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

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

Pneumatic pressure-sensitive lacquer and preparation method thereof

The invention belongs to chemical, aerodynamics, particularly Pneumatic pressure-sensitive lacquer and preparation method thereof.

At present, sensor measuring system is mainly adopted in the wind-tunnel pressure measurement, promptly in the model surface perforate, connects mutually with the hole with fine duct through model inside, and conduit is drawn from the model rear portion, links with outside scanning valvegear and measuring system again.It is costly to set up such wind tunnel model, and can not get measured surperficial successive pressure change data.

The Pneumatic pressure-sensitive lacquer pressure measurement is the wind-tunnel pressure measurement new technology of having developed since the eighties in the world, is used to measure the stream pressure on dummy vehicle surface, and can carries out dynamic measurement to pressure distribution, is known as the revolution of pressure measurement technology.Comparing its advantage with traditional transmitter pressure measurement is: become the successive planar survey by discrete point measurement; Spatial resolution improves, and has overcome difficulties such as difficult cloth pressure tap and point are few; Pressure measurement and dynamometry can be measured simultaneously with same model; Pressure measurement and surperficial fluidised form show to be finished simultaneously; Damage model is not simple to operate, and cost reduces greatly.

Pressure sensitive paint is a kind of polymkeric substance of broadcasting probe molecule.The Pneumatic pressure-sensitive lacquer pressure measurement is based on the photoluminescence and the oxygen quencher principle of light emitting molecule.The pressure sensitive paint of broadcasting the luminescence probe molecule is coated aircraft surface with suitable mode, and when selecting the excitation light irradiation of suitable wavelength for use, the instantaneous visible light that sends a certain wave band of pressure sensitive paint.If excited molecule is collided with oxygen molecule before sending photon, oxygen quencher minimizing photon then takes place emit, corresponding to weakening of luminous intensity.When air-flow process model surface, pressure is different everywhere, and then oxygen partial pressure is also different, causes the quencher degree varies sample to light emitting molecule in the pressure sensitive paint.So the oxygen partial pressure (being local static pressure) of model surface is big more, luminous light intensity is just more little.Be that oxygen concn and luminous intensity meet the Stern-Volmer equation: $\frac{I_0}{I}=1+k_q{\mathrm{\&tau;}}_0\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">O</figure-callout>}}_2\&rsqb;=1+K_{\mathrm{SV}}\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">O</figure-callout>}}_2\&rsqb;---\left(1\right)$

I wherein ₀Luminous intensity when expression does not have quencher, quencher herein is an oxygen molecule; [O ₂] be oxygen concn; I is the actual measurement luminous intensity; k _qFor light emitting molecule by the bimolecular quencher rate constant of oxygen quencher; ${\mathrm{\&tau;}}_0=\frac{1}{k_L+k_C}$ , be the intrinsic life-span of excited state molecule; k _LWith k _cRepresent the rate constant of light emitting molecule radiation and non-radiative process respectively; K _SVClaim the Stern-Volmer quenching constant, characterize characteristic when ground pressure and luminous intensity.

Because I ₀With film thickness, probe molecule concentration, film reflecting properties, reflection angle and light source or the different variations to some extent of low light level instrument probe, be difficult to calibration, so introduce a reference light intensity I with the sample distance _r, when being defined as in wind-tunnel no wind speed, the luminous intensity of molecular detection.And order $\&lsqb;{\mathrm{<figure-callout\; id="2"\; label="O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">O</figure-callout>}}_2\&rsqb;=k\&CenterDot;{\mathrm{<figure-callout\; id="2"\; label="P\; O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">P</figure-callout>}}_{O_{}}$ , can get after mathematic(al) manipulation from Stern-Volmer relational expression (1): $\frac{I_r}{I}=A+B\&CenterDot;\frac{P}{P_r}---\left(2\right)$

Wherein, $A=\frac{1}{1+a{P}_r};B=\frac{a{P}_r}{1+a{P}_r},a=\frac{k\&CenterDot;k_q}{k_L+k_C},$ Obvious A+B=1.If represent reference light intensity I with light intensity under 1 normal atmosphere _r, 1 normal atmosphere is represented reference pressure, then P _r=P ₁, I _r=I ₁

The eighties mid-term, a kind of pressure sensitive paint of Moscow State University and USSR (Union of Soviet Socialist Republics) central fluid power institute cooperation research and development distributes with detecting the coating measuring stress, from 10 ℃ in the room temperature range all to temperature-insensitive.But the response of lacquer is very slow, and the stepped change of pressure is reached two minutes inductive phase.Write down luminous situation with sensitive film, its measuring accuracy is lower, be about ± 10%.(A Deshiwa, " distribute " with detecting the coating measuring stress, applied mechanics and technology physics magazine, 1985 (4), pp.24-31) [M.M.Ardasheva., ＂ Measurement of Pressure Distribution byMeans of Indicator Coatings ＂, Zhurnal Prikladnoi Mekhaniki I TekhnicheskoiFiziki, No.4,1985, pp.24-31].Washington, DC university began to develop pressure sensitive paint in 1987, NASA and Boeing provide the subsidy of research.They have applied for European patent " carrying out surface pressure with the luminescent oxygen quencher measures " in 1991, the probe molecule of its announcement is octaethylporphyrin platinum (PtOEP), and probe molecule is dispersed in the organosilicon polymer, is used for wind-tunnel measurements after filming.With the ultraviolet source irradiation of 380nm, luminescent image is stored and data processing by the CCD record and by computer.After 45 minutes, luminous intensity reduces 40% to probe molecule octaethylporphyrin platinum (PtOEP) in the experimental light sources irradiation.(Gu Teman, Ka Fandi, Gai Leli, Deng, " carrying out surface pressure with the luminescent oxygen quencher measures ", European patent, publication number: 0 472 243 A2, open date of application: on February 26th, 1992) [M.P.Gouterman, J.L.Kavandi, J. (NMI) Gallery, et al, ＂ Surface Pressure Measurement byOxygen Quenching of Luminescence ＂, European Patent 0 472 243 A2,26,02,92].McDonnell-Douglas Corporation 1994 has reported that the time of response short, and with the gaging pressure sensitive paint of excited by visible light photoluminescence, the pressure sensitive paint halogen tungsten lamp is a light source, chooses 400～500nm excited by visible light, and emission light is about 600nm.This is a newer result, but does not announce that break appears in the structure of luminescence probe molecule and the composition of pressure sensitive paint and the school survey curve of pressure sensitive paint, shows that the response pressure variation of pressure sensitive paint is not the successive linear relationship.(Mo Lisi, Duonowan, " application of the responsive lacquer of pressure and temperature in high velocity air ", US Airways is learned and space aeronautics institute collection of thesis, 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 a word, present disclosed pressure sensitive paint probe molecule has only PtOEP.

