CN1111573C

CN1111573C - Pneumatic pressure-sensitive lacquer and its preparing process

Info

Publication number: CN1111573C
Application number: CN99107229A
Authority: CN
Inventors: 王夺元; 蒋峰芝; 许认
Original assignee: Institute of Photographic Chemistry of CAS
Current assignee: Institute of Chemistry CAS
Priority date: 1999-05-12
Filing date: 1999-05-12
Publication date: 2003-06-18
Anticipated expiration: 2019-05-12
Also published as: CN1273992A

Abstract

The present invention particularly relates to pneumatic pressure-sensitive paint and a preparation method thereof, which belongs to chemical aerodynamics. The present invention uses a diimine ruthenium complex as probe molecules, and uses the mixed solution of dimethyl diethoxysilane and gamma-aminopropyltriethoxysilane, etc., as the monomer of an organosilicon polymer. Two different kinds of alkoxy silane are mixed to be dissolved in absolute alcohol or acetone; then alkali or acid is used to regulate the pH value of the mixed solution to the range of 5.2 to 11.0; the mixed solution is stirred under the temperature of 15 DEG C to 35 DEG C for 1 to 12 hours to obtain transparent SiO2 collosol, of which the viscidity is suitable for coating films; 1*10 <4> to 5*10<3> mols of radiant probe molecules are added to 1 liter of transparent SiO2 collosol; after ultrasonic dispersion, the transparent SiO2 collosol is coated on a glass slide vortically to obtain the pressure-sensitive paint with no substrate, or is dropped on a basal plate with different white reflecting substrates to obtain the pressure-sensitive paint with substrates.

Description

Aerodynamic pressure-sensitive paint and preparation method thereof

The invention belongs to chemistry and chemical engineering and aerodynamics, and particularly relates to aerodynamic pressure-sensitive paint and a preparation method thereof.

At present, the wind tunnel pressure measurement mainly adopts a sensor measurement system, namely, a hole is formed on the surface of a model, the hole is connected with the surface of the model through a thin guide pipe inside the model, and the guide pipe is led out from the rear part of the model and is connected with an external scanning valve device and a measurement system. The construction of such a wind tunnel model is very costly and does not allow continuous pressure variation data of the measured surface to be obtained.

The pneumatic pressure-sensitive paint pressure measurement is a new wind tunnel pressure measurement technology developed in the last eighties of the world, is used for measuring the airflow pressure on the surface of an aircraft model, can dynamically measure the pressure distribution, and is called a revolution of a pressure measurement technology. Compare its advantage with traditional sensor pressure measurement and lie in: from discrete point measurements to continuous surface measurements; the spatial resolution is improved, and the difficulties that pressure points are difficult to be distributed and the number of points is small are overcome; the pressure measurement and the force measurement can be simultaneously measured by using the same model; pressure measurement and surface flow state display are completed simultaneously; the model is not damaged, the operation is simple, and the cost is greatly reduced.

A pressure sensitive lacquer is a polymer that is seeded with probe molecules. The pressure measurement of the aerodynamic pressure-sensitive paint is based on the photoluminescence and oxygen quenching principles of luminescent molecules. The pressure-sensitive paint with the luminous probe molecules is coated on the surface of an aircraft in a proper mode, and when exciting light with proper wavelength is selected for irradiation, the pressure-sensitive paint instantly emits visible light with a certain wave band. If the excited molecule collides with an oxygen molecule before emitting a photon, oxygen quenching occurs to reduce photon emission, corresponding to a decrease in luminescence intensity. When the airflow passes through the surface of the model, the pressure on each part is different, and then the oxygen partial pressure is different, so that the quenching degree of the luminescent molecules in the pressure-sensitive paint is different. Therefore, the higher the oxygen partial pressure (i.e., local static pressure) on the surface of the model is, the lower the luminous intensity is. Namely, the oxygen concentration and the luminous intensity conform to the Stern-Volmer equation:

wherein I₀Indicates the luminescence intensity without a quencher, where the quencher is an oxygen molecule; [ O ]₂]Is the oxygen concentration; i is actually measured luminous intensity; k is a radical of_qTo send outA bimolecular quenching rate constant at which the photon molecule is quenched by oxygen;

intrinsic lifetime of the excited molecule; k is a radical of_LAnd k is_cRespectively representing the rate constants of the radiative and non-radiative processes of the luminescent molecule; k_SVThe Stern-Volmer quenching constant is called as the quenching constant, and is used for representing the characteristics of local pressure and luminous intensity.

Due to I₀The film thickness, the probe molecule concentration, the film reflection performance, the reflection angle and the distance between the light source or the weak light instrument probe and the sample are changed, and the calibration is difficult, so a reference light intensity I is introduced_rDefined as the intensity of luminescence of the probe molecule in the absence of wind velocity in the wind tunnel. And order

The relationship (1) from Stern-Volmer is mathematically transformed to obtain:

wherein,

obviously, a + B is 1. If the light intensity at 1 atmosphere is used to represent the reference light intensity I_r1 atmosphere represents a reference pressure, then P_r＝P₁，I_r＝I₁。

Starting in the mid eighties, the university of Moscow and the central fluid dynamics research institute of the former Soviet Union, developed a pressure sensitive paint with a detection coating to measure pressure distribution that was insensitive to temperature from 10 ℃ to room temperature. The paint response is very slow and the step change induction period to pressure is as long as two minutes. The luminescence is recorded by a photosensitive film, and the measurement precision is low, about +/-10%. (Aldishawa, "measuring Pressure Distribution with test coating", journal of applied mechanics and technology physics, 1985(4), pp.24-31) [ M.M. Ardasheva., "Measurement of Pressure Distribution by means of Indicator Coatings", Zhural Prikladnoi Mekhaniki Tekhuchkifiziki, No.4, 1985, pp.24-31 ]. Pressure sensitive paints were developed at the beginning of 1987 at the university of washington, and the research funded by the united states space agency and boeing company. They applied for European patent "surface pressure measurement by luminescent oxygen quenching" in 1991, which published probe molecules as platinum octaethylporphyrin (PtOEP) dispersed in silicone polymer and used for wind tunnel measurement after coating. The light is irradiated by 380nm ultraviolet light source, and the luminous image is recorded by CCD and stored and processed by computer. The probe molecule platinum octaethylporphyrin (PtOEP) has a 40% reduction in luminescence intensity after 45 minutes of irradiation by an experimental light source. (Gouterman, Karman, Gehler force, et al, "Surface Pressure Measurement by luminescent oxygen Quenching", European Patent publication No. 0472243A 2, published application date: 26.2.1992. [ M.P. Gouterman, J.L. Kavandi, J. (NMI) Gallery, et al, "Surface Pressure Measurement by oxygen quench of Luminence," European Patent 0472243A 2, 26, 02, 92 ]. The McTakara 1994 reports a pressure-sensitive paint which has short response time and uses visible light to excite photoluminescence for pressure measurement, the pressure-sensitive paint uses a halogen tungsten lamp as a light source, visible light of 400-500 nm is selected for excitation, and the emitted light is about 600 nm. This is a relatively new result, but the structure of the luminescent probe molecule and the composition of the pressure-sensitive paint are not disclosed, and the calibration curve of the pressure-sensitive paint has a break point, which indicates that the response pressure change of the pressure-sensitive paint is not a continuous linear relationship. (Moris, Douniwan, "Application of Pressure and Temperature Sensitive Paints in High velocity air streams", proceedings of the American institute of aeronautics and astronomy, AIAA 94-2231, 1994) [ M.J.Morrisand J.F.Donovan, "Application of Pressure-and Temperature-Sensitive Paints to High-Speed Flow", AIAA 94-2231, 1994] in conclusion, the Pressure Sensitive paint probe molecules disclosed so far are only PtOEP.

