CN1111573C - Pneumatic pressure-sensitive lacquer and its preparing process - Google Patents

Abstract

The invention belongs to chemical engineering and aerodynamics, in particular to aerodynamic pressure-sensitive paint and a preparation method thereof. It uses the diimine ruthenium complex as the probe molecule, and the monomers of the organosilicon polymer are dimethyldiethoxysilane and γ-aminopropyltriethoxysilane, etc.; the alkoxysilane is mixed and dissolved in absolute ethanol or acetone; adjust the pH to 5.2 to 11.0 with alkali or acid, and stir at 15°C to 35°C for 1 to 12 hours to obtain a transparent SiO ₂ sol with a viscosity suitable for coating; the luminescent probe molecule Add 1×10 ^-4 ~ 5×10 ^-3 mol/l into transparent SiO ₂ sol, after ultrasonic dispersion, spin-coat on glass slide to get pressure-sensitive paint without substrate, or drop on On substrates of different reflective backings in white, backed pressure-sensitive varnishes were obtained.

Description

Aerodynamic pressure-sensitive paint and preparation method thereof

The invention belongs to chemical engineering and aerodynamics, in particular to aerodynamic pressure-sensitive paint and a preparation method thereof.

At present, the wind tunnel pressure measurement mainly adopts the sensor measurement system, that is, opening a hole on the surface of the model, connecting the hole with a thin catheter through the inside of the model, and the catheter is led out from the rear of the model, and then connected with the external scanning valve device and the measurement system. Building such a wind tunnel model is costly, and there is no continuous pressure change data on the measured surface.

Aerodynamic pressure sensitive paint pressure measurement is a new wind tunnel pressure measurement technology developed since the 1980s in the world. It is used to measure the airflow pressure on the surface of the aircraft model, and can dynamically measure the pressure distribution. It is called a revolution in pressure measurement technology. . Compared with the traditional sensor pressure measurement, its advantages are: from discrete point measurement to continuous surface measurement; the spatial resolution is improved, which overcomes the difficulties of difficult distribution of pressure measurement points and few points; the same model can be used for pressure measurement and force measurement Simultaneous measurement; pressure measurement and surface flow state display are completed at the same time; no damage to the model, simple operation, and greatly reduced costs.

The pressure-sensitive varnish is a polymer seeded with probe molecules. Pneumatic pressure sensitive paint pressure measurement is based on the principle of photoluminescence and oxygen quenching of luminescent molecules. The pressure-sensitive paint broadcast with luminescent probe molecules is coated on the surface of the aircraft in an appropriate way, and when the excitation light of an appropriate wavelength is selected for irradiation, the pressure-sensitive paint instantly emits visible light of a certain wavelength. If the excited molecules collide with oxygen molecules before emitting photons, oxygen quenching occurs to reduce the emission of photons, corresponding to the weakening of luminous intensity. When the air flow passes through the surface of the model, the pressure is different everywhere, and the partial pressure of oxygen is also different, resulting in different degrees of quenching of the luminescent molecules in the pressure sensitive paint. Therefore, the greater the partial pressure of oxygen on the surface of the model (that is, the local static pressure), the smaller the luminous intensity. That is, the oxygen concentration and luminous intensity conform to the Stern-Volmer equation: $\frac{I_0}{I}=1+k_q{\mathrm{\&tau;}}_0\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">o</figure-callout>}}_2\&rsqb;=1+K_{\mathrm{SV}}\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">o</figure-callout>}}_2\&rsqb;---\left(1\right)$

Where I ₀ represents the luminous intensity without a quencher, where the quencher is oxygen molecules; [O ₂ ] is the oxygen concentration; I is the measured luminous intensity; k _q is the bimolecular quenching of the luminescent molecule quenched by oxygen Extinction rate constant; ${\mathrm{\&tau;}}_0=\frac{1}{k_L+k_C}$ , is the intrinsic lifetime of the excited state molecule; k _L and k _c represent the rate constants of the radiative and non-radiative processes of the luminescent molecule, respectively; K _SV is called the Stern-Volmer quenching constant, which characterizes the characteristics of the local pressure and luminous intensity.

Since I ₀ varies with film thickness, probe molecular concentration, film reflection performance, reflection angle and the distance between the light source or low-light meter probe and the sample, it is difficult to calibrate, so a reference light intensity I _r is introduced, which is defined as When there is no wind speed in the hole, the luminous intensity of the molecules is detected. and order $\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">o</figure-callout>}}_2\&rsqb;=k\&Center\; Dot;{\mathrm{<figure-callout\; id="2"\; label="P\; o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">P</figure-callout>}}_{o_{}}$ , after mathematical transformation from Stern-Volmer relation (1): $\frac{I_r}{I}=A+B\&Center\; Dot;\frac{P}{P_r}---\left(2\right)$

in, $A=\frac{1}{1+a{P}_r};B=\frac{a{P}_r}{1+a{P}_r},a=\frac{k\&Center\; Dot;k_q}{k_L+k_C},$ Obviously A+B=1. If the light intensity at 1 atmosphere is used to represent the reference light intensity I _r , and 1 atmosphere is used to represent the reference pressure, then P _r =P ₁ , and I _r =I ₁ .

Since the mid-1980s, Moscow University and the Central Institute of Fluid Power of the former Soviet Union have jointly developed a pressure-sensitive paint, which is insensitive to temperature from 10°C to room temperature by using a detection coating to measure the pressure distribution. But the lacquer responds very slowly, with an induction period of up to two minutes for step changes in pressure. Use photosensitive film to record the luminescence, and its measurement accuracy is low, about ±10%. (Ardasheva, "Measuring Pressure Distribution with Detector Coatings", Journal of Applied Mechanics and Technical Physics, 1985(4), pp.24-31) [M.M.Ardasheva., "Measurement of Pressure Distribution by Means of Indicator Coatings", Zhurnal Prikladnoi Mekhaniki I Tekhnicheskoi Fiziki, No. 4, 1985, pp. 24-31]. The University of Washington in the United States began to develop pressure-sensitive paint in 1987, and NASA and Boeing provided research funding. In 1991, they applied for the European patent "Measurement of Surface Pressure by Luminescent Oxygen Quenching". The film is used for wind tunnel measurements. Irradiated by 380nm ultraviolet light source, the luminescent image is recorded by CCD and stored and processed by computer. The luminescence intensity of the probe molecule platinum octaethylporphyrin (PtOEP) was reduced by 40% after being irradiated by the experimental light source for 45 minutes. (Gutmann, Kavandi, Gellerli, et al., "Surface Pressure Measurements Using Luminescent Oxygen Quenching", European Patent, publication number: 0 472 243 A2, published application date: February 26, 1992)[ M.P. Gouterman, J.L. Kavandi, J. (NMI) Gallery, et al, "Surface Pressure Measurement by Oxygen Quenching of Luminescence", European Patent 0 472 243 A2, 26, 02, 92]. McDonnell Douglas reported short response time in 1994, using visible light to excite photoluminescent pressure-sensitive paint for pressure measurement. The pressure-sensitive paint uses a halogen tungsten lamp as the light source, selects 400-500nm visible light for excitation, and emits light at about 600nm. This is a relatively new result, but the structure of the luminescent probe molecule and the composition of the pressure-sensitive paint have not been published, and the calibration curve of the pressure-sensitive paint has an inflection point, indicating that the response of the pressure-sensitive paint to pressure changes is not a continuous linear relationship. (Morris, Donovan, "Application of Pressure and Temperature Sensitive Paints in High Velocity Airflows", Proceedings of the American Institute of Aeronautics and Astronautics, AIAA 94-2231, 1994) [M.J.Morris and J.F.Donovan, "Application of Pressure -and Temperature-Sensitive Paints to High-Speed Flow", AIAA 94-2231, 1994] In short, the only pressure-sensitive paint probe molecule disclosed so far is PtOEP.