Can find out that from above-mentioned bibliographical information the problem that pressure sensitive paint in use exists mainly is:

(1) with UV-light or short wavelength laser as excitation light source, be unfavorable for safety operation, and be easy to make probe molecule generation photodegradation;

(2) itself there is the photodegradation problem in the present probe molecule PtOEP that announces, and the result causes light intensity to weaken with the irradiation time growth, causes tonometric unstable;

(3) time of response slow, promptly the luminous pressure-dependent time of response of pressure sensitive paint is longer.This is because to be used to disperse the matrix of probe molecule at present be silicon resin, there is inductive effect in it, be that excited oxygen combines with chemical mode with organo-silicone rubber, oxygen concn is reduced, thereby cause the response of light is slowed down, in addition, when its ventilation property is relatively poor, probe molecule and oxygen molecule collision time postpone, and make response slack-off;

(4) because dibit quencher phenomenon often appears in the skewness of probe molecule in pressure sensitive paint matrix, causing the school survey curve of pressure sensitive paint not exclusively is the successive straight line, particularly when pressure becomes big, slope reduces, cause downward bias from situation, reduce pressure measurement sensitivity.

The objective of the invention is the problem at present pressure sensitive paint existence, the pressure sensitive paint of probe molecule is made in preparation at the diimine ruthenium complexe of the luminous good light stability of visible-range with excited by visible light.Use specific sol-gel technology of preparing that probe molecule is evenly spread to porousness SiO ₂In the matrix, preparation good permeability, the adjustable pressure sensitive paint system of high-content probe molecule and probe molecule content, make the oxygen quencher of this system effective, time of response is fast, and pressure measurement is highly sensitive, and can have good linear relationship in the pressure range of broad.

Pneumatic pressure-sensitive lacquer of the present invention comprises luminescence probe molecule and organosilicon polymer, and it is to be probe molecule with the diimine ruthenium complexe; The monomer of organosilicon polymer is the mixed solution of dimethyldiethoxysilane and γ-An Bingjisanyiyangjiguiwan, its mol ratio=0～8, or the mixed solution of dimethyldiethoxysilane and tetraethoxysilane, its mol ratio=0～8, or the mixed solution of dimethyldiethoxysilane, γ-An Bingjisanyiyangjiguiwan and tetraethoxysilane, wherein, mol ratio=0～8 of dimethyldiethoxysilane and (γ-An Bingjisanyiyangjiguiwan+tetraethoxysilane); At the transparent SiO that makes by the polycondensation of organoalkoxysilane cohydrolysis ₂In the colloidal sol, luminescence probe molecule add-on is 1 * 10 ^-4～5 * 10 ^-3Mol/l.The luminescence probe molecule of selecting is the diimine ruthenium complexe, specifically bipyridyl ruthenium [Ru (bpy) ₃] Cl ₂6H ₂O, phenanthroline ruthenium [Ru (phen) ₃] Cl ₂3H ₂O and 4,7-phenylbenzene phenanthroline ruthenium [Ru (ph ₂Phen) ₃] Cl ₂5H ₂Three kinds of probe molecules of O.These probe molecules can be visitd reported method by Watts and Kroes and be synthesized.Be about to hydrate ruthenium trichloride and 2,2 '-dipyridyl, or o-phenanthroline, or 4,7-phenylbenzene o-phenanthroline is respectively with 1: 6.6,1: 9.4,1: 5.4 mol ratio is dissolved in the dehydrated alcohol, in the presence of oxammonium hydrochloride,, can obtain bipyridyl ruthenium [Ru (bpy) respectively 120 ℃ of following stirring and refluxing of oil bath temperature 24～60 hours ₃] Cl ₂6H ₂O, phenanthroline ruthenium [Ru (phen) ₃] Cl ₂3H ₂O and 4,7-phenylbenzene phenanthroline ruthenium [Ru (ph ₂Phen) ₃] Cl ₂5H ₂The crude product of three kinds of probe molecules of O, through recrystallization, column chromatography can obtain required probe molecule.(Watts, Kroes is visitd, " ruthenium (II) and iridium (III) and 4; 4 '-phenylbenzene-2,2 '-dipyridyl, 4; 7-phenylbenzene-1; spectral response curve of the title complex that the 10-o-phenanthroline forms ", JACS, 1971,3184-3188) [R.J.Watts and G.A.Crosby, " SpectroscopicCharacterization of Comp] 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].

Sol-gel technique is adopted in the preparation of pressure sensitive paint, at purpose of the present invention, has designed a special preparation technology.This is the fine chemistry industry preparation process of the strict control of needs reaction conditions.

