CN103214846A - Hybrid material resistant to space environment atomic oxygen denudation and preparation method - Google Patents
Hybrid material resistant to space environment atomic oxygen denudation and preparation method Download PDFInfo
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Abstract
The invention relates to a hybrid material resistant to space environment atomic oxygen denudation. The hybrid material is composed of: (A) 100 parts of a polymer; (B) 20-150 parts of a sol-gel precursor; and (C) solvents, a curing agent and a catalyst of different dosages. The preparation method of the hybrid material resistant to space environment atomic oxygen denudation includes the following five steps of: 1. weighing the polymer and the sol-gel precursor according to the mass ratio; 2. preparing a sol-gel precursor solution; 3. preparing a polymer solution; 4. preparing a hybrid material solution resistant to space environment atomic oxygen denudation; and 5. preparing the hybrid material resistant to space environment atomic oxygen denudation. In the invention, by utilizing the hydrolysis-polycondensation reaction in a sol-gel process, an inorganic phase that does not react with atomic oxygen is generated in situ in the polymer, thereby obtaining the organic/inorganic hybrid material. With good atomic oxygen denudation resistance, the hybrid material well solves the problem that high polymer materials suffer from severe denudation by atomic oxygen.
Description
Technical field
The present invention relates to a kind of hybrid material and preparation method of the atomic oxygen erodes of anti-the space environment, it is a kind of novel organic/inorganic hybridization material and a kind of method that improves spacecraft with polymkeric substance and the anti-atomic oxygen erodes performance of polymer matrix composite of anti-atomic oxygen erodes, specifically, be meant and in polymkeric substance, pass through sol-gel method, original position generates not inorganic mutually micro-nano with the atomic oxygen reaction, improves the anti-atomic oxygen erodes performance of spacecraft with polymkeric substance, polymer matrix composite.It belongs to spacecraft material atomic oxygen guard technology field.
Background technology
Polymkeric substance and polymer matrix composite excellent performance have a wide range of applications on spacecraft.
Low Earth Orbit is one of main orbit of spacecraft, and atomic oxygen is the highest, the most active atmospheric constituent of content in the Low Earth Orbit environment, has very strong oxidisability.When spacecraft when space Low Earth Orbit environment high speed is moved because relative movement, the atomic oxygen effect of impact is all bigger in the energy and the flux on spacecraft surface.
The most of polymkeric substance and the polymer matrix composite that use on the spacecraft, comparatively serious degrading arranged under the effect of atomic oxygen in orbital environment, the thickness of material and quality can be lost, surface topography changes, degenerating also can appear in performances such as power, heat, light, electricity, thereby has influenced the works better and the work-ing life of spacecraft.For ensure spacecraft for a long time at the rail reliability service, and prolong its work-ing life, improving spacecraft is very important and necessary with the anti-atomic oxygen erodes performance of polymkeric substance and polymer matrix composite.
At present; anti-atomic oxygen erodes method commonly used on the spacecraft mainly contains: (one) atomic oxygen protective coating: it is to apply or spraying plating last layer supercoat at the material surface that is subject to degrade; atomic oxygen and material surface are kept apart, thereby reach the effect that protecting materials is not subjected to atomic oxygen erodes.This method of atomic oxygen protective coating occurs the earliest, also is at present the most frequently used, and coated material is typically chosen in the atomic oxygen environment more stable, as silicone resin, oxide compound, metal and compound coating etc.The protection effect of these protective coatings has obtained the confirmation of space flight test, and is widely used in the spacecraft surface.Guarantee its high reliability and long lifetime operation as just having used protective coating on the international space station in a large number.But this method can be brought the complicated of spacecraft structure, also can increase the difficulty of parts-moulding and processing.In addition, defectives such as crackle, hole appear in protective coating easily, as: 1. when spacecraft moves in track, (this is called as thermal cycling to its surface temperature changing between ± 80 ° of C approximately, about 90 minutes of cycle), because the thermal expansivity of coating and primer is different, under the effect of long term thermal round-robin, thermal stresses between the two may make coatingsurface crackle occur; 2. the bump of space micrometeorite and rubbish fragment also can make coatingsurface defectives such as hole occur; 3. when the deposition process of coating and component processing moulding, coatingsurface also might produce defective.This shows that the reason that coatingsurface produces defective is many-sided, also unpredictable and be difficult to avoid.These defectives are in case form, and atomic oxygen will pass these defectives and primer reacts, formation sapping, and finally cause coating to lose provide protection even come off, thus bring destruction outside the expected design to spacecraft.Validity of this explanation protective coating depends on the integrity of coating, and must avoid defective such as space junk bump to form mechanism as far as possible, otherwise can bring serious hidden danger to spacecraft equally.