CN102745910A - 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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CN102745910A
CN102745910A CN2012102645651A CN201210264565A CN102745910A CN 102745910 A CN102745910 A CN 102745910A CN 2012102645651 A CN2012102645651 A CN 2012102645651A CN 201210264565 A CN201210264565 A CN 201210264565A CN 102745910 A CN102745910 A CN 102745910A
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preparation
silica fiber
poss
hybrid coating
mol ratio
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CN102745910B (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 surfaces 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
The space flight electromagnetic wave transparent material is meant wavelength at 1～1000nm, frequency in the electromagnetic transmitance of 0.3～300GHz scope greater than 70% material; Belong to photo-electro-magnetic and structure function matrix material category; Be structure-solar heat protection-pass through integrated functional materials of ripple; Can be used for making radome, in space systems such as launch vehicle, airship, guided missile and retrievable satellite, be widely used.The radar seeker radome be tactical missile and with a vitals of other aerospacecraft; Should have water conservancy diversion, solar heat protection, pass through multiple functions such as ripple, carrying, mainly protect the systems such as the communication of aerospacecraft under severe environmental conditions, remote measurement, guidance, ignition can works better.When hypersonic missile flew in dense atmosphere, air received intensive compression and violent rubbing effect, produces " pneumatic heating " phenomenon.Along with the increase of guided missile Mach number, pneumatic heating is very serious.Therefore high temperature wave-transparent material becomes the research focus.
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 that is caused by aerodynamic force and vertical or horizontal acceleration stresses; Require radome material when satisfying, must have the enough mechanical properties and the ability of anti-weathering its resistance toheat and dielectric properties requirement.
What be applied in space flight electromagnetic wave transparent material field at present mainly is siliceous fiber reinforcement phosphoric acid salt.Silica fiber is a kind of SiO 2The spun glass of content high (＞99.95%); Excellent performance is highly suitable for the fortifying fibre as the general radome of tactical missile, but because the phosphoric acid salt matrix has strongly-acid; In the fiber reinforcement phosphate composite material, will have very strong corrodibility to the fiber that plays enhancement.Fiber surface exists-OH and phosphoric acid salt in residue-OH surface reaction will take place to be harmful to; Make matrix material produce too high interface binding power; When material receives mechanical shock; Matrix material produces brittle rupture, and 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, guarantee that the over-all properties of material has important Research Significance silica fiber.
Summary of the invention
The present invention provides a kind of silica fiber surfaces A l in order to solve the technical problem of the existing easy brittle rupture of electromagnetic wave transparent material 2O 3The preparation method of-POSS hybrid coating.
Silica fiber surfaces A l 2O 3The preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2O 3Colloidal sol: according to ethanol and aluminum ions mol ratio is 20～40: 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 the container; In 80 ℃ of water-baths reflux stir to clarify transparent after; According to ethanol and ASBD mol ratio is that 20～40: 1 ratio adds ASBD; Stir transparent after; According to ASBD and deionized water mol ratio is that 1: 0.8 ratio adds deionized water, stirs 6h, obtains Al 2O 3Colloidal sol;
Two, preparation POSS colloidal sol: is 1: 3: 0.005 mixed with vinyltrimethoxy silane, ethanol, formic acid according to mol ratio, and confined reaction 10d in 35 ℃ of water-baths makes POSS colloidal sol;
Three, preparation complex sol: with Al 2O 3Colloidal sol mixes with the mass ratio of POSS colloidal sol by 1: 1, and reaction is 5 days in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, makes complex sol;
Four, will pass through pretreated silica fiber and be put in the complex sol through the pretreated silica fiber of persulfuric acid, be 0.5 * 10 in vacuum tightness 5Pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz; Use deionized water to be washed till washing lotion and be neutrality, the heat-up rate with 5 ℃/min rises to 80 ℃ from room temperature then, keeps 80 ℃ of 0.5h; Be warming up to 120 ℃ with 10 ℃/min again; Keep 120 ℃ of 1h,, promptly get and apply Al again through 550～650 ℃ thermal treatment 2O 3The silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in the step 4 is following: under 98 ℃ condition, silica fiber was soaked in mass concentration 30% dilution heat of sulfuric acid 2 hours.
Preparing method of the present invention at first prepares Al respectively with sol-gel method 2O 3Colloidal sol and POSS colloidal sol mix aging preparation Al then 2O 3-POSS complex sol is again 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; Formed uniform protection layer at fiber surface; Effective isolation the hydroxyl condensation reaction of silica fiber and phosphoric acid salt matrix, reduced under the hot conditions phosphoric acid salt matrix to the corrosive nature of silica fiber, improved the mechanical property that silica fiber strengthens phosphate matrix composite.