Preparation technology's flow process of pressure sensitive paint as shown in Figure 1.Earlier with dimethyldiethoxysilane (being designated as MEOS) and γ-An Bingjisanyiyangjiguiwan (trade(brand)name KH550) in molar ratio=0～8, or dimethyldiethoxysilane and tetraethoxysilane (being designated as TEOS) be in molar ratio=0～8, or dimethyldiethoxysilane and (γ-An Bingjisanyiyangjiguiwan+tetraethoxysilane) to be dissolved in after mixing in molar ratio=0～8 be in 1.0～8.0 times of dehydrated alcohols or acetone solvent of its mixed solution organoalkoxysilane total amount (mole number); Again catalyzer alkali or acid slowly are added drop-wise in the above-mentioned solution adjusting pH=5.2～11.0 after mixing with water.The amount of catalyzer is 2%～8% acid of 1%～5% alkali of organoalkoxysilane total amount (mole number) or organoalkoxysilane total amount (mole number), and the amount of water is 1.1～8.4 times of organoalkoxysilane total amount (mole number).Stirring is 1～12 hour under 15 ℃～35 ℃, need not to leave standstill directly to obtain the transparent SiO that viscosity is suitable for filming ₂Colloidal sol or leave standstill the aging transparent SiO that viscosity is suitable for filming that obtains after 12～48 hours ₂Colloidal sol; With any one probe molecule [Ru (bpy) ₃] Cl ₂6H ₂O, [Ru (phen) ₃] Cl ₂3H ₂O or [Ru (ph ₂Phen) ₃] Cl ₂5H ₂O adds the transparent SiO that the polycondensation of organoalkoxysilane cohydrolysis is made ₂In the colloidal sol, add-on is 1 * 10 ^-4～5 * 10 ^-3Mol/l.Behind ultra-sonic dispersion, be spun on the slide glass, again through drying at room temperature, obtain the pressure sensitive paint at the linerless end, or drip on the substrate of the different reflective that have white the pressure sensitive paint at the bottom of drying at room temperature promptly gets belt material.

In the preparation sol-gel process, raw material is formed and proportioning is crucial, and it is determining the distribution character of probe molecule and the ventilation property of matrix, and then influences the oxygen quencher effect of pressure sensitive paint and the linear relationship that curve is surveyed in the wind-tunnel school.When using TEOS as raw material, hydrolysis rate is very fast, forms highly cross-linked SiO with fast speeds ₂Polymkeric substance, resulting film are easy to cracking; In addition, the intermiscibility of this highly cross-linked collosol and gel and probe molecule is not good, often can observe the surface that probe molecule is enriched in rete, causes skewness.For this reason, we have introduced the siloxanes MEOS of two functional groups, in order to the control degree of crosslinking, have avoided the rimose generation.And owing to the MEOS hydrolytie polycondensation forms the superpolymer PDMS of line style skeleton, it has very high oxygen spread coefficient, helps O ₂See through, so help improving oxygen quencher effect.Replace or partly replace TEOS both to can be used as linking agent because of KH550, control film strength and tackiness with KH550; Can be used as solubilizing agent again, improve the solubleness of probe molecule in sol-gel, improve matrix middle probe molecule content and impel probe molecule uniform distribution in matrix, and do not assemble.MEOS/KH550=3～8th, preferred proportional range, the pressure sensitive paint oxygen quencher for preparing under this scope is respond well, the luminous intensity I in nitrogen _N2With luminous intensity I in the oxygen _O2Ratio I _N2/ I _O2In 7.7～12.4 scopes.The matrix preparation that introducing KH550 is used for pressure sensitive paint is a crucial part of the present invention.Owing to have γ-aminopropyl among the KH550, with the central metallic ions divalent ruthenium of probe molecule to a certain degree mating reaction is arranged, and KH550 is a polar molecule, it and polar probe molecule polar phase seemingly, so the double factor of polarity similar compatibility and coordination has strengthened the solubleness of probe molecule in sol-gel greatly.Good consistency fully is uniformly dispersed probe molecule between probe molecule and matrix in matrix, has avoided the dibit quencher, can make the school survey curve of pressure sensitive paint that good linear relationship is arranged.

In the process of preparation sol-gel, catalyzer plays regulates the pH value, controls reaction speed, thus influence the effect of sol-gel microtexture.When using base catalysis, sodium hydroxide is preferred catalyzer, the base catalysis amount for a long time, speed of response is too fast, the sol-gel outward appearance of formation is muddy and opaque.Have only control alkaline catalysts add-on to be about 1 of organoalkoxysilane total amount～3% o'clock, just can obtain water white sol-gel.It is pointed out that when using acid catalysis, hydrochloric acid is preferred catalyzer because KH550 itself is a strong basicity.If 4～8% hydrochloric acid catalysis with the organoalkoxysilane total amount then can be adjusted to reaction system pH=6.5～9.8, hydrolysis rate is moderate with this understanding, can obtain water white sol-gel, through the test of high magnification scanning electron microscope, it is good to prove with the matrix microhomogeneity of this condition preparation.

The control of water and alcoholic acid amount is to influence one of important factor of the microtexture of gel.When the water yield hour, hydrolysis rate is slow, is difficult to form gel.Yet, when the water yield is big, form highly cross-linked SiO easily rapidly ₂, be unfavorable for improving the ventilation property of gel.Through repeated screening, the add-on of selected water is that 3～7 times of organoalkoxysilane total amount suit.The alcoholic acid adding is the concentration for the diluting reaction thing, is beneficial to form the uniform film of microcosmic, can also prolong the solidified time simultaneously, is beneficial to carrying out smoothly of sprayed coating film technology.The suitable add-on of alcoholic acid is 3～8 times of organoalkoxysilane total amount.