As can be seen from the above reports, the problems of the pressure sensitive paint in use are mainly:

(1) ultraviolet light or short wavelength laser is used as an excitation light source, which is not beneficial to safe operation and is easy to cause the probe molecules to be photodegraded;

(2) the probe molecule PtOEP disclosed at present has the problem of photodegradation, so that the light intensity is weakened along with the increase of the irradiation time, and the instability of pressure measurement is caused;

(3) the response time is slow, namely the response time of the pressure-sensitive paint luminescence along with the pressure change is longer. This is because the matrix used for dispersing the probe molecules at present is silicone, which has an induction effect that excited oxygen is chemically bonded to silicone rubber to reduce the oxygen concentration, thereby resulting in a slow response to light, and in addition, when the permeability of the silicone rubber is poor, the time of collision between the probe molecules and the oxygen molecules is delayed, thereby slowing the response;

(4) the distribution of probe molecules in the pressure-sensitive paint matrix is not uniform, so that the phenomenon of double-position quenching often occurs, the calibration curve of the pressure-sensitive paint is not a continuous straight line completely, particularly, when the pressure is increased, the slope is reduced, the condition of downward deviation is caused, and the pressure measuring sensitivity is reduced.

The invention aims to solve the problems of the existing pressure-sensitive paint, and prepare the pressure-sensitive paint which uses the diimine ruthenium complex which is excited by visible light to emit light in the visible light range and has good light stability as a probe molecule. The specific sol-gel preparation technology is used for uniformly dispersing probe molecules into porous SiO₂In the matrix, a pressure-sensitive paint system with good air permeability, high content of probe molecules and adjustable content of the probe molecules is prepared, so that the system has good oxygen quenching effect, quick response time and high pressure measurement sensitivity, and can have good linear relation in a wider pressure change range.

The aerodynamic pressure-sensitive paint comprises a luminescent probe molecule and an organic silicon polymer, wherein a diimine ruthenium complex is used as the probe molecule; the monomer of the organic silicon polymer is a mixed solution of dimethyl diethoxy silane and gamma-aminopropyl triethoxy silane, the molar ratio of the mixed solution is 0-8, or the mixed solution of dimethyl diethoxy silane and tetraethoxy silane, the molar ratio of the mixed solution is 0-8, or the mixed solution of dimethyl diethoxy silane, gamma-aminopropyl triethoxy silane and tetraethoxy silane, wherein the molar ratio of the dimethyl diethoxy silane to (gamma-aminopropyl triethoxy silane + tetraethoxy silane) is 0-8; in the preparation of transparent SiO by cohydrolytic polycondensation of alkoxysilanes₂In the sol, the adding amount of the luminescent probe molecules is 1 multiplied by 10^-4～5×10^-3mol/l. The selected luminescent probe molecule is a diimine ruthenium complex, in particular bipyridine ruthenium [ Ru (bpy) ]₃]Cl₂·6H₂O, O-phenanthroline ruthenium [ Ru (phen)₃]Cl₂·3H₂O and 4, 7-Diphenylphenanthroline ruthenium [ Ru (ph)₂phen)₃]Cl₂·5H₂And O three probe molecules. These probe molecules can be synthesized according to the methods reported in Watts and Crosbane. Namely, the ruthenium trichloride hydrate and the 2, 2' -bipyridyl, or the o-phenanthroline, or the 4, 7-diphenyl o-phenanthroline are respectively dissolved in absolute ethyl alcohol according to the mol ratio of 1: 6.6, 1: 9.4 and 1: 5.4, and are stirred and refluxed for 24 to 60 hours at the oil bath temperature of 120 ℃ in the presence of hydroxylamine hydrochloride, so that the bipyridyl ruthenium [ Ru (bpy) ]can be respectively obtained₃]Cl₂·6H₂O, phenanthroline ruthenium [ Ru (phen)₃]Cl₂·3H₂O and 4, 7-Diphenylphenanthroline ruthenium [ Ru (ph)₂phen)₃]Cl₂·5H₂And (4) recrystallizing the crude products of the three probe molecules O, and carrying out column chromatography to obtain the required probe molecules. (Watts, Crosbane, "spectral characteristics of complexes of ruthenium (II) and iridium (III) with 4, 4 '-diphenyl-2, 2' -bipyridine, 4, 7-diphenyl-1, 10-phenanthroline", proceedings of the American society of chemistry, 1971, 3184-]exes of Ruthenium(II)and Iridium(III)with4，4’-Diphenyl-2，2’-hipyridine and Diphenyl-1，10-phenan throline″，J.Am.Chem.Soc，1971，3184-3188]。

The preparation of the pressure-sensitive paint adopts a sol-gel technology, and a special preparation process is designed aiming at the purpose of the invention. This is a fine chemical manufacturing process that requires strict control of reaction conditions.