It can be seen from the above literature reports that the main problems in the use of pressure-sensitive paints are:

(1) Using ultraviolet light or short-wavelength laser as the excitation light source is not conducive to safe operation, and it is easy to cause photodegradation of probe molecules;

(2) The currently published probe molecule PtOEP itself has a photodegradation problem, which results in a decrease in light intensity as the irradiation time increases, causing instability in pressure measurement;

(3) The response time is slow, that is, the response time of the pressure-sensitive paint to change with the pressure is longer. This is because the matrix currently used to disperse probe molecules is silicone resin, which has an inductive effect, that is, excited oxygen is chemically combined with silicone rubber to reduce the oxygen concentration, resulting in a slower response to light. , when its gas permeability is poor, the collision time between probe molecules and oxygen molecules is delayed, which slows down the response;

(4) Due to the uneven distribution of probe molecules in the pressure-sensitive paint matrix, double-position quenching often occurs, resulting in the calibration curve of the pressure-sensitive paint not being a continuous straight line, especially when the pressure becomes larger, the slope Reduced, resulting in a downward deviation, reducing the pressure measurement sensitivity.

The purpose of the present invention is to solve the problems existing in the current pressure-sensitive paint, and to prepare a pressure-sensitive paint that uses a diimide ruthenium complex with good photostability to excite light in the visible light range as a probe molecule. Using a specific sol-gel preparation technology to uniformly disperse the probe molecules into the porous _SiO2 matrix to prepare a pressure-sensitive paint system with good air permeability, high content of probe molecules and adjustable probe molecule content, so that the system’s The oxygen quenching effect is good, the response time is fast, the pressure measurement sensitivity is high, and it can have a good linear relationship in a wide range of pressure changes.

The aerodynamic pressure-sensitive paint of the present invention comprises luminescent probe molecules and organosilicon polymers, which use diimide ruthenium complexes as probe molecules; the monomer of the organosilicon polymers is dimethyldiethoxysilane The mixed solution of γ-aminopropyltriethoxysilane, its molar ratio=0～8, or the mixed solution of dimethyldiethoxysilane and tetraethoxysilane, its molar ratio=0～8, Or a mixture of dimethyldiethoxysilane, γ-aminopropyltriethoxysilane and tetraethoxysilane, wherein, dimethyldiethoxysilane and (γ-aminopropyltriethoxy silane+tetraethoxysilane) molar ratio=0~8; in the transparent SiO ₂ sol made by cohydrolysis and polycondensation of alkoxysilane, the added amount of luminescent probe molecule is 1×10 ^-4 ～5× 10 ^-3 mol/l. The selected luminescent probe molecules are diimide ruthenium complexes, specifically bipyridyl ruthenium [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O, o-phenanthroline ruthenium [Ru(phen) ₃ ]Cl ₂ · 3H ₂ O and 4,7-diphenyl-phenanthroline ruthenium [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O three kinds of probe molecules. These probe molecules can be synthesized according to the method reported by Watts and Crossby. That is to say, hydrated ruthenium trichloride and 2,2'-bipyridine, or o-phenanthroline, or 4,7-diphenyl-o-phenanthroline were dissolved in molar ratios of 1:6.6, 1:9.4, and 1:5.4, respectively. In absolute ethanol, in the presence of hydroxylamine hydrochloride, stirred and refluxed at an oil bath temperature of 120°C for 24 to 60 hours, bipyridyl ruthenium [Ru(bpy) ₃ ]Cl ₂ 6H ₂ O, o-phenanthroline Crude products of three kinds of probe molecules of ruthenium[Ru(phen) ₃ ]Cl ₂ ·3H ₂ O and 4,7-diphenyl-phenanthroline ruthenium[Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O , the desired probe molecule can be obtained by recrystallization and column chromatography. (Watts, Crosby, "Ru(II) and Iridium(III) with 4,4'-diphenyl-2,2'-bipyridine, 4,7-diphenyl-1,10-phenanthrene Spectroscopic Characterization of Complexes of Ruthenium(II) and Iridium(III) with 4,4'-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 sol-gel technology, and a special preparation process is designed for the purpose of the present invention. This is a fine chemical preparation process that requires strict control of reaction conditions.

The preparation process of the pressure-sensitive paint is shown in Fig. 1. First mix dimethyldiethoxysilane (referred to as MEOS) and γ-aminopropyltriethoxysilane (trade name KH550) in a molar ratio = 0 to 8, or dimethyldiethoxysilane and tetraethoxysilane Ethoxysilane (denoted as TEOS) molar ratio = 0 ~ 8, or dimethyldiethoxysilane and (γ-aminopropyl triethoxysilane + tetraethoxysilane) molar ratio = 0 ～8 After mixing, dissolve in 1.0～8.0 times of absolute ethanol or acetone solvent of the total amount (number of moles) of alkoxysilane in the mixed liquid; then mix the catalyst base or acid with water and slowly add it dropwise to the above solution , adjust pH=5.2～11.0. The amount of catalyst is 1% to 5% of the total amount of alkoxysilane (moles) or 2% to 8% of the total amount of alkoxysilane (moles) of acid, and the amount of water is alkoxysilane 1.1 to 8.4 times the total amount (number of moles). Stir at 15°C-35°C for 1-12 hours, directly obtain a transparent SiO 2 sol with a viscosity suitable for the coating film without standing still, or _{obtain a transparent SiO 2 sol} with a viscosity suitable for the coating film after standing and aging for 12-48 hours; Any one of the probe molecules [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O, [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O or [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O It is added to the transparent SiO ₂ sol produced by cohydrolysis and polycondensation of alkoxysilane, and the amount of addition is 1×10 ^-4 ~ 5×10 ^-3 mol/l. After ultrasonic dispersion, it is spin-coated on a glass slide, and then dried at room temperature to obtain a pressure-sensitive paint without a substrate, or dripped on a substrate with a different white reflective substrate, and then dried at room temperature to obtain a substrate with a substrate pressure sensitive paint.