The selection of substrate all has a significant effect to the photoluminescence and the oxygen quencher of pressure sensitive paint.Adopting granularity respectively is the neutral SiO of μ m magnitude ₂Or Al ₂O ₃, or granularity is the slightly acidic TiO of nm magnitude ₂Or smoke-like SiO ₂Coat and make substrate on the substrate, the pressure sensitive paint that makes is coated in respectively on the above-mentioned bottom, because the existence of substrate had both helped strengthening incident light exciting probe molecule, also help strengthening the luminous usable reflection of probe molecule, can strengthen oxygen quencher signal doubly.

The pressure sensitive paint that utilizes the inventive method to prepare has following characteristics:

(1) excited by visible light

Probe molecule [Ru (ph ₂Phen) ₃] Cl ₂5H ₂The absorption spectrum of O as shown in Figure 2, the visible region more than 360nm has stronger absorption, at 440nm and 460nm place two strong metal-ligand charge transfer (MLCT) characteristic absorption bands is arranged.In this spectral range, the selective excitation probe molecule can obtain higher luminous efficiency at long-wave band (600-640nm) visible region.

(2) light stability

Fig. 3 has provided probe molecule [Ru (ph ₂Phen) ₃] Cl ₂5H ₂O uses radiation of visible light continuously in air, the relative luminous intensity variation is not more than 0.5% in 2.5 hours, demonstrates good light stability.Promptly under this experiment condition, do not observe the oxidative degradation phenomenon of creating singlet oxygen by using, show that the probe molecule photochemical stability is good probe molecule.

(3) oxygen-permeable is good, and the time of response is short

Fig. 4 is an excitation wavelength when selecting 460nm and emission wavelength to be fixed on 610nm, and sample is carried out time scan (the instrument response time is 0.5s), the time dependent result of resulting luminous intensity respectively under logical nitrogen and logical oxygen.Shown in the figure, when in cell, feeding pure oxygen and purity nitrogen by turns, obtained good oxygen quencher effect with the flow velocity of 4.4ml/s.Wherein linerless end pressure sensitive paint $\left(a\right)\frac{I_{N_2}}{{\mathrm{<figure-callout\; id="2"\; label="I\; O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">I</figure-callout>}}_{O_{}}}=7.7$ The pressure sensitive paint that substrate is arranged $\left(b\right)\frac{I_{N_2}}{{\mathrm{<figure-callout\; id="2"\; label="I\; O"\; filenames="C9910722900211.png,C9910722900214.png"\; state="\{\{state\}\}">I</figure-callout>}}_{O_{}}}=12.4$ 。In this experiment, no matter be logical oxygen or logical nitrogen, luminous intensity variations all can reach balance in the instrument response time.The pressure sensitive paint sample that this Experiment Preparation is described is extremely short inductive phase.This is because use the made SiO of sol-gel method ₂Film is a kind of chemically inert porous matrix material, is characterized in that porosity is big, through characterize the microtexture of enamelled coating with scanning electron microscope, observes the SiO of enamelled coating ₂Matrix is the packed particle of the even size distribution of 10-20nm, piles up the micropore of formation thus also in same order of magnitude scope.Oxygen-permeable is good, helps oxygen molecule and is excited the diffusion collisional quenching of probe molecule, and the creating singlet oxygen by using of its generation is met matrix and inactivation, thereby has solved the problem that needs additional blasting time in the wind1 tunnel trial that brought inductive phase.When repeatedly logical repeatedly oxygen and logical nitrogen, luminous intensity variations shows good repeatability.Above result show the oxygen quenching process be one efficiently, dynamically, the reversible process.

Relatively (a) with (b) also as can be known because the existence of substrate, both helped strengthening incident light to the exciting of probe molecule, also help strengthening the luminous usable reflection of probe molecule, strengthened oxygen quencher signal doubly.

(4) microtexture is even, and calibration curve is good linear relationship

Use sol-gel technique among the present invention and effectively control probe molecule uniform distribution in matrix, carry out the wind tunnel simulation test with the pressure sensitive paint at the bottom of the belt material, survey curve shown in Fig. 5 c obtaining the continually varying school in the pressure range of broad, A=0.25 wherein, B=0.75.From figure as can be known, the prepared pressure sensitive paint of this work is at vacuum zone (1.01 * 10 ⁴-1.01 * 10 ⁵Pa) and low-pressure stage (1.01 * 10 ⁵-4.05 * 10 ⁵Pa) all show good linear relationship, relation conefficient γ=more than 0.99, and the slope unanimity, break does not promptly appear, meet single S tem-Volmer relation.This has simplified computation model greatly, has increased experimental precision.This lacquer sample probe molecule that shows us is evenly distributed, and good air permeability, is a kind of good pressure sensitive paint system.

(5) highly sensitive

Fig. 5 d is that curve is surveyed in the pressure sensitive paint school that provides in the European patent " luminous presser sensor composition ".(Mo Shaluofu, the storehouse is the people now, the Euro husband, Deng, " luminous presser sensor composition ", European patent, publication number: 0,558 771 A1, open date of application: 08,09,93) [V.Mosharov, M.Kuzmin, A.Orlov, et al. ＂ Luminescence PressureSensitive Composition ＂, European Patent, 0,558 771 A1,08,09,93] because reference light intensity I _rThe value difference, thus the numerical range difference of given ordinate zou, but still have comparability.More as can be known, the calibration curve slope of the pressure sensitive paint that the present invention is prepared is higher the wideer external pressure sensitive paint of pressure range internal ratio by c among Fig. 5 and d, and showing has higher susceptibility to stream pressure.