The preparation process flow of the pressure-sensitive paint is shown in figure 1. Firstly, mixing dimethyldiethoxysilane (marked as MEOS) and gamma-aminopropyltriethoxysilane (marked as KH550) according to a molar ratio of 0-8, or mixing dimethyldiethoxysilane and tetraethoxysilane (marked as TEOS) according to a molar ratio of 0-8, or mixing dimethyldiethoxysilane and (gamma-aminopropyltriethoxysilane + tetraethoxysilane) according to a molar ratio of 0-8, and dissolving the mixture in absolute ethyl alcohol or acetone solvent which is 1.0-8.0 times of the total amount (molar number) of the mixed liquid of the alkoxysilanes; and uniformly mixing catalyst alkali or acid with water, slowly and dropwise adding the mixture into the solution, and adjusting the pH value to be 5.2-11.0. The amount of the catalyst is 1 to 5% of the total amount (mole number) of the alkoxysilane, 2 to 8% of the total amount (mole number) of the alkoxysilane, and the amount of water is 1.1 to 8.4 times the total amount (mole number) of the alkoxysilane. Stirring for 1-12 hours at 15-35 ℃, and directly obtaining transparent SiO with viscosity suitable for coating without standing₂Obtaining transparent SiO with viscosity suitable for coating after sol or standing and aging for 12-48 hours₂Sol; any probe molecule [ Ru (bpy) ]₃]Cl₂·6H₂O、[Ru(phen)₃]Cl₂·3H₂O or [ Ru (ph)₂phen)₃]Cl₂·5H₂Transparent SiO prepared by adding alkoxy silane into O and carrying out cohydrolysis and polycondensation₂The addition amount of the sol is 1 × 10^-4～5×10^-3mol/l. After ultrasonic dispersion, spin-coating on a glass slide, and drying at room temperature to obtain the pressure-sensitive paint without a substrate, or dripping on a base plate with white different reflecting substrates, and drying at room temperature to obtain the pressure-sensitive paint with a substrate.

In the process of preparing the sol-gel, the composition and the proportion of raw materials are key, and the distribution characteristics of probe molecules and the air permeability of a substrate are determined, so that the linear relation between the oxygen quenching effect and the wind tunnel calibration curve of the pressure-sensitive paint is influenced. When TEOS is used as a raw material, the hydrolysis rate is high, and highly crosslinked SiO is formed at a high rate₂Polymers, the resulting film is prone to cracking; in addition, the highly crosslinked sol-gel has poor compatibility with probe molecules, and the probe molecules are often observed to be enriched on the surface of the membrane layer, resulting in uneven distribution. To this end, we have introduced difunctional siloxane MEOS to control the degree of crosslinking and avoid cracking. And the high polymer PDMS with linear skeleton formed by MEOS hydrolytic polycondensation has very high oxygen diffusion coefficient and is favorable for O₂Is advantageous in improving the oxygen quenching effect. KH550 is used to replace or partially replace TEOS because KH550 can be used as a cross-linking agent to control the strength and adhesion of the film; and can be used as solubilizer, to improve the solubility of probe molecules in sol-gel, improve the content of probe molecules in matrix, and promote the uniform distribution of probe molecules in matrix without aggregation. The preferred proportion range is 3-8 MEOS/KH550, the pressure sensitive paint prepared in the range has good oxygen quenching effect and luminous intensity I in nitrogen_N2And luminous intensity in oxygen I_O2Ratio of (1)_N2/I_O2Within the range of 7.7 to 12.4. The introduction of KH550 for the matrix preparation of pressure-sensitive paints is a key aspect of the present invention. Because the gamma-aminopropyl exists in the KH550, the gamma-aminopropyl has a certain degree of coordination with the divalent ruthenium of the central metal ion of the probe molecule, and the KH550 is polarThe molecule, which has similar polarity to the polar probe molecule, greatly enhances the solubility of the probe molecule in the sol-gel due to compatibility of similar polarity and dual factors of coordination. The good compatibility between the probe molecules and the matrix ensures that the probe molecules are fully and uniformly dispersed in the matrix, thereby avoiding double-site quenching and ensuring that the calibration curve of the pressure-sensitive paint has good linear relation.

In the process of preparing the sol-gel, the catalyst plays a role in adjusting the pH value and controlling the reaction speed so as to influence the microstructure of the sol-gel. Sodium hydroxide is the preferred catalyst when catalyzed with a base, and when the amount of the catalytic base is large, the reaction rate is too fast and the formed sol-gel is cloudy and opaque in appearance. Only when the addition amount of the alkali catalyst is controlled to be about 1-3% of the total amount of the alkoxy silane, colorless and transparent sol-gel can be obtained. It is noted that since KH550 itself is strongly basic, hydrochloric acid is the preferred catalyst when catalyzed with an acid. If hydrochloric acid accounting for 4-8% of the total amount of the alkoxy silane is used for catalysis, the pH value of a reaction system can be adjusted to be 6.5-9.8, the hydrolysis speed is moderate under the condition, colorless and transparent sol-gel can be obtained, and high-magnification electron scanning microscope tests prove that the microstructure of the substrate prepared under the condition is good in uniformity.

Control of the amount of water and ethanol is one of the important factors affecting the microstructure of the gel. When the amount of water is small, the hydrolysis rate is slow and gel formation is difficult. However, when the amount of water is large, highly crosslinked SiO is easily and rapidly formed₂It is not favorable for improving the air permeability of the gel. After repeated screening, the addition of water is preferably 3-7 times of the total amount of the alkoxy silane. The ethanol is added to dilute the concentration of the reactant, so as to be beneficial to forming a microcosmic uniform film, prolong the curing time and be beneficial to smoothly carrying out the spraying and coating process. The amount of the ethanol added is 3 to 8 times of the total amount of the alkoxysilane.

The choice of substrate has a significant impact on both photoluminescence and oxygen quenching of the pressure sensitive lacquer. Respectively adopting neutral SiO with granularity of mum order₂Or Al₂O₃Or with a particle size in the order of nmSlightly acidic TiO₂Or fumed SiO₂The prepared pressure-sensitive paint is coated on a substrate as a substrate, and is respectively coated on the bottom layers, so that the excitation of incident light to probe molecules is enhanced, the effective reflection of the luminescence of the probe molecules is enhanced, and the oxygen quenching signal can be doubly enhanced.

The pressure-sensitive paint prepared by the method has the following characteristics:

(1) visible light excitation

Probe molecule [ Ru (ph)₂phen)₃]Cl₂·5H₂The absorption spectrum of O is shown in FIG. 2, which has strong absorption in the visible region above 360nm and two strong absorption bands characteristic of metal-ligand charge transfer (MLCT) at 440nm and 460 nm. In the spectral range, probe molecules are selectively excited, and higher luminous efficiency can be obtained in a long-wavelength band (600-640nm) visible light region.

(2) Light stability

FIG. 3 shows the probe molecule [ Ru (ph)₂phen)₃]Cl₂·5H₂O is continuously irradiated by visible light in the air, the change of relative luminous intensity is not more than 0.5 percent within 2.5 hours, and good light stability is shown. That is, under the present experimental conditions, no oxidative degradation phenomenon of singlet oxygen on the probe molecule is observed, indicating that the probe molecule has good photochemical stability.