In the process of preparing sol-gel, the composition and ratio of raw materials are the key, which determine the distribution characteristics of probe molecules and the gas permeability of the matrix, and then affect the oxygen quenching effect of pressure-sensitive paint and the linear relationship between the wind tunnel calibration curve . When TEOS is used as a raw material, the hydrolysis rate is faster, and a highly cross-linked _SiO2 polymer is formed at a faster rate, and the resulting film is easy to crack; in addition, this highly cross-linked sol-gel and probe molecules The compatibility is not good, and it is often observed that the probe molecules are enriched on the surface of the film layer, resulting in uneven distribution. For this reason, we introduced MEOS, a difunctional siloxane, to control the degree of crosslinking and avoid cracking. Moreover, due to the hydrolysis and polycondensation of MEOS to form a linear skeleton polymer PDMS, it has a high oxygen diffusion coefficient, which is conducive to the penetration of O ₂ , so it is beneficial to improve 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; it can also be used as a solubilizer to improve the solubility of probe molecules in sol-gel and improve the stability of probe molecules in the matrix. content and promote the uniform distribution of probe molecules in the matrix without aggregation. MEOS/KH550=3～8 is the preferred ratio range, the oxygen quenching effect of the pressure-sensitive paint prepared under this range is good, the ratio of the luminous intensity I _N2 in nitrogen and I _O2 in oxygen is I _N2 /I _O2 In the range of 7.7 to 12.4. The introduction of KH550 for the matrix preparation of pressure-sensitive paints is the key point of the present invention. Due to the presence of γ-aminopropyl in KH550, it has a certain degree of coordination with the central metal ion of the probe molecule, divalent ruthenium, and KH550 is a polar molecule, which is similar in polarity to the polar probe molecule, so the polarity The dual factors of similar compatibility and coordination greatly enhanced the solubility of probe molecules in sol-gel. The good compatibility between the probe molecules and the matrix enables the probe molecules to be fully and evenly dispersed in the matrix, avoiding double-position quenching, and enabling the calibration curve of the pressure-sensitive paint to have a good linear relationship.

In the process of preparing sol-gel, the catalyst plays the role of adjusting the pH value and controlling the reaction speed, thereby affecting the microstructure of the sol-gel. When using basic catalysis, sodium hydroxide is a preferred catalyst. When the amount of basic catalysis is large, the reaction speed is too fast, and the sol-gel formed is cloudy and opaque in appearance. The colorless and transparent sol-gel can be obtained only when the amount of the alkali catalyst is controlled to about 1-3% of the total amount of the alkoxysilane. It should be pointed out that since KH550 itself is strongly basic, hydrochloric acid is the preferred catalyst when it is catalyzed by acid. If it is catalyzed by 4-8% hydrochloric acid of the total amount of alkoxysilane, the reaction system can be adjusted to pH=6.5-9.8. Under this condition, the hydrolysis rate is moderate, and a colorless and transparent sol-gel can be obtained. The magnification scanning electron microscope test proves that the microstructure uniformity of the matrix prepared under this condition is good.

The 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 it is difficult to form a gel. However, when the amount of water is large, it is easy to quickly form highly cross-linked SiO ₂ , which is not conducive to improving the gas permeability of the gel. After repeated screening, it is appropriate to select the amount of water added to be 3 to 7 times the total amount of alkoxysilane. The addition of ethanol is to dilute the concentration of the reactants to facilitate the formation of a microscopically uniform film, and at the same time prolong the curing time, which is beneficial to the smooth progress of the spray coating process. The suitable addition amount of ethanol is 3-8 times of the total amount of alkoxysilane.

The choice of substrate has a significant impact on both the photoluminescence and oxygen quenching of the pressure sensitive paint. Neutral SiO ₂ or Al ₂ O ₃ with a particle size of the order of μm, or slightly acidic TiO ₂ or fume-like SiO ₂ with a particle size of the order of nm are respectively used as substrates, and the prepared pressed Sensitive varnishes are coated on the above bottom layers respectively. Due to the existence of the substrate, it is not only beneficial to enhance the excitation of the probe molecules by the incident light, but also to enhance the effective reflection of the probe molecules’ luminescence, which can double enhance the oxygen quenching signal.

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

(1) Visible light excitation

The absorption spectrum of the probe molecule [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O is shown in Figure 2. It has strong absorption in the visible region above 360nm, and there are two strong metals at 440nm and 460nm. - Ligand charge transfer (MLCT) characteristic absorption bands. In this spectral range, the probe molecules are selectively excited, and higher luminous efficiency can be obtained in the long-wavelength (600-640nm) visible light region.

(2) Photostability

Figure 3 shows that the probe molecule [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O was continuously irradiated with visible light in the air, and the relative luminous intensity did not change more than 0.5% within 2.5 hours, showing very good light stability. That is, under the experimental conditions, no oxidative degradation of the probe molecules by singlet oxygen was observed, indicating that the probe molecules had good photochemical stability.

(3) Good oxygen permeability and short response time

Figure 4 shows the time-scanning results of the luminous intensity over time when the excitation wavelength is selected to be 460nm and the emission wavelength is fixed at 610nm, and the sample is time-scanned under nitrogen and oxygen respectively (the response time of the instrument is 0.5s). The figure shows that when pure oxygen and pure nitrogen are alternately fed into the measuring cell at a flow rate of 4.4ml/s, a good oxygen quenching effect is obtained. No substrate pressure sensitive varnish $\left(a\right)\frac{I_{N_2}}{{\mathrm{<figure-callout\; id="2"\; label="I\; o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">I</figure-callout>}}_{o_{}}}=7.7$ ;Pressure-sensitive paint with backing $\left(b\right)\frac{I_{N_2}}{{\mathrm{<figure-callout\; id="2"\; label="I\; o"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">I</figure-callout>}}_{o_{}}}=12.4$ . In this experiment, whether it is oxygen or nitrogen, the change of luminous intensity can reach equilibrium within the response time of the instrument. It shows that the induction period of the pressure-sensitive paint sample prepared in this experiment is extremely short. This is because the SiO ₂ film prepared by the sol-gel method is a chemically inert porous matrix material, which is characterized by large porosity. The microstructure of the paint layer was characterized by scanning electron microscopy, and the SiO ₂ film in the paint layer was observed. The matrix is stacked particles with a uniform size distribution of 10-20nm, and the micropores formed by the stacks are also in the same order of magnitude. Oxygen permeability is good, which is conducive to the diffusion and collision quenching of oxygen molecules and stimulated probe molecules, and the singlet oxygen produced by it will be inactivated when it encounters the matrix, thus solving the need for additional drums in the wind tunnel test brought about by the induction period. The problem of wind time. When repeatedly passing oxygen and nitrogen, the change of luminous intensity shows good repeatability. The above results indicate that the oxygen quenching process is an efficient, dynamic and reversible process.