Description of drawings:

Fig. 1: Pneumatic pressure-sensitive lacquer preparation flow synoptic diagram of the present invention;

Fig. 2: probe molecule of the present invention [Ru (ph ₂Phen) ₃] Cl ₂5H ₂The electronic absorption spectroscopy of O in methyl alcohol;

Fig. 3: probe molecule of the present invention [Ru (ph ₂Phen) ₃] Cl ₂5H ₂The light stability experiment of O;

Fig. 4: the time resolution characteristics of the present invention's pressure sensitive paint oxygen quencher in silica membrane;

A. linerless end b. plus substrate

Fig. 5: curve ratio is surveyed in the wind tunnel simulation school of pressure sensitive paint of the present invention;

C. the pressure sensitive paint of present method preparation, excited by visible light, B=0.75

D. document European Patent, the pressure sensitive paint of 0,558 771 A1 preparation, ultraviolet excitation, B=0.67

Fig. 6: probe molecule of the present invention [Ru (ph ₂Phen) ₃] Cl ₂5H ₂The oxygen quencher characteristic of O in solid film;

E. example 1 gained 1 ^#Sol-gel

F. example 2 gained 2 ^#Sol-gel

Fig. 7: the gaging pressure profile of pressure sensitive paint jet flow bump convex surface of the present invention;

G. the black-and-white photograph in the pressure Measurements of Pressure-sensitive Paint

H. the pseudo-colours pressure profile of pressure Measurements of Pressure-sensitive Paint

Embodiment 1

With 1molKH550 and 8molMEOS (this moment MEOS: KH550=8) be dissolved in the 30mol dehydrated alcohol, stir slowly add 0.09mol sodium hydroxide and 28mol water down mixing back gained solution, the initial pH=9.0 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 3.3 times and 3.1 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 1.0% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 5 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 18.9mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 3 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 7 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=8.4.Use it for the wind tunnel simulation test, obtained result as Fig. 6 e.

Embodiment 2

With 1molKH550 and 3molMEOS (this moment MEOS: KH550=3) be dissolved in the 14mol dehydrated alcohol, stir slowly add 0.24mol hydrochloric acid and 12.6mol water down mixing back gained solution, the initial pH=7.8 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 3.5 times and 3.2 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 6.0% of an organoalkoxysilane total amount.15 ℃ are continued down to stir 5 hours, leave standstill then aging 12 hours, make the transparent SiO that can film ₂Sol-gel.

With 7.5mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 3ml, and this moment, concentration was 2 * 10 ^-3Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 9 days.Enamelled coating is transparent, and probe molecule is evenly distributed.

Carry out the time scan of emmission spectrum with the pressure sensitive paint at the linerless end of gained, record I _N2/ I _O2=7.7.Use it for oxygen quencher experiment, and make its Stem-Volmer correlogram, obtained result as Fig. 6 f.

Embodiment 3

With 2molKH550 and 2molMEOS (this moment MEOS: KH550=1) be dissolved in the 7mol dehydrated alcohol, stir slowly add 0.12mol sodium hydroxide and 14mol water down mixing back gained solution, the initial pH=9.2 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 1.8 times and 3.5 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 3.0% of an organoalkoxysilane total amount.35 ℃ are continued down to stir 3 hours, need not to leave standstill the aging transparent SiO that can film of promptly obtaining ₂Sol-gel.

With 12.6mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 1 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have Al ₂O ₃On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 7 days.

Carry out the time scan of emmission spectrum with the pressure sensitive paint at the bottom of the belt material, record I _N2/ I _O2=2.4.

Embodiment 4

With 4molTEOS (this moment MEOS: TEOS=0) be dissolved in the 20mol dehydrated alcohol, the mixing solutions that slowly adds 0.12mol hydrochloric acid and 24mol water under the violent stirring, the initial pH=6.0 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 5 times and 6 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 3.0% of an organoalkoxysilane total amount.30 ℃ are continued down to stir 2 hours, need not to leave standstill the aging transparent SiO that is suitable for filming of can obtaining ₂Sol-gel.

With 18.7mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 5 * 10 ^-3Mol/l after ultra-sonic dispersion is even, is spun on band TiO ₂On the sheet glass of bottom, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 3 days.Naked eyes can see that a spot of probe molecule is enriched in the top layer of lacquer, and the enamelled coating be full of cracks is more serious.

Carry out the time scan of emmission spectrum with the pressure sensitive paint at the bottom of the gained belt material, record I _N2/ I _O2=3.5.

Embodiment 5

With 10molMEOS, 0.5molKH550 and 1.5molTEOS (this moment MEOS: (KH550+TEOS)=5) is dissolved in the 12mol acetone, the mixing solutions that adds 0.24mol hydrochloric acid and 33mol water under the violent stirring, the initial pH=8.2 of conditioned reaction liquid, this moment the amount of solvent acetone and water amount be respectively 1 times of the organoalkoxysilane total amount and 2.g doubly, the amount of catalyzer hydrochloric acid is 2.0% of an organoalkoxysilane total amount.33 ℃ are descended stirring can obtain the transparent SiO that is suitable for filming after 1 hour ₂Sol-gel.

With 1.26mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 1 * 10 ^-4Mol/l after ultra-sonic dispersion is even, is spun on and is covered with smoke-like SiO ₂Sheet glass on, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 15 days.Enamelled coating is followed slight crackle.

The pressure sensitive paint at the linerless end of gained is carried out the test of luminescent spectrum respectively in nitrogen, oxygen and air atmosphere, record I _N2/ I _Air=1.1; I _N2/ I _O2=1.3.