(3) Good oxygen permeability and short response time

FIG. 4 shows the time-dependent change of the luminescence intensity of a sample scanned with nitrogen and oxygen (instrument response time 0.5s) with the excitation wavelength selected to be 460nm and the emission wavelength fixed at 610 nm. It is shown that a very good oxygen quenching effect is obtained when pure oxygen and pure nitrogen are alternately fed into the cell at a flow rate of 4.4 ml/s. Wherein the pressure sensitive paint is not provided with a substrate

(a) \frac{I_{N_{2}}}{I_{O_{2}}} = 7.7

(ii) a Pressure sensitive paint with substrate

(b) \frac{I_{N_{2}}}{I_{O_{2}}} = 12.4

. In this experiment, the change in luminescence intensity was balanced within the response time of the instrument, whether oxygen or nitrogen was applied. The induction period of the pressure-sensitive paint sample prepared by the experiment is extremely short. This is because SiO is produced by the sol-gel process₂The film is a chemically inert porous matrix material, and is characterized by large porosity, and the SiO of the paint layer is observed by using a scanning electron microscope to represent the microstructure of the paint layer₂The matrix is a uniformly distributed, packed particle of 10-20nm size, and the micropores formed by the packing are also in the same order of magnitude range. The oxygen permeability is good, diffusion collision quenching between oxygen molecules and excited probe molecules is facilitated, and singlet oxygen generated by the oxygen is inactivated when meeting a matrix, so that the problem that additional blowing time is needed in a wind tunnel test caused by an induction period is solved. When oxygen and nitrogen are introduced repeatedly, the change of the luminous intensity shows good repeatability. The above results indicate that the oxygen quenching process is an efficient, dynamic, reversible process.

Comparing (a) and (b) also shows that the presence of the substrate is beneficial to enhancing the excitation of the probe molecules by the incident light and the effective reflection of the luminescence of the probe molecules, and doubly enhancing the oxygen quenching signal.

(4) The microstructure is uniform, and the correction curve shows good linear relation

In the invention, the sol-gel technology is used to effectively control the uniform distribution of probe molecules in the matrix, a wind tunnel simulation test is carried out by using the pressure-sensitive paint with the substrate, and a continuously-changing calibration curve is obtained in a wider pressure change range and is shown as a graph in fig. 5c, wherein A is 0.25, and B is 0.75. As can be seen from the figure, this workerThe pressure-sensitive paint prepared is in a vacuum section (1.01X 10)⁴-1.01×10⁵Pa) and low-pressure section (1.01X 10)⁵-4.05×10⁵Pa) shows a good linear relationship, the correlation coefficient γ is 0.99 or more, and the slopes are consistent, i.e., no break point occurs, and a single Stem-Volmer relationship is met. This greatly simplifies the computational model and increases experimental accuracy. This shows that the paint-like probe molecules are uniformly distributed and have good air permeability, and the paint-like probe is a good pressure-sensitive paint system.

(5) High sensitivity

FIG. 5d is a calibration curve of the pressure-sensitive paint given in the European patent "luminous pressure-sensitive composition". (Mosarov, Kuzmen, Ourov, et al, "luminescent pressure sensitive Composition", European Patent, publication No. 0558771A 1, published application date: 08, 09, 93) [ V.Mosharov, M.Kuzmin, A.Orlov, et al, "Luminescence pressure sensitive Composition", European Patent, 0558771A 1, 08, 09, 93]Due to reference light intensity I_rThe values are different, so the range of values given for the ordinate is different, but still comparable. As can be seen from comparison of c and d in FIG. 5, the slope of the calibration curve of the pressure-sensitive paint prepared according to the present invention is higher than that of the foreign pressure-sensitive paint in a wider pressure variation range, and shows higher sensitivity to the air flow pressure.

Description of the drawings:

FIG. 1: the invention discloses a preparation process schematic diagram of aerodynamic pressure-sensitive paint;

FIG. 2: probe molecule [ Ru (ph) of the invention₂phen)₃]Cl₂·5H₂Electron absorption spectrum of O in methanol;

FIG. 3: probe molecule [ Ru (ph) of the invention₂phen)₃]Cl₂·5H₂O photostability test;

FIG. 4: the invention has the time response characteristic of pressure sensitive paint oxygen quenching in a silicon dioxide film;

a. substrate-less b

FIG. 5: the wind tunnel simulation calibration curve of the pressure-sensitive paint is compared;

c. the pressure-sensitive paint prepared by the method has visible light excitation, and B is 0.75

d. Pressure-sensitive paints prepared in the document European Patent, 0558771A 1, UV-excited, B ═ 0.67

FIG. 6: probe molecule [ Ru (ph) of the invention₂phen)₃]Cl₂·5H₂Oxygen quenching characteristics of O in solid thin films;

e. example 1 obtained 1^#Sol-gel

f. Example 2 result 2^#Sol-gel

FIG. 7: the invention relates to a pressure distribution diagram of pressure-sensitive paint jet flow impact convex surface pressure measurement;

g. black and white photograph in pressure sensitive paint manometry

h. Pseudo-color pressure distribution diagram for pressure measurement of pressure-sensitive paint

Example 1

1mol KH550 and 8mol MEOS (MEOS: KH550 is 8) were dissolved in 30mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.09mol of sodium hydroxide and 28mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 9.0, in which the amount of the solvent anhydrous ethanol and the amount of water were 3.3 times and 3.1 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 1.0% of the total amount of alkoxysilane. Stirring at 25 deg.C for 5 hr, standing and aging for 24 hr to obtain transparent SiO film₂Sol-gel.

18.9mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 5ml of the above sol-gel at a concentration of 3X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂Reflective bottom layerDrying the substrate at room temperature for 7 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O28.4. It was used in a wind tunnel simulation test and the results as shown in fig. 6e were obtained.

Example 2

1mol KH550 and 3mol MEOS (MEOS: KH550 is 3) were dissolved in 14mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.24mol of hydrochloric acid and 12.6mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 7.8, in which the amount of the solvent anhydrous ethanol and the amount of water were 3.5 times and 3.2 times the total amount of alkoxysilane, respectively, and the amount of the catalyst hydrochloric acid was 6.0% of the total amount of alkoxysilane. Stirring at 15 deg.C for 5 hr, standing and aging for 12 hr to obtain transparent SiO film₂Sol-gel.

7.5mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 3ml of the above sol-gel at a concentration of 2X 10^-3And (3) uniformly dispersing by using ultrasonic waves, spin-coating on a glass plate, and drying at room temperature for 9 days to obtain the pressure-sensitive paint without the substrate. The paint layer is transparent, and the distribution of the probe molecules is uniform.