Comparing (a) and (b), it can also be seen that due to the existence of the substrate, it is not only beneficial to enhance the excitation of the probe molecules by the incident light, but also to enhance the effective reflection of the luminescence of the probe molecules, which double enhances the oxygen quenching signal .

(4) The microstructure is uniform, and the calibration curve shows a good linear relationship

In the present invention, the sol-gel technology is used to effectively control the uniform distribution of the probe molecules in the matrix, and the pressure-sensitive paint with a substrate is used for wind tunnel simulation tests, and a continuously changing calibration curve is obtained in a wide range of pressure changes As shown in Figure 5c, where A=0.25 and B=0.75. It can be seen from the figure that the pressure-sensitive paint prepared in this work shows a good linear relationship in both the vacuum section (1.01×10 ⁴ -1.01×10 ⁵ Pa) and the low pressure section (1.01×10 ⁵ -4.05×10 ⁵ Pa). , the correlation coefficient γ=0.99 or more, and the slopes are consistent, that is, there is no turning point, which conforms to a single Stem-Volmer relationship. This greatly simplifies the computational model and increases experimental precision. This shows that our paint-like probe has uniform molecular distribution and good air permeability, which is a good pressure-sensitive paint system.

(5) High sensitivity

Fig. 5d is the calibration curve of the pressure sensitive paint given in the European Patent "Luminescent Pressure Sensitive Composition". (Mosharov, Kuzmin, Oulov, etc., "luminescent pressure-sensitive composition", European patent, publication number: 0558 771 A1, open application date: 08,09,93) [V.Mosharov, M. Kuzmin, A.Orlov, et al."Luminescence PressureSensitive Composition", European Patent, 0558 771 A1, 08, 09, 93] Due to the different values of the reference light intensity _Ir , the value range of the ordinate given is different, But still comparable. From the comparison of c and d in Figure 5, it can be seen that the slope of the calibration curve of the pressure-sensitive paint prepared by the present invention is higher than that of foreign pressure-sensitive paints in a wider pressure range, showing higher sensitivity to airflow pressure .

Description of drawings:

Figure 1: Schematic diagram of the preparation process of the aerodynamic pressure-sensitive paint of the present invention;

Figure 2: The electronic absorption spectrum of the probe molecule [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in methanol of the present invention;

Figure 3: Photostability experiment of the probe molecule [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O of the present invention;

Fig. 4: The time response characteristic of the oxygen quenching of the pressure-sensitive lacquer in the silicon dioxide thin film of the present invention;

a. Without substrate b. With substrate

Fig. 5: Comparison of the wind tunnel simulation calibration curves of the pressure-sensitive paint of the present invention;

c. The pressure-sensitive paint prepared by this method, excited by visible light, B=0.75

d. Pressure-sensitive paint prepared by document European Patent, 0558 771 A1, excited by ultraviolet light, B=0.67

Figure 6: Oxygen quenching characteristics of the probe molecule [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in the solid film of the present invention;

E. example 1 gained 1 ^# sol-gel

f. Example 2 gained 2 ^# sol-gel

Fig. 7: The pressure distribution diagram of the pressure measurement of the pressure-sensitive paint jet impinging on the convex surface of the present invention;

g. Black-and-white photographs in pressure-sensitive paint manometry

h. Pseudo-color pressure distribution map of pressure-sensitive paint pressure measurement

Example 1

Dissolve 1 mol KH550 and 8 mol MEOS (MEOS: KH550=8 at this time) in 30 mol absolute ethanol, slowly add 0.09 mol sodium hydroxide and 28 mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 9.0. The amount of solvent absolute ethanol and the amount of water are respectively 3.3 times and 3.1 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 1.0% of the total amount of alkoxysilane. Stirring was continued for 5 hours at 25 °C, followed by static aging for 24 hours to obtain a transparent SiO _sol -gel that could be film-coated.

Dissolve 18.9 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 5 ml of the above sol-gel at a concentration of 3×10 ^-3 mol/l, and after ultrasonic dispersion, spray on the SiO ₂ reflected on the bottom substrate, and after drying at room temperature for 7 days, the pressure-sensitive paint with substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 8.4. It is used for wind tunnel simulation test, and the result shown in Figure 6e is obtained.

Example 2

Dissolve 1 mol KH550 and 3 mol MEOS (MEOS: KH550=3 at this time) in 14 mol absolute ethanol, slowly add 0.24 mol hydrochloric acid and 12.6 mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 7.8. The amount of solvent absolute ethanol and water are respectively 3.5 times and 3.2 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 6.0% of the total amount of alkoxysilane. Stirring was continued for 5 hours at 15 °C, followed by static aging for 12 hours to obtain a transparent SiO _sol -gel that could be coated.

Dissolve 7.5 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 3 ml of the above sol-gel at a concentration of 2×10 ^-3 mol/l. After ultrasonic dispersion is uniform, spin-coat on glass After drying at room temperature for 9 days, a substrate-free pressure-sensitive paint was obtained. The paint layer is transparent and the probe molecules are evenly distributed.

A time scan of the emission spectrum was carried out with the resulting substrate-free pressure-sensitive varnish, and it was determined that I _N2 /I _O2 =7.7. It was used in the oxygen quenching experiment, and its Stem-Volmer correlation diagram was made, and the result shown in Figure 6f was obtained.

Example 3

Dissolve 2 mol KH550 and 2 mol MEOS (MEOS: KH550=1 at this time) in 7 mol absolute ethanol, slowly add 0.12 mol sodium hydroxide and 14 mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 9.2. The amount of solvent absolute ethanol and the amount of water are respectively 1.8 times and 3.5 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 3.0% of the total amount of alkoxysilane. Stirring was continued for 3 hours at 35 °C, and a transparent SiO _sol -gel that could be coated was obtained without standing aging.