Embodiment 6

With 4molKH550 (this moment MEOS: KH550=0) be dissolved in the 24mol acetone, the mixing solutions that adds 0.05mol sodium hydroxide and 19.2mol water under the violent stirring, the initial pH=9.4 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 6 times and 4.8 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 1.2% of an organoalkoxysilane total amount.20 ℃ are continued down to stir 5 hours, leaving standstill to obtain the transparent SiO that is suitable for filming in aging 12 hours ₂Sol-gel.

With 3.8mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 5 * 10 ^-4Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 4 days.The pressure sensitive paint at the linerless end of gained is carried out the test of luminescent spectrum respectively in nitrogen, oxygen and air atmosphere, record I _N2/ I _Air=1.8; I _N2/ I _O2=2.6.

Embodiment 7

With 3molKH550 and 6molMEOS (this moment MEOS: KH550=2) be dissolved in the 36mol acetone, stir slowly add 0.45mol hydrochloric acid and 63mol water down mixing back gained solution, the initial pH=8.8 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 4 times and 7 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 5.0% of an organoalkoxysilane total amount.18 ℃ are continued down to stir 12 hours, leave standstill then aging 20 hours, make the transparent SiO that can film ₂Sol-gel.

With 6.3mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 5 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have TiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 5 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=4.3.

Embodiment 8

With 2molTEOS and 8molMEOS (this moment MEOS: TEOS=4) be dissolved in the 60mol acetone, stir slowly add 0.37mol hydrochloric acid and 84mol water down mixing back gained solution, the initial pH=5.2 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 6 times and 8.4 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 3.7% of an organoalkoxysilane total amount.26 ℃ are continued down to stir 9 hours, leave standstill then aging 21 hours, make the transparent SiO that can film ₂Sol-gel.

With 7.5mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 6 * 10 ^-4Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 7 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=3.1.

Embodiment 9

With 6molMEOS, 0.5molKH550 and 0.5molTEOS (this moment MEOS: (KH550+TEOS)=6) is dissolved in the 35mol acetone, stir slowly add 0.49mol hydrochloric acid and 31mol water down mixing back gained solution, the initial pH=7.0 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 5 times and 4.4 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 7.0% of an organoalkoxysilane total amount.24 ℃ are continued down to stir 12 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 1.5mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 20ml, and this moment, concentration was 1 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 9 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=5.0.

Embodiment 10

With 1molKH550 and 7molMEOS (this moment MEOS: KH550=7) be dissolved in the 16mol acetone, stir slowly add 0.60mol hydrochloric acid and 17mol water down mixing back gained solution, the initial pH=7.4 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 2 times and 2.1 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 7.5% of an organoalkoxysilane total amount.28 ℃ are continued down to stir 11.5 hours, leave standstill then aging 20 hours, make the transparent SiO that can film ₂Sol-gel.

With 6.9mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 9 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have TiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 18 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=10.2.

Embodiment 11

With 4molKH550 and 6molMEOS (this moment MEOS: KH550=1.5) be dissolved in the 24mol acetone, stir slowly add 0.8mol hydrochloric acid and 24mol water down mixing back gained solution, the initial pH=9.8 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water all was 2.4 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 8.0% of an organoalkoxysilane total amount.30 ℃ are continued down to stir 5 hours, leave standstill then aging 30 hours, make the saturating SiO that can film ₂Bright sol-gel.

With 6.1mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 8 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have Al ₂O ₃On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 5 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=3.8.

Embodiment 12

With 2molTEOS and 5molMEOS (this moment MEOS: TEOS=2.5) be dissolved in the 56mol dehydrated alcohol, stir slowly add 0.28mol hydrochloric acid and 54mol water down mixing back gained solution, the initial pH=6.5 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 8.0 times and 7.7 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 4.0% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 10 hours, leave standstill then aging 48 hours, make the transparent SiO that can film ₂Sol-gel.

With 7.5mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 1 * 10 ^-3Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 8 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=2.4.

Embodiment 13

With 7molMEOS, 1molKH550 and 1molTEOS (this moment MEOS: (KH550+TEOS)=3.5) are dissolved in the 21mol dehydrated alcohol, stir slowly add 0.22mol hydrochloric acid and 42mol water down mixing back gained solution, the initial pH=7.9 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 2.3 times and 4.7 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 2.5% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 10.5 hours, leave standstill then aging 40 hours, make the transparent SiO that can film ₂Sol-gel.

With 4.5mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 6 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 3 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=4.2.

Embodiment 14

With 2molKH550 and 9molMEOS (this moment MEOS: KH550=4.5) be dissolved in the 44mol dehydrated alcohol, stir slowly add 0.72mol hydrochloric acid and 72mol water down mixing back gained solution, the initial pH=8.3 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 4 times and 6.5 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 6.5% of an organoalkoxysilane total amount.20 ℃ are continued down to stir 11.5 hours, leave standstill then aging 36 hours, make the transparent SiO that can film ₂Sol-gel.

With 6.0mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 8 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have TiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 10 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=10.6.

Embodiment 15

With 11molMEOS, 0.5molKH550 and 1.5molTEOS (this moment MEOS: (KH550+TEOS)=5.5) is dissolved in the 62mol acetone, stir slowly add 0.72mol hydrochloric acid and 31mol water down mixing back gained solution, the initial pH=6.7 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 4.8 times and 2.4 times of organoalkoxysilane total amount, and the amount of catalyzer hydrochloric acid is 5.5% of an organoalkoxysilane total amount.19 ℃ are continued down to stir 11 hours, leave standstill then aging 12 hours, make the transparent SiO that can film ₂Sol-gel.

With 2.5mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 2 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have Al ₂O ₃On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 12 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=4.8.

Embodiment 16

With 13molMEOS, 1molKH550 and 1molTEOS (this moment MEOS: (KH550+TEOS)=6.5) are dissolved in the 30mol dehydrated alcohol, stir slowly add 0.75mol sodium hydroxide and 16.5mol water down mixing back gained solution, the initial pH=11.0 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 2 times and 1.1 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 5.0% of an organoalkoxysilane total amount.26 ℃ are continued down to stir 4 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 8.8mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 7 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 17 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=5.4.