Description of drawings
Fig. 1 is the XPS spectrum figure on different pretreatment process silica fibers surface;
Fig. 2 is the infrared absorption spectrum spectrogram of complex sol in the 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 scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment silica fiber surfaces A l 2O 3The preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2O 3Colloidal sol: according to ethanol and aluminum ions mol ratio is 20～40: 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 the container; In 80 ℃ of water-baths reflux stir to clarify transparent after; According to ethanol and ASBD mol ratio is that 20～40: 1 ratio adds ASBD; Stir transparent after; According to ASBD and deionized water mol ratio is that 1: 0.8 ratio adds deionized water, stirs 6h, obtains Al 2O 3Colloidal sol;
Two, preparation POSS colloidal sol: is 1: 3: 0.005 mixed with vinyltrimethoxy silane, ethanol, formic acid according to mol ratio, and confined reaction 10d in 35 ℃ of water-baths makes POSS colloidal sol;
Three, preparation complex sol: with Al 2O 3Colloidal sol mixes with the mass ratio of POSS colloidal sol by 1: 1, and reaction is 5 days in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, makes complex sol;
Four, will pass through pretreated silica fiber and be put in the complex sol through the pretreated silica fiber of persulfuric acid, be 0.5 * 10 in vacuum tightness 5Pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz; Use deionized water to be washed till washing lotion and be neutrality, the heat-up rate with 5 ℃/min rises to 80 ℃ from room temperature then, keeps 80 ℃ of 0.5h; Be warming up to 120 ℃ with 10 ℃/min again; Keep 120 ℃ of 1h,, promptly get and apply Al again through 550～650 ℃ thermal treatment 2O 3The silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in the step 4 is following: under 98 ℃ condition, silica fiber was soaked in mass concentration 30% dilution heat of sulfuric acid 2 hours.
Embodiment two: what this embodiment and embodiment one were different is that ethanol described in the step 1 and aluminum ions mol ratio are 22～38: 1.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is that ethanol described in the step 1 and aluminum ions mol ratio are 25～35: 1.Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is that ethanol described in the step 1 and aluminum ions mol ratio are 30: 1.Other is identical with embodiment one.
Embodiment five: what this embodiment and embodiment one were different is that sequestrant described in the step 1 and aluminum ions mol ratio are 0.31～0.38: 1.Other is identical with embodiment one.
Embodiment six: what this embodiment and embodiment one were different is that sequestrant described in the step 1 and aluminum ions mol ratio are 0.35: 1.Other is identical with embodiment one.
Embodiment seven: what this embodiment and embodiment one were different is that ethanol described in the step 1 and ASBD mol ratio are 30: 1.Other is identical with embodiment one.
Embodiment eight: this embodiment and embodiment one are different is to be 0.5 * 10 in vacuum tightness described in the step 1 5Pa or ultrasonic frequency are to flood 0.8～2.8h under the condition of 200Hz.Other is identical with embodiment one.
Embodiment nine: this embodiment and embodiment one are different is to be 0.5 * 10 in vacuum tightness described in the step 1 5Pa or ultrasonic frequency are to flood 1～2.5h under the condition of 200Hz.Other is identical with embodiment one.
Embodiment ten: this embodiment and embodiment one are different is to be 0.5 * 10 in vacuum tightness described in the step 1 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 surfaces 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; Add the 24.632g ASBD after stirring, heated and stirred to clear shape (making the abundant complexing of central aluminum atom separate too fast to prevent water) dropwise adds the 1.44g deionized water again; Stirred 6 hours 80 ℃ of temperature constant state refluxed, obtain the Al of transparent and stable 2O 3Colloidal sol;
Two, preparation POSS colloidal sol: 45.67g vinyltrimethoxy silane and 45.10g ethanol are joined in the beaker; Use concentration to carry out catalysis, utilize preservative film that beaker is sealed, put beaker is gone in the water-bath as the formic acid 15.43g of 0.1mol/L; 35 ℃ of isothermal reactions 10 days, make POSS colloidal sol;
Three, preparation complex sol: with Al 2O 3Colloidal sol mixes with the mass ratio of POSS colloidal sol by 1: 1, and reaction is 5 days in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, makes complex sol;
Four, will pass through pretreated silica fiber and be put in the complex sol through the pretreated silica fiber of persulfuric acid, be 0.5 * 10 in vacuum tightness 5Pa or ultrasonic frequency are to flood 2h under the condition of 200Hz, use deionized water to be washed till washing lotion and are neutrality, and the heat-up rate with 5 ℃/min rises to 80 ℃ from room temperature then; Keep 80 ℃ of 0.5h, be warming up to 120 ℃ with 10 ℃/min again, keep 120 ℃ of 1h; Through 550 ℃ thermal treatment, promptly get and apply Al again 2O 3The silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in the step 4 is following: under 98 ℃ condition, silica fiber was soaked in mass concentration 30% dilution heat of sulfuric acid 2 hours.