Dissolve 12.6 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel at a concentration of 1×10 ^-3 mol/l, and after ultrasonic dispersion, spray on the Al ₂ O ₃ reflective base substrate, after drying at room temperature for 7 days, the pressure-sensitive paint with substrate was obtained.

A time scan of the emission spectrum was carried out with the pressure sensitive varnish on the backing and it was determined that I _N2 /I _O2 = 2.4.

Example 4

Dissolve 4mol TEOS (MEOS:TEOS=0 at this time) in 20mol absolute ethanol, slowly add a mixed solution of 0.12mol hydrochloric acid and 24mol water under vigorous stirring, and adjust the initial pH of the reaction solution=6.0, at this time the solvent absolute ethanol The amount of hydrochloric acid and the amount of water are respectively 5 times and 6 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 3.0% of the total amount of alkoxysilane. Stirring was continued for 2 hours at 30°C, and a transparent SiO _sol -gel suitable for film coating was obtained without standing aging.

Dissolve 18.7 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 5 ml of the above sol-gel at a concentration of 5×10 ^-3 mol/l. After ultrasonic dispersion, spin-coat the TiO ₂ The bottom glass plate was dried at room temperature for 3 days to give the backed pressure sensitive lacquer. It can be seen with the naked eye that a small amount of probe molecules are enriched on the surface of the paint, and the cracks in the paint layer are serious.

A time scan of the emission spectrum was carried out with the obtained pressure-sensitive varnish with substrate, and it was determined that I _N2 /I _O2 = 3.5.

Example 5

Dissolve 10mol MEOS, 0.5mol KH550 and 1.5mol TEOS (MEOS at this time: (KH550+TEOS)=5) in 12mol acetone, add a mixed solution of 0.24mol hydrochloric acid and 33mol water under vigorous stirring, and adjust the initial pH of the reaction solution to 8.2, At this time, the amount of the solvent acetone and the amount of water are respectively 1 time and 2.g times of the total amount of the alkoxysilane, and the amount of the catalyst hydrochloric acid is 2.0% of the total amount of the alkoxysilane. A transparent SiO sol _- gel suitable for film coating can be obtained after stirring for 1 h at 33 °C.

Dissolve 1.26 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel at a concentration of 1×10 ^-4 mol/l. After ultrasonic dispersion, spin-coat on the A glass plate with fumed SiO ₂ was dried at room temperature for 15 days to obtain a pressure-sensitive paint with a substrate. Paint layer with slight cracks.

The obtained substrate-free pressure-sensitive varnish was tested for luminescence spectrum in nitrogen, oxygen and air atmospheres respectively, and it was measured that I _N2 /I _air =1.1; I _N2 /I _O2 =1.3.

Example 6

4mol KH550 (MEOS at this time: KH550=0) was dissolved in 24mol acetone, and a mixed solution of 0.05mol sodium hydroxide and 19.2mol water was added under vigorous stirring to adjust the initial pH of the reaction solution=9.4. At this time, the amount of solvent acetone and The amount of water is respectively 6 times and 4.8 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 1.2% of the total amount of alkoxysilane. Stirring was continued for 5 hours at 20°C, and then aged for 12 hours to obtain a transparent SiO ₂ sol-gel suitable for film coating.

Dissolve 3.8 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 10 ml of the above sol-gel at a concentration of 5×10 ^-4 mol/l, disperse uniformly by ultrasonic, and spin-coat on a glass plate , After drying at room temperature for 4 days, a substrate-free pressure-sensitive paint was obtained. The obtained substrate-free pressure-sensitive varnish was tested for luminescence spectrum in nitrogen, oxygen and air atmospheres respectively, and it was measured that I _N2 /I _air =1.8; I _N2 /I _O2 =2.6.

Example 7

Dissolve 3mol KH550 and 6mol MEOS (MEOS: KH550=2 at this time) in 36mol acetone, slowly add 0.45mol hydrochloric acid and 63mol water to mix the obtained solution after stirring, adjust the initial pH of the reaction solution=8.8, at this time the solvent acetone The amount of hydrochloric acid and the amount of water are respectively 4 times and 7 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 5.0% of the total amount of alkoxysilane. Stirring was continued for 12 hours at 18 °C, followed by static aging for 20 hours to obtain a transparent SiO _sol -gel that could be coated.

Dissolve 6.3 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel at a concentration of 5×10 ^-4 mol/l, and after ultrasonic dispersion, spray on the TiO ₂ reflected on the substrate of the bottom layer, and after drying at room temperature for 5 days, the pressure-sensitive paint with substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 4.3.

Example 8

Dissolve 2mol TEOS and 8mol MEOS (MEOS: TEOS=4 at this time) in 60mol acetone, slowly add 0.37mol hydrochloric acid and 84mol water to mix the obtained solution after stirring, adjust the initial pH of the reaction solution=5.2, at this time the solvent acetone The amount of hydrochloric acid and the amount of water are respectively 6 times and 8.4 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 3.7% of the total amount of alkoxysilane. Stirring was continued for 9 h at 26 °C, followed by static aging for 21 h, resulting in a film-coatable transparent SiO _sol -gel.

Dissolve 7.5mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10ml of the above sol-gel at a concentration of 6×10 ^-4 mol/l, disperse evenly by ultrasonic, spin-coat on glass After drying for 7 days at room temperature, a pressure-sensitive paint without a backing was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 3.1.

Example 9

Dissolve 6mol MEOS, 0.5mol KH550 and 0.5mol TEOS (MEOS at this time: (KH550+TEOS) = 6) in 35mol acetone, slowly add 0.49mol hydrochloric acid and 31mol water to the solution after stirring, and adjust the initial pH of the reaction solution =7.0, the amount of solvent acetone and the amount of water are respectively 5 times and 4.4 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 7.0% of the total amount of alkoxysilane. Stirring was continued for 12 hours at 24 °C, followed by static aging for 24 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 1.5 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 20 ml of the above sol-gel at a concentration of 1×10 ^-4 mol/l. After ultrasonic dispersion, spray on the surface with SiO ₂ On the substrate with a reflective bottom layer, after drying at room temperature for 9 days, a pressure-sensitive paint with a substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 5.0.