Embodiment 17

With 2molKH550 and 15molMEOS (this moment MEOS: KH550=7.5) be dissolved in the 51mol dehydrated alcohol, stir slowly add 0.34mol sodium hydroxide and 90mol water down mixing back gained solution, the initial pH=10.2 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 3 times and 5.3 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 2.0% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 7 hours, leave standstill then aging 12 hours, make the transparent SiO that can film ₂Sol-gel.

With 5.0mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 4 * 10 ^-4Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 16 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=8.2

Embodiment 18

With 2molKH550 and 10molMEOS (this moment MEOS: KH550=5) be dissolved in the 54mol acetone, stir slowly add 0.31mol sodium hydroxide and 78mol water down mixing back gained solution, the initial pH=9.7 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 4.5 times and 6.5 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 2.6% of an organoalkoxysilane total amount.35 ℃ are continued down to stir 5 hours, leave standstill then aging 48 hours, make the transparent SiO that can film ₂Sol-gel.

With 9.7mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 1.3 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have Al ₂O ₃On the soft substrate plate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 5 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=12.4.And use it for the pressure sensitive paint plate of air jet bump convex surface and carry out pressure survey, on very little area, obtained complicated pressure distribution structure.The black-and-white photograph of using the taken pressure sensitive paint of CCD in the pressure measurement is shown in Fig. 7 (g).Can find out that from figure each position bright-dark degree of lacquer painting is different, show light intensity difference everywhere, just the grey scale difference.This has shown that suffered stream pressure is different everywhere, and pressure is big more, and then lacquer is dark more, and vice versa.Nozzle is attached has as can be seen from Figure seen that is a trumpet-shaped shadow, and this shows that the one's respective area pressure is bigger.We have also carried out the pseudo-colours processing to black-and-white photograph, and different grey scales is represented with different colours respectively, have obtained more intuitive well-bedded pseudo-colours pressure profile shown in Fig. 7 (h).Along the direction of nozzle, along with nozzle between distance different, pressure is obviously different everywhere, shows abundant pressure distribution level.Illustrate that pressure sensitive paint can well express the difference of the relative pressure everywhere of test surfaces, have very high spatial resolution.

Embodiment 19

With 1molTEOS and 6molMEOS (this moment MEOS: TEOS=6) be dissolved in the 14mol acetone, stir slowly add 0.21mol sodium hydroxide and 16mol water down mixing back gained solution, the initial pH=7.6 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 2 times and 2.3 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 3.0% of an organoalkoxysilane total amount.23 ℃ are continued down to stir 12 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 15.0mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 2 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 14 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=6.2.

Embodiment 20

With 2molKH550 and 8molMEOS (this moment MEOS: KH550=4) be dissolved in the 37mol dehydrated alcohol, stir slowly add 0.45mol sodium hydroxide and 66mol water down mixing back gained solution, the initial pH=10.6 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 3.7 times and 6.6 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 4.5% of an organoalkoxysilane total amount.20 ℃ are continued down to stir 8 hours, leave standstill then aging 36 hours, make the transparent SiO that can film ₂Sol-gel.

With 11.2mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 3 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have TiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 11 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=9.2.

Embodiment 21

With 14molMEOS, 0.5molKH550 and 1.5molTEOS (this moment MEOS: (KH550+TEOS)=7.0) is dissolved in the 48mol dehydrated alcohol, stir slowly add 0.4mol sodium hydroxide and 71mol water down mixing back gained solution, the initial pH=9.9 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 3.0 times and 4.4 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 2.5% of an organoalkoxysilane total amount.20 ℃ are continued down to stir 10 hours, leave standstill then aging 30 hours, make the transparent SiO that can film ₂Sol-gel.

With 7.7mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 1 * 10 ^-3Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 15 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=6.O.

Embodiment 22

With 2molTEOS and 16molMEOS (this moment MEOS: TEOS=8) be dissolved in the 47mol dehydrated alcohol, stir slowly add 0.63mol sodium hydroxide and 40mol water down mixing back gained solution, the initial pH=7.8 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 2.6 times and 2.2 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 3.7% of an organoalkoxysilane total amount.15 ℃ are continued down to stir 12 hours, leave standstill then aging 48 hours, make the transparent SiO that can film ₂Sol-gel.

With 19.2mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 5 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 18 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=6.7.

Embodiment 23

With 8molMEOS, 1molKH550 and 1molTEOS (this moment MEOS: (KH550+TEOS)=4.0) are dissolved in the 50mol acetone, stir slowly add 0.42mol sodium hydroxide and 46mol water down mixing back gained solution, the initial pH=10.4 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 5.0 times and 4.6 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 4.2% of an organoalkoxysilane total amount.19 ℃ are continued down to stir 10 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 11.5mg[Ru (phen) ₃] Cl ₂3H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 3 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have Al ₂O ₃On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 10 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=4.5.

Embodiment 24

With 8molMEOS, 4molKH550 and 4molTEOS (this moment MEOS: (KH550+TEOS)=1.O) be dissolved in the 112mol dehydrated alcohol, stir slowly add 0.3mol sodium hydroxide and 88mol water down mixing back gained solution, the initial pH=10.8 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 7 times and 5.5 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 1.9% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 7 hours, leave standstill then aging 15 hours, make the transparent SiO that can film ₂Sol-gel.

With 11.3mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 9 * 10 ^-4Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have smoke-like SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 7 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=1.9.