The resulting substrate-free pressure-sensitive lacquer was used for the time scanning of the emission spectrum, and I was determined_N2/I_O27.7. This was used in an oxygen quenching experiment and plotted against its Stem-Volmer correlation, giving the results shown in figure 6 f.

Example 3

2molKH550 and 2molMEOS (MEOS: KH 550. RTM. 1) were dissolved in 7mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.12mol of sodium hydroxide and 14mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 9.2, in which the amount of the solvent anhydrous ethanol and the amount of water were 1.8 times and 3.5 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 3.0% of the total amount of alkoxysilane. Stirring for 3 hours at 35 ℃ without standing and aging to obtain the transparent SiO capable of being coated₂Sol-gel.

12.6mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 1X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on Al-bearing materials₂O₃And drying the substrate with the reflecting bottom layer at room temperature for 7 days to obtain the pressure-sensitive paint with the substrate.

The emission spectra were scanned over time with a pressure-sensitive lacquer with a substrate, and I was determined_N2/I_O2＝2.4。

Example 4

4mol of TEOS (MEOS: TEOS ═ 0 in this case) was dissolved in 20mol of anhydrous ethanol, and a mixed solution of 0.12mol of hydrochloric acid and 24mol of water was slowly added with vigorous stirring to adjust the initial pH of the reaction solution to 6.0, in which the amount of the solvent anhydrous ethanol and the amount of water were 5 times and 6 times, respectively, the total amount of alkoxysilane and the amount of the catalyst hydrochloric acid was 3.0% of the total amount of alkoxysilane. Stirring is continued for 2 hours at 30 ℃, and transparent SiO suitable for coating can be obtained without standing and aging₂Sol-gel.

18.7mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 5ml of the above sol-gel at a concentration of 5X 10^-3mol/l, after ultrasonic dispersion is uniform, spin coating on the TiO tape₂Drying the glass plate on the bottom layer at room temperature for 3 days to obtain the pressure-sensitive paint with the substrate. A small amount of probe molecules can be seen to be enriched on the surface layer of the paint by naked eyes, and the crack of the paint layer is serious.

The resulting pressure-sensitive lacquer with the substrate was used for a time-scanning of the emission spectrum, and I was determined_N2/I_O2＝3.5。

Example 5

10molMEOS, 0.5molKH550 and 1.5molTEOS (in this case, MEOS: (KH550+ TEOS): 5) were dissolved in 12mol of acetone, and a mixed solution of 0.24mol of hydrochloric acid and 33mol of water was added with vigorous stirring to adjust the initial pH of the reaction solution to 8.2, in which the amount of acetone as a solvent and the amount of water were 1 times and 2.g times the total amount of alkoxysilane, respectively, and the amount of hydrochloric acid as a catalyst was 2.0% of the total amount of alkoxysilane. Stirring at 33 deg.CAfter 1 hour, transparent SiO suitable for coating can be obtained₂Sol-gel.

1.26mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 1X 10^-4mol/l, after ultrasonic dispersion is uniform, the mixture is coated on the aerosol SiO by spin coating₂Drying the glass plate for 15 days at room temperature to obtain the pressure-sensitive paint with the substrate. The paint layer was accompanied by slight cracking.

The obtained pressure-sensitive paint without the substrate is respectively subjected to luminescence spectrum test in nitrogen, oxygen and air atmosphere to obtain I_N2/I_air＝1.1；I_N2/I_O2＝1.3。

Example 6

4mol KH550 (MEOS: KH550 is 0) was dissolved in 24mol of acetone, and a mixed solution of 0.05mol of sodium hydroxide and 19.2mol of water was added with vigorous stirring to adjust the initial pH of the reaction solution to 9.4, in which the amount of acetone and the amount of water as solvents were 6 times and 4.8 times the total amount of alkoxysilane, respectively, and the amount of sodium hydroxide as a catalyst was 1.2% of the total amount of alkoxysilane. Stirring at 20 deg.C for 5 hr, standing and aging for 12 hr to obtain transparent SiO suitable for coating₂Sol-gel.

3.8mg of [ Ru (phen)₃]Cl₂·3H₂O was dissolved in 10ml of the above sol-gel at a concentration of 5X 10^-4And (3) mol/l, after uniform ultrasonic dispersion, spin-coating on a glass plate, and drying at room temperature for 4 days to obtain the pressure-sensitive paint without the substrate. The obtained pressure-sensitive paint without the substrate is respectively subjected to luminescence spectrum test in nitrogen, oxygen and air atmosphere to obtain I_N2/I_air＝1.8；I_N2/I_O2＝2.6。

Example 7

Dissolving 3molKH550 and 6molMEOS (MEOS: KH 550. RTM.2) in 36mol of acetone, slowly adding 0.45mol of hydrochloric acid and 63mol of water under stirring, and uniformly mixing to obtain a solution, and adjusting the initial pH of the reaction solution to 8.8, wherein the acetone and water are respectively 4 times and 7 times the total amount of alkoxysilaneThe amount of catalyst hydrochloric acid was 5.0% of the total amount of alkoxysilane. Stirring at 18 deg.C for 12 hr, standing and aging for 20 hr to obtain transparent SiO film₂Sol-gel.

6.3mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 5X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with TiO₂And drying the substrate with the reflecting bottom layer for 5 days at room temperature to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝4.3。

Example 8

2mol TEOS and 8mol MEOS (MEOS: TEOS is 4) are dissolved in 60mol acetone, 0.37mol hydrochloric acid and 84mol water are slowly added with stirring to obtain a solution which is uniformly mixed, the initial pH of the reaction solution is adjusted to 5.2, the amount of acetone and the amount of water are 6 times and 8.4 times of the total amount of the alkoxysilane respectively, and the amount of hydrochloric acid serving as a catalyst is 3.7% of the total amount of the alkoxysilane. Stirring at 26 deg.C for 9 hr, standing and aging for 21 hr to obtain transparent SiO film₂Sol-gel.

7.5mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 6X 10^-4And (3) uniformly dispersing by using ultrasonic, spin-coating on a glass plate, and drying at room temperature for 7 days to obtain the pressure-sensitive paint without the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝3.1。

Example 9

6mol of MEOS, 0.5mol of KH550 and 0.5mol of TEOS (in this case, MEOS: (KH550+ TEOS): 6) were dissolved in 35mol of acetone, and a solution obtained by uniformly mixing 0.49mol of hydrochloric acid and 31mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 7.0, in which case the amount of acetone as a solvent and the amount of water as a solvent were adjusted to be equal to each other5 times and 4.4 times of the total amount of the alkoxysilane, and the amount of the catalyst hydrochloric acid was 7.0% of the total amount of the alkoxysilane. Stirring at 24 deg.C for 12 hr, standing and aging for 24 hr to obtain transparent SiO film₂Sol-gel.