(2) surface modification of material: mainly be the surface-element composition that changes material by surface silicon alkanisation or ion implantation (aluminium, silicon, yttrium plasma) these two kinds of approach, make its surface contain elements such as abundant aluminium, silicon, can form oxide skin (silicon oxide, aluminum oxide etc.) thereby make under the effect of material atomic oxygen in space environment.Because these oxide compounds are not react with atomic oxygen, and are covered in material surface, thereby have just reduced the atomic oxygen erodes degree of material, have improved the anti-atomic oxygen erodes performance of material.This method is actually and has changed the elementary composition of material surface certain depth, and then under given conditions, material surface just can generate the new texture or the protective layer of anti-atomic oxygen.Spacecraft material after this method is handled, protective layer only is to exist in material surface certain thickness scope, if suffer the bump of micrometeorite and rubbish fragment, equally also can lose efficacy.Simultaneously, the present difficulty of parts is still bigger greatly adopting this method to handle the spacecraft outside surface.(3) matrix strengthening technology: mainly be by methods such as blend, doping, copolymerization, sol-gels, group of anti-atomic oxygen the or anti-atomic oxygen component are introduced in the polymkeric substance, to obtain the novel material of anti-atomic oxygen.For example on the main chain of polymkeric substance, add element, group or component that some can anti-atomic oxygen, as silicon, fluorine, zirconium, tin, phosphorus-oxygen groups etc. or SiO
2, Al
2O
3, nano imvite, ZrO
2, TiO
2Etc. inorganic anti-atomic oxygen component, to improve the anti-atomic oxygen erodes performance of material.Compare with surface modification with coating, matrix strengthening has the following advantages: 1. if the surface is destroyed, and fault location still can form new protective layer, has self-repair function; 2. avoided the sapping of atomic oxygen through holiday; 3. can make film, block, also can be used as the resin matrix of matrix material.Therefore it more has superiority than protective coating and surface modification, is the developing direction that improves the anti-atomic oxygen performance of material at present, and research trends have in recent years also proved this point both at home and abroad.
Summary of the invention
1, purpose: the objective of the invention is to be subjected to serious problem of Low Earth Orbit environment atomic oxygen erodes and the deficiency that has anti-atomic oxygen erodes technology now at polymkeric substance that uses on the spacecraft and polymer matrix composite, reaction characteristics and rule according to atomic oxygen and polymkeric substance and polymer matrix composite, a kind of hybrid material and preparation method of the atomic oxygen erodes of anti-the space environment are provided, and it is a kind ofly can significantly improve the novel method of the anti-atomic oxygen erodes performance of spacecraft polymer-based material and novel organic/inorganic hybridization material.
The present invention a kind ofly generates the inorganic micro-nano method that improves spacecraft with polymkeric substance and the anti-atomic oxygen erodes performance of polymer matrix composite mutually by sol-gel method original position in polymkeric substance, it proportionally, in reactor, polymer precursor or polymkeric substance, solvent, solidifying agent, sol-gel presoma, catalyzer, coupling agent etc. are mixed, make mixing solutions, this is a single stage method.Perhaps (1) mixes polymer precursor or polymkeric substance, solvent etc. in reactor, makes polymers soln; (2) sol-gel presoma, solvent, catalyzer etc. are mixed, treat its hydrolysis after leaving standstill for some time, make the sol-gel liquid solution.Then two kinds of solution are mixed, this is a two-step approach.Single stage method and two-step approach all can obtain the hybrid material mixing solutions of anti-atomic oxygen erodes; Behind hybrid material mixing solutions uniform mixing, utilize predetermined moulding process, prepare the organic/inorganic hybridization material of anti-atomic oxygen erodes.