Example 10

Dissolve 1 mol KH550 and 7 mol MEOS (MEOS: KH550=7 at this time) in 16 mol acetone, slowly add 0.60 mol hydrochloric acid and 17 mol water under stirring and mix the resulting solution to adjust the initial pH of the reaction solution=7.4, at this time the solvent acetone The amount of hydrochloric acid and the amount of water are respectively 2 times and 2.1 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 7.5% of the total amount of alkoxysilane. Stirring was continued for 11.5 h at 28 °C, followed by static aging for 20 h to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 6.9 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 10 ml of the above sol-gel, the concentration at this time is 9×10 ^-4 mol/l, after ultrasonic dispersion, spray on the surface with TiO ₂ On the substrate of the reflective bottom layer, after drying at room temperature for 18 days, the pressure-sensitive paint with the substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 10.2.

Example 11

Dissolve 4mol KH550 and 6mol MEOS (MEOS: KH550=1.5 at this time) in 24mol acetone, slowly add 0.8mol hydrochloric acid and 24mol water to mix the obtained solution after stirring, adjust the initial pH of the reaction solution=9.8, at this time the solvent acetone Both the amount of water and the amount of alkoxysilane are 2.4 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 8.0% of the total amount of alkoxysilane. Stirring was continued at 30°C for 5 hours, and then left to age for 30 hours to obtain a SiO ₂ -transparent gelsol-gel that could be coated.

Dissolve 6.1 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 10 ml of the above-mentioned sol-gel, the concentration is 8×10 ^-4 mol/l at this time, after ultrasonic dispersion, spray on the surface with Al ₂ O ₃ reflected on the substrate of the bottom layer, and after drying at room temperature for 5 days, the pressure-sensitive paint with the substrate was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 3.8 was measured.

Example 12

Dissolve 2mol TEOS and 5mol MEOS (MEOS:TEOS=2.5 at this time) in 56mol of absolute ethanol, slowly add 0.28mol of hydrochloric acid and 54mol of water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 6.5. At this time, the solvent The amount of absolute ethanol and water are respectively 8.0 times and 7.7 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 4.0% of the total amount of alkoxysilane. Stirring was continued for 10 h at 25 °C, followed by static aging for 48 h, resulting in a transparent SiO _sol -gel that could be film-coated.

Dissolve 7.5 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 10 ml of the above sol-gel at a concentration of 1×10 ^-3 mol/l, disperse evenly by ultrasonic, and spin-coat on a glass plate , After drying at room temperature for 8 days, a substrate-free pressure-sensitive paint was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 2.4.

Example 13

Dissolve 7mol MEOS, 1mol KH550 and 1mol TEOS (MEOS: (KH550+TEOS) = 3.5 at this time) in 21mol of absolute ethanol, slowly add 0.22mol of hydrochloric acid and 42mol of water under stirring, and mix the obtained solution to adjust the initial pH of the reaction solution =7.9, now the amount of solvent absolute ethanol and the amount of water are respectively 2.3 times and 4.7 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 2.5% of the total amount of alkoxysilane. Stirring was continued for 10.5 hours at 25 °C, followed by static aging for 40 hours to obtain a transparent SiO _sol -gel that could be film-coated.

Dissolve 4.5 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 10 ml of the above sol-gel, the concentration is 6×10 ^-4 mol/l at this time, after ultrasonic dispersion, spray on the surface with SiO ₂ On the substrate of the reflective bottom layer, after drying at room temperature for 3 days, the pressure-sensitive paint with the substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 4.2.

Example 14

Dissolve 2mol KH550 and 9mol MEOS (MEOS: KH550=4.5 at this time) in 44mol absolute ethanol, slowly add 0.72mol hydrochloric acid and 72mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 8.3. At this time, the solvent The amount of absolute ethanol and water are respectively 4 times and 6.5 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 6.5% of the total amount of alkoxysilane. Stirring was continued for 11.5 hours at 20 °C, followed by static aging for 36 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 6.0 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 10 ml of the above sol-gel, the concentration is 8×10 ^-4 mol/l at this time, after ultrasonic dispersion, spray on the surface with TiO ₂ On the substrate of the reflective bottom layer, after drying at room temperature for 10 days, the pressure-sensitive paint with the substrate is obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 10.6 was measured.

Example 15

Dissolve 11mol MEOS, 0.5mol KH550 and 1.5mol TEOS (MEOS at this time: (KH550+TEOS) = 5.5) in 62mol acetone, slowly add 0.72mol hydrochloric acid and 31mol water under stirring and mix the obtained solution to adjust the initial pH of the reaction solution =6.7, now the amount of solvent acetone and the amount of water are respectively 4.8 times and 2.4 times of the total amount of alkoxysilane, and the amount of catalyst hydrochloric acid is 5.5% of the total amount of alkoxysilane. Stirring was continued for 11 hours at 19 °C, followed by static aging for 12 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 2.5 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel, the concentration is 2×10 ^-4 mol/l at this time, after ultrasonic dispersion, spray on the Al ₂ O ₃ reflective base substrate, after drying at room temperature for 12 days, the pressure-sensitive paint with substrate was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 4.8 was measured.

Example 16

Dissolve 13mol MEOS, 1mol KH550 and 1mol TEOS (MEOS: (KH550+TEOS) = 6.5 at this time) in 30mol of absolute ethanol, slowly add 0.75mol of sodium hydroxide and 16.5mol of water under stirring and mix the obtained solution to adjust the reaction solution The initial pH=11.0, the amount of solvent absolute ethanol and the amount of water are respectively 2 times and 1.1 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 5.0% of the total amount of alkoxysilane. Stirring was continued for 4 h at 26 °C, followed by static aging for 24 h, resulting in a film-coatable transparent SiO _sol -gel.

Dissolve 8.8 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel at a concentration of 7×10 ^-4 mol/l, and after ultrasonic dispersion, spray on the SiO ₂ reflected on the bottom substrate, after drying at room temperature for 17 days, the pressure-sensitive paint with substrate was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 5.4 was measured.

Example 17

Dissolve 2mol KH550 and 15mol MEOS (MEOS: KH550=7.5 at this time) in 51mol of absolute ethanol, slowly add 0.34mol of sodium hydroxide and 90mol of water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 10.2. The amount of solvent absolute ethanol and the amount of water are respectively 3 times and 5.3 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 2.0% of the total amount of alkoxysilane. Stirring was continued for 7 h at 25 °C, followed by static aging for 12 h to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 5.0 mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10 ml of the above sol-gel at a concentration of 4×10 ^-4 mol/l, disperse uniformly by ultrasonic, and spin-coat on glass After drying at room temperature for 16 days, a substrate-free pressure-sensitive paint was obtained.