Claims (10)

1. silica fiber surfaces A l 2O 3The preparation method of-POSS hybrid coating is characterized in that silica fiber surfaces A l 2O 3The preparation method of-POSS hybrid coating carries out according to the following steps:
One, preparation Al 2O 3Colloidal sol: according to ethanol and aluminum ions mol ratio is 20～40: 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 the container; In 80 ℃ of water-baths reflux stir to clarify transparent after; According to ethanol and ASBD mol ratio is that 20～40: 1 ratio adds ASBD; Stir transparent after; According to ASBD and deionized water mol ratio is that 1: 0.8 ratio adds deionized water, stirs 6h, obtains Al 2O 3Colloidal sol;
Two, preparation POSS colloidal sol: is 1: 3: 0.005 mixed with vinyltrimethoxy silane, ethanol, formic acid according to mol ratio, and confined reaction 10d in 35 ℃ of water-baths makes POSS colloidal sol;
Three, preparation complex sol: with Al 2O 3Colloidal sol mixes with the mass ratio of POSS colloidal sol by 1: 1, and reaction is 5 days in the closed reactor that 35 ℃, 1 standard atmosphere are depressed, and then the uncovered reaction kettle for reaction of depressing at 1 standard atmosphere 2 days, makes complex sol;
Four, will pass through pretreated silica fiber and be put in the complex sol through the pretreated silica fiber of persulfuric acid, be 0.5 * 10 in vacuum tightness 5Pa or ultrasonic frequency are to flood 0.5～3h under the condition of 200Hz; Use deionized water to be washed till washing lotion and be neutrality, the heat-up rate with 5 ℃/min rises to 80 ℃ from room temperature then, keeps 80 ℃ of 0.5h; Be warming up to 120 ℃ with 10 ℃/min again; Keep 120 ℃ of 1h,, promptly get and apply Al again through 550～650 ℃ thermal treatment 2O 3The silica fiber of-POSS hybrid coating;
The preprocessing process of silica fiber described in the step 4 is following: under 98 ℃ condition, silica fiber was soaked in mass concentration 30% dilution heat of sulfuric acid 2 hours.
2. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that ethanol described in the step 1 and aluminum ions mol ratio are 22～38: 1.
3. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that ethanol described in the step 1 and aluminum ions mol ratio are 25～35: 1.
4. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that ethanol described in the step 1 and aluminum ions mol ratio are 30: 1.
5. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that sequestrant described in the step 1 and aluminum ions mol ratio are 0.31～0.38: 1.
6. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that sequestrant described in the step 1 and aluminum ions mol ratio are 0.35: 1.
7. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that ethanol described in the step 1 and ASBD mol ratio are 30: 1.
8. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that described in the step 1 in vacuum tightness being 0.5 * 10 5Pa or ultrasonic frequency are to flood 0.8～2.8h under the condition of 200Hz.
9. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that described in the step 1 in vacuum tightness being 0.5 * 10 5Pa or ultrasonic frequency are to flood 1～2.5h under the condition of 200Hz.
10. according to the said silica fiber surfaces A of claim 1 l 2O 3The preparation method of-POSS hybrid coating is characterized in that described in the step 1 in vacuum tightness being 0.5 * 10 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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114535037A (en) * 2022-01-21 2022-05-27 无锡松煜科技有限公司 Quartz boat surface treatment method
CN115321842A (en) * 2022-09-16 2022-11-11 四川轻化工大学 Corrosion-resistant basalt fiber and preparation method thereof

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Publication number Priority date Publication date Assignee Title
JPH0748150A (en) * 1993-08-03 1995-02-21 Mitsubishi Cable Ind Ltd Method for applying carbon to optical glass
CN1264769A (en) * 2000-02-15 2000-08-30 中国人民解放军国防科学技术大学 Technology for continuously coating hetergeneous organic-inorganic sol on surface of inorganic fibres
US20020071904A1 (en) * 2000-12-08 2002-06-13 Paek Un Chul Method for metal coating of optical fiber grating with a long period
CN101591148A (en) * 2008-11-21 2009-12-02 中材高新材料股份有限公司 The preparation method of alumina coat on quartz fibre surface
CN102604536A (en) * 2012-01-16 2012-07-25 南昌航空大学 Method for preparing temperature-resistant and corrosion-resistant aluminum oxide/organic silicon/silicon dioxide hybridized coating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0748150A (en) * 1993-08-03 1995-02-21 Mitsubishi Cable Ind Ltd Method for applying carbon to optical glass
CN1264769A (en) * 2000-02-15 2000-08-30 中国人民解放军国防科学技术大学 Technology for continuously coating hetergeneous organic-inorganic sol on surface of inorganic fibres
US20020071904A1 (en) * 2000-12-08 2002-06-13 Paek Un Chul Method for metal coating of optical fiber grating with a long period
CN101591148A (en) * 2008-11-21 2009-12-02 中材高新材料股份有限公司 The preparation method of alumina coat on quartz fibre surface
CN102604536A (en) * 2012-01-16 2012-07-25 南昌航空大学 Method for preparing temperature-resistant and corrosion-resistant aluminum oxide/organic silicon/silicon dioxide hybridized coating

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114535037A (en) * 2022-01-21 2022-05-27 无锡松煜科技有限公司 Quartz boat surface treatment method
CN115321842A (en) * 2022-09-16 2022-11-11 四川轻化工大学 Corrosion-resistant basalt fiber and preparation method thereof
CN115321842B (en) * 2022-09-16 2023-05-05 四川轻化工大学 Corrosion-resistant basalt fiber and preparation method thereof

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