1.5mg of [ Ru (phen)₃]Cl₂·3H₂O is dissolved in 20ml of the above sol-gel, at a concentration of 1X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 9 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝5.0。

Example 10

1mol KH550 and 7mol MEOS (MEOS: KH 550. RTM.7) were dissolved in 16mol of acetone, and a solution obtained by uniformly mixing 0.60mol of hydrochloric acid and 17mol of water was slowly added with stirring to adjust the initial pH of the reaction solution to 7.4, in which the amount of acetone as a solvent and the amount of water were 2 times and 2.1 times the total amount of alkoxysilane, respectively, and the amount of hydrochloric acid as a catalyst was 7.5% of the total amount of alkoxysilane. Stirring at 28 deg.C for 11.5 hr, standing and aging for 20 hr to obtain transparent SiO film₂Sol-gel.

6.9mg of [ Ru (phen)₃]Cl₂·3H₂O was dissolved in 10ml of the above sol-gel at a concentration of 9X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with TiO₂And drying the substrate with the reflecting bottom layer at room temperature for 18 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝10.2。

Example 11

4molKH550 and 6molMEOS (in this case, MEOS: KH 550. RTM. 1.5) were dissolved in 24mol of acetone, and a solution obtained by uniformly mixing 0.8mol of hydrochloric acid and 24mol of water was slowly added with stirring to adjust the initial pH of the reaction solution to 9.8 in this case, acetone was used as a solventThe amount of the catalyst hydrochloric acid and the amount of water are both 2.4 times of the total amount of the alkoxysilane, and the amount of the catalyst hydrochloric acid is 8.0% of the total amount of the alkoxysilane. Stirring at 30 deg.C for 5 hr, standing and aging for 30 hr to obtain SiO-permeable film₂Gelatin sol-gel.

6.1mg of [ Ru (phen)₃]Cl₂·3H₂O was dissolved in 10ml of the above sol-gel at a concentration of 8X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on Al-bearing materials₂O₃And drying the substrate with the reflecting bottom layer for 5 days at room temperature to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝3.8。

Example 12

2mol TEOS and 5mol MEOS (MEOS: TEOS 2.5) were dissolved in 56mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.28mol of hydrochloric acid and 54mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 6.5, in which the amount of the anhydrous ethanol as a solvent and the amount of water were 8.0 times and 7.7 times the total amount of alkoxysilane, respectively, and the amount of hydrochloric acid as a catalyst was 4.0% of the total amount of alkoxysilane. Stirring for 10 hours at 25 ℃, standing and aging for 48 hours to obtain transparent SiO capable of being coated₂Sol-gel.

7.5mg of [ Ru (bpy)₃]Cl₂·6H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 1X 10^-3And (3) uniformly dispersing by using ultrasonic, spin-coating on a glass plate, and drying at room temperature for 8 days to obtain the pressure-sensitive paint without the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝2.4。

Example 13

Dissolving 7mol of MEOS, 1mol of KH550 and 1mol of TEOS (in this case, MEOS: (KH550+ TEOS): 3.5) in 21mol of anhydrous ethanol, slowly adding a solution obtained by uniformly mixing 0.22mol of hydrochloric acid and 42mol of water while stirring, and adjusting the initial reaction solutionThe pH was 7.9, at which the amount of the solvent absolute ethanol and the amount of water were 2.3 times and 4.7 times, respectively, the amount of the catalyst hydrochloric acid was 2.5% of the total amount of the alkoxysilane. Stirring at 25 deg.C for 10.5 hr, standing and aging for 40 hr to obtain transparent SiO film₂Sol-gel.

4.5mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 10ml of the above sol-gel at a concentration of 6X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 3 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝4.2。

Example 14

2molKH550 and 9molMEOS (in this case, MEOS: KH 550: 4.5) were dissolved in 44mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.72mol of hydrochloric acid and 72mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 8.3, in which the amount of the solvent anhydrous ethanol and the amount of water were 4 times and 6.5 times the total amount of alkoxysilane, respectively, and the amount of the catalyst hydrochloric acid was 6.5% of the total amount of alkoxysilane. Stirring at 20 deg.C for 11.5 hr, standing and aging for 36 hr to obtain transparent SiO film₂Sol-gel.

6.0mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 10ml of the above sol-gel at a concentration of 8X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with TiO₂And drying the substrate with the reflecting bottom layer at room temperature for 10 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝10.6。

Example 15

11mol of MEOS, 0.5mol of KH550 and 1.5mol of TEOS (in this case MEOS: (KH550+ TEOS): 5.5) are dissolved in 62mol of acetone and 0.72mol of salt is slowly added with stirringThe initial pH of the reaction solution was adjusted to 6.7 by uniformly mixing the acid and 31mol of water, in which the amount of acetone and the amount of water were 4.8 times and 2.4 times, respectively, the total amount of alkoxysilane and the amount of hydrochloric acid as a catalyst was 5.5% of the total amount of alkoxysilane. Stirring at 19 deg.C for 11 hr, standing and aging for 12 hr to obtain transparent SiO film₂Sol-gel.

2.5mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 2X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on Al-bearing materials₂O₃And drying the substrate with the reflecting bottom layer at room temperature for 12 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝4.8。

Example 16

13molMEOS, 1molKH550 and 1molTEOS (in this case, MEOS: (KH550+ TEOS): 6.5) were dissolved in 30mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.75mol of sodium hydroxide and 16.5mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 11.0, in which the amount of the solvent anhydrous ethanol and the amount of water were 2 times and 1.1 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 5.0% of the total amount of alkoxysilane. Stirring for 4 hours at 26 ℃, standing and aging for 24 hours to prepare transparent SiO capable of being coated with a film₂Sol-gel.

8.8mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 7X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 17 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝5.4。

Example 17

2molKH550 and 15molMEOS (in this case, MEOS: KH 550. RTM.7.5) were dissolved in 51mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.34mol of sodium hydroxide and 90mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 10.2, in which the amount of the solvent anhydrous ethanol and the amount of water were 3 times and 5.3 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 2.0% of the total amount of alkoxysilane. Stirring for 7 hours at 25 ℃, then standing and aging for 12 hours to prepare transparent SiO capable of being coated with a film₂Sol-gel.