The pressure-sensitive paint obtained above was subjected to time scanning of the emission spectrum, and it was measured that I _N2 /I _O2 = 8.2

Example 18

Dissolve 2 mol KH550 and 10 mol MEOS (MEOS: KH550=5 at this time) in 54 mol acetone, slowly add 0.31 mol sodium hydroxide and 78 mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 9.7. At this time, the solvent The amount of acetone and water are respectively 4.5 times and 6.5 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 2.6% of the total amount of alkoxysilane. Stirring was continued for 5 h at 35 °C, followed by static aging for 48 h to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 9.7mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 10ml of the above sol-gel, the concentration is 1.3×10 ^-3 mol/l, after ultrasonic dispersion, spray on the surface with Al ₂ O ₃ reflected on the soft substrate of the bottom layer, and after drying at room temperature for 5 days, the pressure-sensitive paint with the substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 12.4. And it is used for pressure measurement when air jet impinges on a convex pressure-sensitive paint panel, and a complex pressure distribution structure is obtained on a small area. The black-and-white photo of the pressure-sensitive paint taken by CCD in the pressure measurement is shown in Fig. 7(g). It can be seen from the figure that the lightness and darkness of each position on the paint surface are different, indicating that the light intensity is different everywhere, that is, the gray level is different. This shows that the pressure of the airflow is not the same everywhere, the greater the pressure, the darker the paint, and vice versa. It can be seen from the figure that a trumpet-shaped black shadow is seen near the nozzle, which indicates that the pressure in this area is relatively high. We also performed pseudo-color processing on black and white photos, representing different gray levels with different colors, and obtained a more intuitive pseudo-color pressure distribution map with clear layers, as shown in Figure 7(h). Along the direction of the nozzle, as the distance from the nozzle is different, the pressure on each place is obviously different, showing rich pressure distribution levels. It shows that the pressure-sensitive paint can well express the difference of relative pressure on the test surface, and has a high spatial resolution.

Example 19

Dissolve 1 mol TEOS and 6 mol MEOS (MEOS:TEOS=6 at this time) in 14 mol acetone, slowly add 0.21 mol sodium hydroxide and 16 mol water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 7.6. At this time, the solvent The amount of acetone and water are respectively 2 times and 2.3 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 3.0% of the total amount of alkoxysilane. Stirring was continued for 12 hours at 23 °C, followed by static aging for 24 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 15.0 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 10 ml of the above sol-gel at a concentration of 2×10 ^-3 mol/l. After ultrasonic dispersion, spray on _the After 14 days of drying at room temperature on the substrate of the reflective bottom layer, the pressure-sensitive paint with the backing was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 6.2 was measured.

Example 20

Dissolve 2 mol KH550 and 8 mol MEOS (MEOS: KH550=4 at this time) in 37 mol absolute ethanol, slowly add 0.45 mol sodium hydroxide and 66 mol water under stirring and mix the obtained solution to adjust the initial pH of the reaction solution to 10.6. The amount of solvent absolute ethanol and the amount of water are respectively 3.7 times and 6.6 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 4.5% of the total amount of alkoxysilane. Stirring was continued for 8 hours at 20 °C, followed by static aging for 36 hours to obtain a transparent SiO _sol -gel that could be film-coated.

Dissolve 11.2 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 5 ml of the above sol-gel at a concentration of 3×10 ^-3 mol/l, and after ultrasonic dispersion, spray on the surface with TiO ₂ After drying for 11 days at room temperature on the substrate of the reflective bottom layer, the pressure-sensitive paint with the substrate was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 9.2 was measured.

Example 21

Dissolve 14mol MEOS, 0.5mol KH550 and 1.5mol TEOS (MEOS: (KH550+TEOS) = 7.0 at this time) in 48mol absolute ethanol, slowly add 0.4mol sodium hydroxide and 71mol water to mix evenly with stirring, and adjust the reaction The initial pH of the solution=9.9, the amount of solvent absolute ethanol and the amount of water are respectively 3.0 times and 4.4 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 2.5% of the total amount of alkoxysilane . Stirring was continued for 10 hours at 20 °C, followed by static aging for 30 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 7.7 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 10 ml of the above sol-gel at a concentration of 1×10 ^-3 mol/l, disperse evenly by ultrasonic, and spin-coat on a glass plate , After drying at room temperature for 15 days, a substrate-free pressure-sensitive paint was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 6.0.

Example 22

Dissolve 2 mol TEOS and 16 mol MEOS (MEOS:TEOS=8 at this time) in 47 mol absolute ethanol, slowly add 0.63 mol sodium hydroxide and 40 mol water to the solution obtained after mixing evenly under stirring, adjust the initial pH of the reaction solution=7.8, then The amount of solvent absolute ethanol and the amount of water are respectively 2.6 times and 2.2 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 3.7% of the total amount of alkoxysilane. Stirring was continued for 12 h at 15 °C, followed by static aging for 48 h, resulting in a film-coatable transparent SiO _sol -gel.

Dissolve 19.2 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 5 ml of the above sol-gel at a concentration of 5×10 ^-3 mol/l. After ultrasonic dispersion, spray on the surface with SiO ₂ On the substrate of the reflective bottom layer, after drying at room temperature for 18 days, the pressure-sensitive paint with the substrate was obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 6.7 was measured.

Example 23

Dissolve 8mol MEOS, 1mol KH550 and 1mol TEOS (at this time MEOS: (KH550+TEOS) = 4.0) in 50mol of acetone, slowly add 0.42mol of sodium hydroxide and 46mol of water under stirring to obtain the mixed solution, adjust the initial pH of the reaction solution =10.4, now the amount of solvent acetone and the amount of water are respectively 5.0 times and 4.6 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 4.2% of the total amount of alkoxysilane. Stirring was continued for 10 h at 19 °C, followed by static aging for 24 h, resulting in a transparent SiO _sol -gel that could be film-coated.

Dissolve 11.5 mg of [Ru(phen) ₃ ]Cl ₂ ·3H ₂ O in 5 ml of the above sol-gel at a concentration of 3×10 ^-3 mol/l. After ultrasonic dispersion, spray on the surface with Al ₂ O ₃ reflected on the substrate of the bottom layer, and after drying at room temperature for 10 days, the pressure-sensitive paint with the substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive varnish obtained above, it was measured that I _N2 /I _O2 = 4.5.

Example 24

Dissolve 8mol MEOS, 4mol KH550 and 4mol TEOS (MEOS at this time: (KH550+TEOS) = 1.0) in 112mol absolute ethanol, slowly add 0.3mol sodium hydroxide and 88mol water with stirring and mix the resulting solution to adjust the reaction The initial pH of the solution=10.8, the amount of solvent absolute ethanol and the amount of water are respectively 7 times and 5.5 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 1.9% of the total amount of alkoxysilane . Stirring was continued for 7 hours at 25 °C, followed by static aging for 15 hours to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 11.3mg of [Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O in 10ml of the above-mentioned sol-gel, the concentration is 9×10 ^-4 mol/l at this time, after ultrasonic dispersion, spray on the Fume-like SiO ₂ reflected on the substrate of the bottom layer, and after drying at room temperature for 7 days, the pressure-sensitive paint with substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 1.9.

