, and air-drying by using an electric hair drier, so that the pretreated pure titanium matrix is obtained;
immersing bright and clean pure titanium into degreasing liquid, wherein the degreasing liquid is 10% sodium hydroxide solution, the temperature is 60 ℃, performing ultrasonic cleaning for 10min, taking out the pure titanium, cleaning the pure titanium with clear water for 3 times, and drying by using an electric hair drier to obtain a pure titanium matrix after ultrasonic treatment;
2. preparing micro-arc oxidation electrolyte
The micro-arc oxidation electrolyte comprises 8g/L sodium phosphate, 1g/L sodium stannate, 2g/L sodium tungstate and 1g/L sodium tungstate, wherein 3L deionized water is firstly added into an electrolytic tank, and then a proper amount of sodium phosphate, sodium tungstate and sodium stannate are added for full dissolution. The micro-arc oxidation electrolyte needs to be replaced every time of micro-arc oxidation operation, and the micro-arc oxidation electrolyte prepared every time needs to be used within 24 hours to prevent the micro-arc oxidation electrolyte from deteriorating;
(1) 8g/L sodium phosphate+1 g/L sodium stannate+1 g/L sodium tungstate;
(2) 8g/L sodium phosphate+1 g/L sodium stannate+2 g/L sodium tungstate;
(3) 8g/L sodium phosphate+2 g/L sodium stannate+1 g/L sodium tungstate;
(4) 8g/L sodium silicate+2 g/L sodium stannate+2 g/L sodium tungstate;
3. micro-arc oxidation
Placing the pure titanium subjected to surface pretreatment into micro-arc oxidation electrolyte, wherein the pure titanium is connected with the positive electrode of a power supply, the pure titanium is used as the positive electrode, an electrolytic tank of stainless steel is connected with the negative electrode of the power supply, and the pure titanium is used as the negative electrode, and the distance between the positive electrode and the negative electrode is controlled at 10cm; opening the refrigerating device, and controlling the temperature to be 30 ℃; the micro-arc oxidation alternating current pulse power supply is adopted to start power supply, under a constant current mode, positive current is preset to be 4A, negative current is preset to be 3A, the current rising mode is that the current is started from 0A, every 0.5A is gradually increased, and positive and negative directions are synchronously carried out until a preset value is reached. The pulse frequency is fixed to be 0.2Hz, the duty ratio is set to be 80%, the micro-arc oxidation time is 4min, and then pure titanium with a micro-arc oxidation coating on the surface is obtained;
4. ion sputtering
Covering the mask plate on the surface of the micro-arc oxidation coating, fixing the mask plate in a vacuum ion sputtering instrument, controlling the sputtering current to be unchanged, preparing the interdigital electrode by adopting a cyclic sputtering method, wherein the sputtering time is 90 seconds each time, and sputtering for 6 cycles.
5. Adhesion of copper wires
And after sputtering, detecting the conductivity by using a universal meter, and testing the processing quality of the interdigital electrode. And then, the copper wire is stuck on the interdigital electrode by using conductive silver paste, and is dried for 2 hours at 80 ℃ to ensure good contact of the sensor circuit.
SEM and EDS images of the sensor coating prepared according to the present invention referring to fig. 1 and 2, it can be seen from the SEM of fig. 1 that a film layer is preparedThe surface pores are uniform, the pore diameter can reach the micrometer to nanometer level, and the gas-sensitive performance of the porous ceramic material is facilitated. As can be seen from the EDS shown in FIG. 2, sn element, W element and the like are successfully doped into micro-arc TiO 2 The surface of the film layer.
With reference to the detection system shown in fig. 3, a heating platform is arranged in a closed space, and the sensor prepared by the invention is arranged on the heating platform, copper wires are stuck on interdigital electrodes through conductive silver paste and are connected with a universal meter, and the universal meter establishes data transmission with a computer;
the method comprises the steps of injecting a quantitative volatile gas solution into a closed space, enabling the volatile gas solution to volatilize into gas rapidly through the action of a heating platform, enabling the volatile gas solution to react with a sensor in a contact manner to generate a signal, enabling a thermometer to be used for indicating the temperature of the closed space, and enabling a fan to rapidly exhaust the detected volatile gas after detection is completed.
The results of FIG. 4 are the results of the detection of the specific NO resistance sensitivity (K=Ra/Rg) under different electrolyte conditions, and as can be seen from FIG. 4, the sensitivity to 0.1-200 ppm NO is highest when the sodium stannate concentration is 2g/L and the sodium tungstate concentration is 2g/L.
Example 2: influence of different tin and tungsten doping concentrations on gas-sensitive performance of low nitric oxide concentration
1. Test method
Reference is made to example 1;
2. influence of different coatings on nitric oxide detection
The preparation method of reference example 1 is different in that the electrolyte composition is adjusted;
(1) 10g/L sodium phosphate+1 g/L sodium stannate+1 g/L sodium tungstate;
(2) 10g/L sodium phosphate+1 g/L zinc stannate+2 g/L sodium tungstate;
(3) 10g/L sodium phosphate+2 g/L sodium stannate+1 g/L sodium tungstate;
(4) 10g/L sodium phosphate+2 g/L sodium stannate+2 g/L sodium tungstate;
(5) 12g/L sodium phosphate+1 g/L sodium stannate+1 g/L sodium tungstate;
(6) 12g/L sodium phosphate+1 g/L sodium stannate+2 g/L sodium tungstate;
(7) 12g/L sodium phosphate+2 g/L sodium stannate+1 g/L sodium tungstate;
(8) 12g/L sodium phosphate+2 g/L sodium stannate+2 g/L sodium tungstate;
the specific resistance sensitivity (k=ra/Rg) of the above 8 sets of electrolytes was measured, and the results are shown in fig. 5 and 6;
the results in FIG. 5 show that at a sodium phosphate concentration of 10g/L and a sodium stannate concentration of 1g/L, sodium tungstate concentration of 2g/L, exhibited a better response to NO, but much less than the response of the parameters of example 1.