Adding 5.0mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 4X 10^-4And (3) uniformly dispersing by using ultrasonic waves, spin-coating on a glass plate, and drying at room temperature for 16 days to obtain the pressure-sensitive paint without the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝8.2

Example 18

2molKH550 and 10molMEOS (in this case, MEOS: KH 550. RTM.5) were dissolved in 54mol of acetone, and a solution obtained by uniformly mixing 0.31mol of sodium hydroxide and 78mol of water was slowly added with stirring, to adjust the initial pH of the reaction solution to 9.7, in which the amount of acetone as a solvent and the amount of water were 4.5 times and 6.5 times the total amount of alkoxysilane, respectively, and the amount of sodium hydroxide as a catalyst was 2.6% of the total amount of alkoxysilane. Stirring at 35 deg.C for 5 hr, standing and aging for 48 hr to obtain transparent SiO film₂Sol-gel.

9.7mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 10ml of the above sol-gel at a concentration of 1.3X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on Al-bearing materials₂O₃And drying the soft substrate with the reflecting bottom layer for 5 days at room temperature to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O212.4. And used for air jet impinging on the projectionThe surface pressure sensitive paint plate is used for pressure measurement, and a complex pressure distribution structure is obtained on a small area. A black and white photograph of the pressure-sensitive paint taken with the CCD in the manometry is shown in fig. 7 (g). It can be seen from the figure that the brightness of each position of the painted surface is different, which indicates that the light intensity is different, i.e. the gray scale is different. This indicates that the air flow pressure varies from place to place, with the greater the pressure, the darker the paint and vice versa. It can be seen that the nozzle has a horn-like black image, indicating that the pressure is greater in this region. We also performed pseudo-color processing on black and white photographs, and expressed different gray scales with different colors, respectively, to obtain a more intuitive and well-defined pseudo-color pressure distribution diagram as shown in fig. 7 (h). Along the direction of the nozzle, along with the different distances from the nozzle, the pressure applied to each part is obviously different, and abundant pressure distribution layers are shown. The pressure sensitive paint can well express the difference of relative pressure of each part of the test surface and has high spatial resolution.

Example 19

1mol TEOS and 6mol MEOS (MEOS: TEOS is 6) are dissolved in 14mol acetone, 0.21mol sodium hydroxide and 16mol water are slowly added under stirring to obtain a uniformly mixed solution, the initial pH of the reaction solution is adjusted to 7.6, the amount of acetone and the amount of water as solvents are 2 times and 2.3 times of the total amount of alkoxysilane respectively, and the amount of sodium hydroxide as a catalyst is 3.0% of the total amount of alkoxysilane. Stirring at 23 deg.C for 12 hr, standing and aging for 24 hr to obtain transparent SiO film₂Sol-gel.

15.0mg of [ Ru (bpy)₃]Cl₂·6H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 2X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 14 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝6.2。

Example 20

2molKH550 and 8molMEOS (in this case, MEOS: KH 550. RTM.4) were dissolved in 37mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.45mol of sodium hydroxide and 66mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 10.6, in which the amount of the solvent anhydrous ethanol and the amount of water were 3.7 times and 6.6 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 4.5% of the total amount of alkoxysilane. Stirring at 20 deg.C for 8 hr, standing and aging for 36 hr to obtain transparent SiO film₂Sol-gel.

11.2mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 5ml of the above sol-gel at a concentration of 3X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on the surface with TiO₂And drying the substrate with the reflecting bottom layer at room temperature for 11 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝9.2。

Example 21

14mol of MEOS, 0.5mol of KH550 and 1.5mol of TEOS (in this case, MEOS: (KH550+ TEOS): 7.0) were dissolved in 48mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.4mol of sodium hydroxide and 71mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 9.9, in which case the amount of the solvent anhydrous ethanol and the amount of the water were 3.0 times and 4.4 times, respectively, the amount of the catalyst sodium hydroxide was 2.5% of the total amount of alkoxysilane. Stirring for 10 hours at 20 ℃, standing and aging for 30 hours to prepare transparent SiO capable of being coated₂Sol-gel.

7.7mg of [ Ru (phen)₃]Cl₂·3H₂O is dissolved in 10ml of the above sol-gel, at a concentration of 1X 10^-3And (3) uniformly dispersing by using ultrasonic, spin-coating on a glass plate, and drying at room temperature for 15 days to obtain the pressure-sensitive paint without the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝6.O。

Example 22

2mol TEOS and 16mol MEOS (MEOS: TEOS is 8) are dissolved in 47mol of absolute ethyl alcohol, 0.63mol of sodium hydroxide and 40mol of water are slowly added under stirring to obtain a solution, the initial pH of the reaction solution is adjusted to 7.8, the amount of the absolute ethyl alcohol and the amount of the water are 2.6 times and 2.2 times of the total amount of the alkoxysilane respectively, and the amount of the sodium hydroxide serving as a catalyst is 3.7% of the total amount of the alkoxysilane. Stirring at 15 deg.C for 12 hr, standing and aging for 48 hr to obtain transparent SiO film₂Sol-gel.

19.2mg of [ Ru (phen)₃]Cl₂·3H₂O was dissolved in 5ml of the above sol-gel at a concentration of 5X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 18 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝6.7。

Example 23

8mol of MEOS, 1mol of KH550 and 1mol of TEOS (in this case, MEOS: (KH550+ TEOS): 4.0) were dissolved in 50mol of acetone, and a solution obtained by uniformly mixing 0.42mol of sodium hydroxide and 46mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 10.4, in which the amount of acetone as a solvent and the amount of water were 5.0 times and 4.6 times the total amount of alkoxysilane, respectively, and the amount of sodium hydroxide as a catalyst was 4.2% of the total amount of alkoxysilane. Stirring for 10 hours at 19 ℃, then standing and aging for 24 hours to prepare transparent SiO capable of being coated with a film₂Sol-gel.

11.5mg of [ Ru (phen)₃]Cl₂·3H₂O was dissolved in 5ml of the above sol-gel at a concentration of 3X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on Al-bearing materials₂O₃And drying the substrate with the reflecting bottom layer at room temperature for 10 days to obtain the pressure-sensitive paint with the substrate.