Example 25

Dissolve 4mol TEOS and 6mol MEOS (MEOS: TEOS=1.5 at this time) in 42mol absolute ethanol, slowly add 0.16mol sodium hydroxide and 56mol water to the obtained solution after stirring, and adjust the initial pH of the reaction solution to 7.5. The amount of solvent absolute ethanol and the amount of water are respectively 4.2 times and 5.6 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 1.6% of the total amount of alkoxysilane. Stirring was continued for 10 h at 25 °C, followed by static aging for 24 h to obtain a film-coatable transparent SiO _sol -gel.

Dissolve 18.7 mg of [Ru(bpy) ₃ ]Cl ₂ ·6H ₂ O in 5 ml of the above sol-gel at a concentration of 5×10 ^-3 mol/l, disperse uniformly by ultrasonic, and spin-coat on a glass plate , After drying at room temperature for 5 days, the pressure-sensitive paint without substrate was obtained.

Time-scanning the emission spectrum of the pressure-sensitive paint obtained above, it was measured that I _N2 /I _O2 = 2.5.

Example 26

Dissolve 2mol TEOS and 6mol MEOS (MEOS:TEOS=3 at this time) in 56mol of acetone, slowly add 0.38mol of sodium hydroxide and 54mol of water under stirring to obtain the mixed solution, and adjust the initial pH of the reaction solution to 8.1. At this time, the solvent The amount of acetone and water are respectively 7.0 times and 6.8 times of the total amount of alkoxysilane, and the amount of catalyst sodium hydroxide is 4.8% of the total amount of alkoxysilane. Stirring was continued for 6 hours at 35 °C, followed by static aging for 24 hours to obtain a film-coatable transparent SiO _sol -gel.

19.2mg[Ru(ph ₂ phen) ₃ ]Cl ₂ ·5H ₂ O was dissolved in 10ml of the above sol-gel, the concentration at this time was 2.5×10 ^-3 mol/l, after ultrasonic dispersion, sprayed on the surface with SiO _2. On the substrate of the reflective bottom layer, after drying at room temperature for 8 days, the pressure-sensitive paint with the substrate is obtained.

Time scanning of the emission spectrum of the pressure-sensitive paint obtained above was carried out, and I _N2 /I _O2 = 3.7 was measured.

Claims (9)

1. An aerodynamic pressure-sensitive paint, comprising luminescent probe molecules and organosilicon polymers, is characterized in that taking diimide ruthenium complexes as probe molecules; the monomer of organosilicon polymers is dimethyldiethoxy A mixture of dimethylsilane and γ-aminopropyltriethoxysilane, the molar ratio = 0 to 8, or a mixture of dimethyldiethoxysilane and tetraethoxysilane, the molar ratio = 0 to 8 8, or a mixture of dimethyldiethoxysilane, γ-aminopropyltriethoxysilane and tetraethoxysilane, wherein dimethyldiethoxysilane and (γ-aminopropyltriethoxysilane Ethoxysilane + tetraethoxysilane) molar ratio = 0 ~ 8; in the transparent SiO ₂ sol made by cohydrolysis and polycondensation of alkoxysilane, the amount of luminescent probe molecules added is 1×10 ¹ ~ 5 ×10 ³ mol/l. 2. A kind of aerodynamic pressure-sensitive paint as claimed in claim 1, it is characterized in that described diimine ruthenium complex is bipyridyl ruthenium, o-phenanthroline ruthenium and 4,7-diphenyl o-phenanthrole ruthenium. 3. An aerodynamic pressure-sensitive paint as claimed in claim 1, characterized in that the molar ratio of dimethyldiethoxysilane to γ-aminopropyltriethoxysilane is 3-8. 4. the preparation method of a kind of aerodynamic pressure-sensitive paint as claimed in claim 1 is characterized in that earlier dimethyl diethoxysilane and gamma-aminopropyl triethoxysilane are molar ratio=0～ 8, or dimethyldiethoxysilane and tetraethoxysilane molar ratio = 0 ~ 8, or dimethyldiethoxysilane and (γ-aminopropyl triethoxysilane + tetraethoxy base silane) mixed with molar ratio = 0-8 and then dissolved in anhydrous ethanol or acetone solvent which is 1.0-8.0 times of the total amount of alkoxy silane in the mixed solution; then mix the catalyst base or acid with water evenly and then slowly drop Add it to the above solution, adjust pH=5.2~11.0, stir at 15°C~35°C for 1~12 hours, you can directly get a transparent SiO ₂ sol with a viscosity suitable for coating without standing still, or stand and age for 12~48 hours Finally, a transparent SiO ₂ sol with a viscosity suitable for the coating film is obtained; the luminescent probe molecules are added to the transparent SiO ₂ sol produced by cohydrolysis and polycondensation of alkoxysilane, and the addition ratio is 1×10 ^-4 ~ 5×10 ^-3 mol /l; After ultrasonic dispersion, spin-coat on a glass slide, and then dry at room temperature to obtain a pressure-sensitive paint without a substrate, or drop it on a substrate with a different white reflective substrate, and dry at room temperature to obtain Pressure sensitive lacquer with backing. 5. The preparation method of a kind of aerodynamic pressure-sensitive paint as claimed in claim 4, it is characterized in that the addition of described catalyst is the alkali of 1%～5% of the total amount of alkoxysilane, or alkoxy 2% to 8% acid of the total amount of silane. 6. A method for preparing an aerodynamic pressure-sensitive paint as claimed in claim 4 or 5, wherein the alkali is sodium hydroxide, and the acid is hydrochloric acid. 7. The method for producing an aerodynamic pressure-sensitive paint as claimed in claim 4, characterized in that the amount of water added is 1.1 to 8.4 times the total amount of alkoxysilane. 8. the preparation method of a kind of aerodynamic pressure-sensitive paint as claimed in claim 4 is characterized in that described luminescent probe molecule is bipyridyl ruthenium, o-phenanthroline ruthenium or 4,7-diphenyl o-phenanthrene ruthenium pyroline. 9. the preparation method of a kind of pneumatic pressure-sensitive paint as claimed in claim 4 is characterized in that the mol ratio=3 of described dimethyldiethoxysilane and gamma-aminopropyltriethoxysilane ~8.

Images