The results in FIG. 6 show that sodium tungstate at a sodium phosphate concentration of 12g/L and sodium stannate at a sodium stannate concentration of 2g/L showed better response to NO but much less than the parameters of example 1.
Example 3: eliminating the influence of substances in the electrolyte on the NO gas-sensitive performance
1. Test method
Reference is made to example 1;
2. influence of different coatings on nitric oxide detection
The preparation method of reference example 1 is different in that the electrolyte composition is adjusted;
(1) 8g/L sodium phosphate+2 g/L sodium stannate;
(2) 8g/L sodium phosphate+2 g/L sodium tungstate;
the results of fig. 7 show that the prepared gas-sensitive film layer has poor response to NO, lower than the parameter responses of example 1 and example 2, and poor sensing performance.
Example 4: influence of substances in the replacement electrolyte on NO gas-sensitive properties
1. Test method
Reference is made to example 1;
2. influence of different coatings on nitric oxide detection
The preparation method of reference example 1 is different in that the electrolyte composition is adjusted;
(1) 8g/L sodium phosphate+2 g/L sodium stannate+2 g/L sodium borate;
(2) 8g/L sodium phosphate+2 g/L sodium stannate+2 g/L sodium molybdate;
(3) 8g/L sodium phosphate+2 g/L sodium tungstate+2 g/L sodium borate;
(4) 8g/L sodium phosphate+2 g/L sodium tungstate+2 g/L sodium molybdate;
the results of fig. 8 show that the prepared gas-sensitive film layer has poor response to NO, lower than the parameter responses of example 1 and example 2, and poor sensing performance.
Example 5: gas selectivity test and fitting curve
1. Gas selectivity test
With reference to the optimal electrolyte set and detection system of example 1, the sensor starts to drop a solution of a preset gas (20 ppm nitric oxide, triethylamine, ethanol, acetone, formaldehyde) when the preset temperature is stable. The results are shown in FIG. 9; the results in fig. 9 show that 20ppm NO exhibits excellent response at 210 ℃, and that the specific resistance and sensitivity of each gas show significantly higher NO response than the other several volatile gases, indicating extremely high sensitivity and strong selectivity to ammonia.
2. Fitting curve test of different concentrations
With reference to the optimal electrolyte set and the detection system of this embodiment 1, when the sensor is stabilized at the preset temperature, nitric oxide solutions with different concentrations (0.1 ppm/0.5 ppm/1 ppm/5 ppm/10 ppm/20 ppm/50 ppm/80 ppm/100 ppm/150 ppm/200 ppm) are added dropwise. The results of FIG. 10 show that the inventive sensor for detecting nitric oxide exhibits a good linear relationship (R 2 ＝0.96)。
3. Optimum operating temperature
The optimal electrolyte set and the detection system of example 1 were referred to for testing, and the prepared gas-sensitive film layers were placed in different temperature environments (150 ℃ C. To 240 ℃ C.) respectively, and the response thereof at 20ppm was observed, and the optimal working temperature of the NO-sensitive film layer was 210 ℃ from FIG. 11.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The pure titanium material coating sensor for detecting nitric oxide is characterized by comprising a pure titanium material, a micro-arc oxidation coating and an electrode; the micro-arc oxidation coating is arranged on the surface of the pure titanium material through micro-arc oxidation of electrolyte of sodium phosphate, sodium tungstate and sodium stannate, and the electrode is arranged on the micro-arc oxidation coating.
2. The sensor of claim 1, wherein the pure titanium material comprises TA 1-TA 4 industrial pure titanium material.
3. The sensor of claim 1, wherein the electrodes are interdigitated electrodes.
4. The sensor of claim 1, wherein the concentration of sodium phosphate in the electrolyte is 8-12 g/L, the concentration of sodium tungstate is 1-2 g/L, and the concentration of sodium stannate is 1-2 g/L.
5. Use of the sensor according to any of claims 1-4 for detecting nitric oxide or for preparing a nitric oxide detecting product.
6. The use according to claim 5, wherein the nitric oxide comprises 0.1-20 ppm nitric oxide.
7. A method of manufacturing a sensor according to claim 1, comprising:
step 1, polishing, degreasing and cleaning pretreatment of a pure titanium material;
step 2, performing micro-arc oxidation on the pretreated pure titanium material in sodium phosphate, sodium tungstate and sodium stannate electrolyte to form a micro-arc oxidation coating;
and step 3, setting an electrode on the micro-arc oxidation coating to obtain the sensor.
8. A product for detecting nitric oxide comprising a device for recording a change in resistance and a sensor according to any of claims 1-4, said device and electrodes on the sensor being connected by wires.
9. The article of claim 8, wherein the means for recording a change in resistance comprises a multimeter and a data processor.
10. A method for detecting nitric oxide, characterized in that the sensor according to any one of claims 1-4 is placed in nitric oxide standard samples with different concentrations, and a standard curve of resistance change data and nitric oxide concentration is established through equipment for recording resistance value changes; and then placing the sensor in an environment to be detected, obtaining resistance value change data, and obtaining the concentration of nitric oxide in the environment to be detected through a standard curve.
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