CN102745910B - Preparation method of aluminum-polysilsesquioxane (AL2O3-POSS) hybrid coating on surface of quartz fiber - Google Patents

Preparation method of aluminum-polysilsesquioxane (AL2O3-POSS) hybrid coating on surface of quartz fiber Download PDF

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CN102745910B
CN102745910B CN201210264565.1A CN201210264565A CN102745910B CN 102745910 B CN102745910 B CN 102745910B CN 201210264565 A CN201210264565 A CN 201210264565A CN 102745910 B CN102745910 B CN 102745910B
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preparation
silica fiber
poss
hybrid coating
mol ratio
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CN102745910A (en
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张兴文
张颖
卢艳
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention relates to a preparation method of a hybrid coating, in particular to the preparation method of an AL2O3-POSS hybrid coating on the surface of a quartz fiber to solve the technical problem that the existing wave-transmitting material is prone to brittle fracture. The preparation method includes preparing an AL2O3 sol, preparing a POSS sol, preparing a composite sol, placing a quartz fiber after preprocessing of sulfuric acid in the composite sol for impregnation, and subjecting the quartz fiber to drying and heat treatment to obtain the coating. The AL2O3-POSS hybrid coating has good adhesion with the quartz fiber, an even protective coating is formed on the surface of the fiber, a hydroxyl condensation reaction between the quartz fiber and a phosphate matrix is isolated effectively, the corrosive action of the phosphate matrix on the quartz fiber under a high temperature condition is reduced, and the mechanical property of quartz fiber reinforced composites of phosphate matrixes is improved.