Embodiment 25

With 4molTEOS and 6molMEOS (this moment MEOS: TEOS=1.5) be dissolved in the 42mol dehydrated alcohol, stir slowly add 0.16mol sodium hydroxide and 56mol water down mixing back gained solution, the initial pH=7.5 of conditioned reaction liquid, this moment, the amount and the amount of water of solvent dehydrated alcohol were respectively 4.2 times and 5.6 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 1.6% of an organoalkoxysilane total amount.25 ℃ are continued down to stir 10 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

With 18.7mg[Ru (bpy) ₃] Cl ₂6H ₂O is dissolved in the above-mentioned sol-gel of 5ml, and this moment, concentration was 5 * 10 ^-3Mol/l after ultra-sonic dispersion is even, is spun on the sheet glass, and drying at room temperature promptly gets the pressure sensitive paint at the linerless end after 5 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=2.5.

Embodiment 26

With 2molTEOS and 6molMEOS (this moment MEOS: TEOS=3) be dissolved in the 56mol acetone, stir slowly add 0.38mol sodium hydroxide and 54mol water down mixing back gained solution, the initial pH=8.1 of conditioned reaction liquid, this moment, the amount of the amount of solvent acetone and water was respectively 7.0 times and 6.8 times of organoalkoxysilane total amount, and the amount of catalyzer sodium hydroxide is 4.8% of an organoalkoxysilane total amount.35 ℃ are continued down to stir 6 hours, leave standstill then aging 24 hours, make the transparent SiO that can film ₂Sol-gel.

19.2mg[Ru (ph ₂Phen) ₃] Cl ₂5H ₂O is dissolved in the above-mentioned sol-gel of 10ml, and this moment, concentration was 2.5 * 10 ^-3Mol/l, ultra-sonic dispersion evenly after, be sprayed at and have SiO ₂On the substrate of reflective bottom layer, drying at room temperature promptly gets the pressure sensitive paint at the bottom of the belt material after 8 days.

The pressure sensitive paint of above-mentioned gained is carried out the time scan of emmission spectrum, record I _N2/ I _O2=3.7.

Claims (9)

1. a Pneumatic pressure-sensitive lacquer comprises luminescence probe molecule and organosilicon polymer, it is characterized in that with the diimine ruthenium complexe be probe molecule; The monomer of organosilicon polymer is the mixed solution of dimethyldiethoxysilane and γ-An Bingjisanyiyangjiguiwan, its mol ratio=0～8, or the mixed solution of dimethyldiethoxysilane and tetraethoxysilane, its mol ratio=0～8, or the mixed solution of dimethyldiethoxysilane, γ-An Bingjisanyiyangjiguiwan and tetraethoxysilane, wherein, mol ratio=0～8 of dimethyldiethoxysilane and (γ-An Bingjisanyiyangjiguiwan+tetraethoxysilane); At the transparent SiO that makes by the polycondensation of organoalkoxysilane cohydrolysis ₂In the colloidal sol, luminescence probe molecule add-on is 1 * 10 ¹～5 * 10 ³Mol/l.

2. a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 1 is characterized in that described diimine ruthenium complexe is bipyridyl ruthenium, phenanthroline ruthenium and 4,7-phenylbenzene phenanthroline ruthenium.

3. a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 1 is characterized in that mol ratio=3～8 of described dimethyldiethoxysilane and γ-An Bingjisanyiyangjiguiwan.

4. the method for making of a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 1, it is characterized in that earlier dimethyldiethoxysilane and γ-An Bingjisanyiyangjiguiwan in molar ratio=0～8, or dimethyldiethoxysilane and tetraethoxysilane be in molar ratio=0～8, or dimethyldiethoxysilane and (γ-An Bingjisanyiyangjiguiwan+tetraethoxysilane) to be dissolved in after mixing in molar ratio=0～8 be in 1.0～8.0 times of dehydrated alcohols or acetone solvent of its mixed solution organoalkoxysilane total amount; Again catalyzer alkali or acid slowly are added drop-wise in the above-mentioned solution after mixing with water, regulate pH=5.2～11.0,, need not to leave standstill and directly to obtain the transparent SiO that viscosity is suitable for filming 15 ℃～35 ℃ stirrings 1～12 hour down ₂Colloidal sol, or leave standstill the aging transparent SiO that viscosity is suitable for filming that obtains after 12～48 hours ₂Colloidal sol; The luminescence probe molecule is added the transparent SiO that the polycondensation of organoalkoxysilane cohydrolysis is made ₂In the colloidal sol, additional proportion is 1 * 10 ^-4～5 * 10 ^-3Mol/l; Behind ultra-sonic dispersion, be spun on the slide glass, again through drying at room temperature, obtain the pressure sensitive paint at the linerless end, or drip on the substrate of the different reflective that have white the pressure sensitive paint at the bottom of drying at room temperature promptly gets belt material.

5. the method for making of a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 4, the add-on that it is characterized in that described catalyzer are 1%～5% alkali of organoalkoxysilane total amount, or 2%～8% acid of organoalkoxysilane total amount.

6. as the method for making of claim 4 or 5 described a kind of Pneumatic pressure-sensitive lacquers, it is characterized in that described alkali is sodium hydroxide, acid is hydrochloric acid.

7. the method for making of a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 4, the add-on that it is characterized in that described water is 1.1～8.4 times of organoalkoxysilane total amount.

8. the method for making of a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 4 is characterized in that described luminescence probe molecule is bipyridyl ruthenium, phenanthroline ruthenium or 4,7-phenylbenzene phenanthroline ruthenium.

9. the method for making of a kind of Pneumatic pressure-sensitive lacquer as claimed in claim 4 is characterized in that mol ratio=3～8 of described dimethyldiethoxysilane and γ-An Bingjisanyiyangjiguiwan.

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