Mixing the aboveThe resulting pressure-sensitive paint was subjected to a time-scan of the emission spectrum to determine I_N2/I_O2＝4.5。

Example 24

8mol of MEOS, 4mol of KH550 and 4mol of TEOS (in this case, MEOS: (KH550+ TEOS) ═ 1.O) were dissolved in 112mol of anhydrous ethanol, and a solution obtained by uniformly mixing 0.3mol of sodium hydroxide and 88mol of water was slowly added with stirring, and the initial pH of the reaction solution was adjusted to 10.8, in which the amount of the solvent anhydrous ethanol and the amount of water were 7 times and 5.5 times the total amount of alkoxysilane, respectively, and the amount of the catalyst sodium hydroxide was 1.9% of the total amount of alkoxysilane. Stirring for 7 hours at 25 ℃, then standing and aging for 15 hours to prepare transparent SiO capable of being coated with a film₂Sol-gel.

11.3mg of [ Ru (ph)₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 9X 10^-4mol/l, after ultrasonic dispersion is uniform, spraying on SiO with smoke₂And drying the substrate with the reflecting bottom layer at room temperature for 7 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝1.9。

Example 25

4mol TEOS and 6mol MEOS (MEOS: TEOS is 1.5) are dissolved in 42mol of absolute ethyl alcohol, 0.16mol of sodium hydroxide and 56mol of water are slowly added under stirring to obtain a uniformly mixed solution, the initial pH of the reaction solution is adjusted to 7.5, the amount of the absolute ethyl alcohol and the amount of the water are respectively 4.2 times and 5.6 times of the total amount of the alkoxysilane as a solvent, and the amount of the sodium hydroxide as a catalyst is 1.6% of the total amount of the alkoxysilane. Stirring for 10 hours at 25 ℃, standing and aging for 24 hours to prepare transparent SiO capable of being coated₂Sol-gel.

18.7mg of [ Ru (bpy)₃]Cl₂·6H₂O was dissolved in 5ml of the above sol-gel at a concentration of 5X 10^-3mol/l, after ultrasonic dispersion is uniform, spin coating on a glass plate, drying for 5 days at room temperature to obtain the productPressure sensitive lacquer of the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝2.5。

Example 26

2mol TEOS and 6mol MEOS (MEOS: TEOS is 3) are dissolved in 56mol acetone, 0.38mol sodium hydroxide and 54mol water are slowly added with stirring to obtain a solution, the initial pH of the reaction solution is adjusted to 8.1, the amount of acetone and the amount of water are 7.0 times and 6.8 times of the total amount of alkoxysilane respectively, and the amount of sodium hydroxide as a catalyst is 4.8% of the total amount of alkoxysilane. Stirring for 6 hours at 35 ℃, standing and aging for 24 hours to prepare transparent SiO capable of being coated₂Sol-gel.

19.2mg[Ru(ph₂phen)₃]Cl₂·5H₂O was dissolved in 10ml of the above sol-gel at a concentration of 2.5X 10^-3mol/l, after ultrasonic dispersion is uniform, spraying on the surface with SiO₂And drying the substrate with the reflecting bottom layer at room temperature for 8 days to obtain the pressure-sensitive paint with the substrate.

The pressure-sensitive paint obtained above is subjected to time scanning of emission spectrum to obtain I_N2/I_O2＝3.7。

Claims

1. The aerodynamic pressure-sensitive paint comprises luminescent probe molecules and organic silicon polymers, and is characterized in that diimine ruthenium complex is used as the probe molecules; the monomer of the organic silicon polymer is a mixed solution of dimethyl diethoxy silane and gamma-aminopropyl triethoxy silane with the molar ratio of 0-8, or a mixed solution of dimethyl diethoxy silane and tetraethoxy silane with the molar ratio of 0-8, or a mixed solution of dimethyl diethoxy silane, gamma-aminopropyl triethoxy silane and tetraethoxy silane, wherein the dimethyl diethoxy silane and (gamma-aminopropyl triethoxy silane and tetraethoxy silane)The molar ratio of (a) to (b) is 0 to 8; in the preparation of transparent SiO by cohydrolytic polycondensation of alkoxysilanes₂In the sol, the adding amount of the luminescent probe molecules is 1 multiplied by 10¹～5×10³mol/l。

2. An aerodynamic pressure-sensitive paint according to claim 1 wherein said diimine ruthenium complex is bipyridine ruthenium, phenanthroline ruthenium and 4, 7-diphenyl phenanthroline ruthenium.

3. An aerodynamic pressure sensitive paint as claimed in claim 1 wherein the molar ratio of dimethyldiethoxysilane to gamma-aminopropyltriethoxysilane is 3-8.

4. A method for preparing a pneumatic pressure-sensitive paint as claimed in claim 1, wherein the dimethyldiethoxysilane and γ -aminopropyltriethoxysilane are mixed at a molar ratio of 0-8, or the dimethyldiethoxysilane and tetraethoxysilane are mixed at a molar ratio of 0-8, or the dimethyldiethoxysilane and (γ -aminopropyltriethoxysilane + tetraethoxysilane) are mixed at a molar ratio of 0-8 and dissolved in an absolute ethanol or acetone solvent which is 1.0-8.0 times the total amount of the alkoxysilanes of the mixture; uniformly mixing catalyst alkali or acid with water, slowly dripping the mixture into the solution, adjusting the pH value to be 5.2-11.0, stirring the mixture for 1-12 hours at the temperature of 15-35 ℃, and directly obtaining transparent SiO with viscosity suitable for coating without standing₂Sol, or standing and aging for 12-48 hours to obtain transparent SiO with viscosity suitable for coating₂Sol; transparent SiO prepared by adding luminous probe molecules into alkoxy silane for cohydrolysis and polycondensation₂Adding into sol at a ratio of 1 × 10^-4～5×10^-3mol/l; after ultrasonic dispersion, spin-coating on a glass slide, and drying at room temperature to obtain the pressure-sensitive paint without a substrate, or dripping on a base plate with white different reflecting substrates, and drying at room temperature to obtain the pressure-sensitive paint with a substrate.

5. A process for preparing an aerodynamic pressure-sensitive paint as claimed in claim 4, wherein the catalyst is added in an amount of base 1-5% of the total amount of alkoxysilane or acid 2-8% of the total amount of alkoxysilane.

6. A process for preparing an aerodynamic pressure-sensitive paint as claimed in claim 4 or claim 5, wherein the base is sodium hydroxide and the acid is hydrochloric acid.

7. The method for producing an aerodynamic pressure-sensitive paint according to claim 4, wherein the amount of water added is 1.1 to 8.4 times the total amount of alkoxysilane.

8. The method according to claim 4, wherein the luminescent probe molecule is ruthenium bipyridine, ruthenium phenanthroline or ruthenium 4, 7-diphenyl phenanthroline.

9. The method for preparing an aerodynamic pressure-sensitive paint as claimed in claim 4, wherein the molar ratio of dimethyldiethoxysilane to gamma-aminopropyltriethoxysilane is 3-8.