Description

Silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating
Technical field
The present invention relates to a kind of preparation method of hybrid coating.
Background technology
Space flight electromagnetic wave transparent material refers to the material that wavelength is greater than to 70% in 1～1000nm, frequency in the electromagnetic transmitance of 0.3～300GHz scope, belong to photoelectromagnetism and structure function matrix material category, for structure-solar heat protection-wave transparent integrated function material, can be used for making radome, in the space systems such as launch vehicle, airship, guided missile and retrievable satellite, be widely used.Radar seeker radome is tactical missile and a vitals with other aerospacecraft; should there is the several functions such as water conservancy diversion, solar heat protection, wave transparent, carrying, mainly protect the systems such as the communication of aerospacecraft under severe environmental conditions, remote measurement, guidance, ignition normally to work.When hypersonic missile flies in dense atmosphere, air is subject to strong compression and violent rubbing effect, produces " Aerodynamic Heating " phenomenon.Along with the increase of guided missile Mach number, Aerodynamic Heating is very serious.Therefore high temperature wave-transparent material becomes study hotspot.
High temperature wave-transparent material will have following characteristics: have lower specific inductivity and dielectric loss, and dielectric properties do not produce significant variation with the change of temperature, frequency; Simultaneously, aloft radome also will bear the mechanical stress being caused by aerodynamic force and vertical or horizontal acceleration, require radome material when meeting its resistance toheat and dielectric properties requirement, must there is enough mechanical properties and the ability of anti-weathering.
What be applied at present space flight electromagnetic wave transparent material field is mainly siliceous fiber reinforcement phosphoric acid salt.Silica fiber is a kind of SiO 2the glass fibre of content high (> 99.95%), excellent performance, be highly suitable for the fortifying fibre as the general radome of tactical missile, but because phosphate matrix has strongly-acid, in fiber reinforcement phosphate composite material, will the fiber that play enhancement be had to very strong corrodibility.In exist-OH of fiber surface and phosphoric acid salt will there is harmful surface reaction in residue-OH, make matrix material produce too high interface binding power, when material is subject to mechanical shock, matrix material produces brittle rupture, the highly malleablized effect of fiber is not brought into play, thereby has reduced the mechanical property of matrix material.Therefore, adopt the method for fiber surface coating protective film to prevent the acid attack of resin matrix to silica fiber, guarantee that the over-all properties of material has important Research Significance.
Summary of the invention
The present invention, in order to solve the technical problem of the easy brittle rupture of existing electromagnetic wave transparent material, provides a kind of silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating.
Silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2o 3colloidal sol: be 20～40 according to ethanol and aluminum ions mol ratio: 1, sequestrant and aluminum ions mol ratio are that 0.3～0.4: 1 ratio joins aluminic acid butyl ester, ethanol and methyl aceto acetate in container, in 80 ℃ of water-baths reflux stir to clarify transparent after, the ratio that is 20～40: 1 according to ethanol and aluminium secondary butylate mol ratio adds aluminium secondary butylate, stir transparent after, the ratio that is 1: 0.8 according to aluminium secondary butylate and deionized water mol ratio adds deionized water, stir 6h, obtain Al 2o 3colloidal sol;
Two, preparation POSS colloidal sol: the ratio that is 1: 3: 0.005 according to mol ratio by vinyltrimethoxy silane, ethanol, formic acid is mixed, and confined reaction 10d in 35 ℃ of water-baths, makes POSS colloidal sol;
Three, prepare complex sol: by Al 2o 3colloidal sol mixes by the mass ratio of 1: 1 with POSS colloidal sol, in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, reacts 5 days, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, make complex sol;
Four, by being put in complex sol through the silica fiber of sulfur acid pretreatment through pretreated silica fiber, in vacuum tightness, be 0.5 × 10 5pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz, it is neutral with deionized water, being washed till washing lotion, then with the heat-up rate of 5 ℃/min, from room temperature, rise to 80 ℃, keep 80 ℃ of 0.5h, with 10 ℃/min, be warming up to 120 ℃ again, keep 120 ℃ of 1h, then through the thermal treatment of 550～650 ℃, must apply Al 2o 3the silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in step 4 is as follows: silica fiber is soaked in mass concentration 30% dilution heat of sulfuric acid to 2 hours under the condition of 98 ℃.
First preparation method of the present invention prepares respectively Al by sol-gel method 2o 3colloidal sol and POSS colloidal sol, then mix aging preparation Al 2o 3-POSS complex sol, then at silica fiber surface-coated Al 2o 3-POSS hybrid coating, makes and is coated with Al 2o 3the silica fiber of-POSS hybrid coating; hybrid coating and silica fiber adhesivity are good; at fiber surface, formed uniform protective layer; effectively isolated the hydroxyl condensation reaction of silica fiber and phosphate matrix; reduce the corrosive nature of phosphate matrix to silica fiber under hot conditions, improved the mechanical property of silica fiber enhancing phosphate matrix composite.
Accompanying drawing explanation
Fig. 1 is the XPS spectrum figure on different pretreatments method silica fiber surface;
Fig. 2 is the infrared absorption spectrum spectrogram of complex sol in experiment one;
Fig. 3 applies Al 2o 3the SEM figure on the silica fiber surface of rete;
Fig. 4 is the SEM figure that applies the silica fiber surface of POSS rete;
Fig. 5 applies Al 2o 3the SEM figure on the silica fiber surface of-POSS hybrid coating.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2o 3colloidal sol: be 20～40 according to ethanol and aluminum ions mol ratio: 1, sequestrant and aluminum ions mol ratio are that 0.3～0.4: 1 ratio joins aluminic acid butyl ester, ethanol and methyl aceto acetate in container, in 80 ℃ of water-baths reflux stir to clarify transparent after, the ratio that is 20～40: 1 according to ethanol and aluminium secondary butylate mol ratio adds aluminium secondary butylate, stir transparent after, the ratio that is 1: 0.8 according to aluminium secondary butylate and deionized water mol ratio adds deionized water, stir 6h, obtain Al 2o 3colloidal sol;
Two, preparation POSS colloidal sol: the ratio that is 1: 3: 0.005 according to mol ratio by vinyltrimethoxy silane, ethanol, formic acid is mixed, and confined reaction 10d in 35 ℃ of water-baths, makes POSS colloidal sol;
Three, prepare complex sol: by Al 2o 3colloidal sol mixes by the mass ratio of 1: 1 with POSS colloidal sol, in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, reacts 5 days, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, make complex sol;
Four, by being put in complex sol through the silica fiber of sulfur acid pretreatment through pretreated silica fiber, in vacuum tightness, be 0.5 × 10 5pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz, it is neutral with deionized water, being washed till washing lotion, then with the heat-up rate of 5 ℃/min, from room temperature, rise to 80 ℃, keep 80 ℃ of 0.5h, with 10 ℃/min, be warming up to 120 ℃ again, keep 120 ℃ of 1h, then through the thermal treatment of 550～650 ℃, must apply Al 2o 3the silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in step 4 is as follows: silica fiber is soaked in mass concentration 30% dilution heat of sulfuric acid to 2 hours under the condition of 98 ℃.
Embodiment two: what present embodiment was different from embodiment one is that ethanol described in step 1 and aluminum ions mol ratio are 22～38: 1.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one is that ethanol described in step 1 and aluminum ions mol ratio are 25～35: 1.Other is identical with embodiment one.
Embodiment four: what present embodiment was different from embodiment one is that ethanol described in step 1 and aluminum ions mol ratio are 30: 1.Other is identical with embodiment one.
Embodiment five: what present embodiment was different from embodiment one is that sequestrant described in step 1 and aluminum ions mol ratio are 0.31～0.38: 1.Other is identical with embodiment one.
Embodiment six: what present embodiment was different from embodiment one is that sequestrant described in step 1 and aluminum ions mol ratio are 0.35: 1.Other is identical with embodiment one.
Embodiment seven: what present embodiment was different from embodiment one is that ethanol described in step 1 and aluminium secondary butylate mol ratio are 30: 1.Other is identical with embodiment one.
Embodiment eight: present embodiment is different from embodiment one is described in step 1 to be 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 0.8～2.8h under the condition of 200Hz.Other is identical with embodiment one.
Embodiment nine: present embodiment is different from embodiment one is described in step 1 to be 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 1～2.5h under the condition of 200Hz.Other is identical with embodiment one.
Embodiment ten: present embodiment is different from embodiment one is described in step 1 to be 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 2h under the condition of 200Hz.Other is identical with embodiment one.
Adopt following experimental verification effect of the present invention:
Experiment one:
Silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2o 3colloidal sol: water bath with thermostatic control is warming up to 80 ℃, in there-necked flask, add 138g ethanol, 3.9g methyl aceto acetate, after stirring, add 24.632g aluminium secondary butylate, heated and stirred is to clear shape (make the abundant complexing of central aluminum atom too fast with precaution of hydrolysis), dropwise add again 1.44g deionized water, return stirring 6 hours under 80 ℃ of temperature constant states, the Al of acquisition transparent and stable 2o 3colloidal sol;
Two, preparation POSS colloidal sol: 45.67g vinyltrimethoxy silane and 45.10g ethanol are joined in beaker, the formic acid 15.43g that is 0.1mol/L by concentration carries out catalysis, utilizes preservative film that beaker is sealed, and puts beaker is entered in water-bath, 35 ℃ of isothermal reactions 10 days, make POSS colloidal sol;
Three, prepare complex sol: by Al 2o 3colloidal sol mixes by the mass ratio of 1: 1 with POSS colloidal sol, in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, reacts 5 days, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, make complex sol;
Four, by being put in complex sol through the silica fiber of sulfur acid pretreatment through pretreated silica fiber, in vacuum tightness, be 0.5 × 10 5pa or ultrasonic frequency are to flood 2h under the condition of 200Hz, and it is neutral with deionized water, being washed till washing lotion, then with the heat-up rate of 5 ℃/min, from room temperature, rises to 80 ℃, keep 80 ℃ of 0.5h, then be warming up to 120 ℃ with 10 ℃/min, keep 120 ℃ of 1h, through the thermal treatment of 550 ℃, must apply Al again 2o 3the silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in step 4 is as follows: silica fiber is soaked in mass concentration 30% dilution heat of sulfuric acid to 2 hours under the condition of 98 ℃.

Claims (10)

1. silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating, is characterized in that silica fiber surface A l 2o 3the preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2o 3colloidal sol: be that 20～40 ﹕ 1, sequestrant and aluminum ions mol ratio are that the ratio of 0.3～0.4 ﹕ 1 joins aluminic acid butyl ester, ethanol and methyl aceto acetate in container according to ethanol and aluminum ions mol ratio, in 80 ℃ of water-baths reflux stir to clarify transparent after, the ratio that is 20～40 ﹕ 1 according to ethanol and aluminium secondary butylate mol ratio adds aluminium secondary butylate, stir transparent after, the ratio that is 1:0.8 according to aluminium secondary butylate and deionized water mol ratio adds deionized water, stir 6h, obtain Al 2o 3colloidal sol;
Two, preparation POSS colloidal sol: the ratio that is 1 ﹕ 3 ﹕ 0.005 according to mol ratio by vinyltrimethoxy silane, ethanol, formic acid is mixed, and confined reaction 10d in 35 ℃ of water-baths, makes POSS colloidal sol;
Three, prepare complex sol: by Al 2o 3colloidal sol mixes by the mass ratio of 1:1 with POSS colloidal sol, in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, reacts 5 days, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, make complex sol;
Four, the silica fiber through sulfur acid pretreatment being put in complex sol, is 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz, it is neutral with deionized water, being washed till washing lotion, then with the heat-up rate of 5 ℃/min, from room temperature, rise to 80 ℃, keep 80 ℃ of 0.5h, with 10 ℃/min, be warming up to 120 ℃ again, keep 120 ℃ of 1h, then through the thermal treatment of 550～650 ℃, must apply Al 2o 3the silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in step 4 is as follows: silica fiber is soaked in mass concentration 30% dilution heat of sulfuric acid to 2 hours under the condition of 98 ℃.
2. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that ethanol described in step 1 and aluminum ions mol ratio are 22～38 ﹕ 1.
3. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that ethanol described in step 1 and aluminum ions mol ratio are 25～35 ﹕ 1.
4. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that ethanol described in step 1 and aluminum ions mol ratio are 30 ﹕ 1.
5. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that sequestrant described in step 1 and aluminum ions mol ratio are 0.31～0.38 ﹕ 1.
6. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that sequestrant described in step 1 and aluminum ions mol ratio are 0.35 ﹕ 1.
7. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that ethanol described in step 1 and aluminium secondary butylate mol ratio are 30 ﹕ 1.
8. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that described in step 4 being 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 0.8～2.8h under the condition of 200Hz.
9. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that described in step 4 being 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 1～2.5h under the condition of 200Hz.
10. silica fiber surface A l according to claim 1 2o 3the preparation method of-POSS hybrid coating, is characterized in that described in step 4 being 0.5 × 10 in vacuum tightness 5pa or ultrasonic frequency are to flood 2h under the condition of 200Hz.
CN201210264565.1A 2012-07-27 2012-07-27 Preparation method of aluminum-polysilsesquioxane (AL2O3-POSS) hybrid coating on surface of quartz fiber Expired - Fee Related CN102745910B (en)

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