2, technical scheme:
1) hybrid material of a kind of atomic oxygen erodes of anti-space environment of the present invention, the consisting of of this hybrid material (by weight),
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a kind of in polyimide resin, polyamide resin, vibrin, Resins, epoxy, resol, polysulfones, polyether-ether-ketone, the polymethylmethacrylate;
(B) sol-gel presoma, consumption is 20～150 parts, this presoma is silicoorganic compound or the organo-metallic alkoxide cpd that can hydrolysis generates not with the inorganic component of atomic oxygen reaction, a kind of as in tetraethoxy, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, the dimethyl cyclooctadiene platinum etc.; Generated in-situ inorganic phase particle diameter is 5～5000 nanometers.
(C) this solvent orange 2 A is N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol, and its consumption is 100～500 parts; This solvent B is water and ethanol or water and acetone, and its consumption is 10～30 parts in a water, 20～60 parts in ethanol or acetone; This catalyzer is dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone etc., and its consumption is 0.02～0.1 part; This coupling agent is vinyltriethoxysilane (A151) or γ-An Jibingjisanyiyangjiguiwan (KH550) or γ-(2,3-epoxy third oxygen) a kind of in propyl trimethoxy silicane (KH560) or γ-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (the dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401), its consumption by 0.005～0.05 part of the inorganic phase quality of generation;
2) preparation method of the hybrid material of a kind of atomic oxygen erodes of anti-space environment of the present invention, these method concrete steps are as follows: step 1: take by weighing polymkeric substance and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
Step 2: preparation sol-gel precursor solution
Choose a kind of in tetraethoxy in silicoorganic compound or the organo-metallic alkoxide cpd, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, the dimethyl cyclooctadiene platinum;
Choosing solvent is water and ethanol or acetone;
Choose catalyzer and be a kind of in dilute hydrochloric acid, ammoniacal liquor, tosic acid, benzyldimethylamine, the methyl ethyl diketone;
Choose not inorganic mutually required coupling agent with the atomic oxygen reaction, its coupling agent can be a kind of in vinyltriethoxysilane (A151), γ-An Jibingjisanyiyangjiguiwan (KH550), γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), tetra isopropyl (the dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
By silicoorganic compound or organo-metallic alkoxide cpd: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.10 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; And put it in the reactor and mix, make the sol-gel precursor solution; Normal temperature and pressure stirs down, and stirring velocity is 400～800 rev/mins;
The sol-gel precursor solution is left standstill for some time, make its hydrolysis, time of repose is 0.5～2 hour;
Step 3: preparation polymers soln
Choose a kind of in polymer precursor or polymer monomer or the oligopolymer;
Choose solvent and be a kind of in N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or the acetone or alcohol;
Take by weighing above-mentioned materials by polymer precursor or polymer monomer or oligopolymer: solvent=100:100～500, and put it in the reactor and mix, make polymers soln;
Step 4: the organic/inorganic hybridization material solution for preparing anti-atomic oxygen erodes
Behind the solution for preparing above-mentioned steps three, step 3 gained solution in stirring, reactor is added in the solution that obtains in the above-mentioned steps two, make the compound organic/inorganic hybridization material solution of antigen oxygen peeling after mixing;
Step 5: the organic/inorganic hybridization material for preparing anti-atomic oxygen erodes
Through selecting predetermined moulding process and equipment for use, as the solution-cast moulding process, extrude die press technology for forming, injection moulding blow molding technology etc.,, make the organic/inorganic hybridization material of anti-atomic oxygen erodes according to predetermined heating schedule curing molding.
Perhaps the preparation method of the hybrid material of a kind of anti-atomic oxygen erodes of the present invention comprises the following steps:
(a) step 1: take by weighing polymkeric substance and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
(b) step 2: the organic/inorganic hybridization material solution for preparing anti-atomic oxygen erodes
Choose a kind of in polymer precursor or monomer or the oligopolymer;
Choose solvent and be a kind of in N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or the acetone or alcohol;
Choose a kind of of tetraethoxy in silicoorganic compound or the organo-metallic alkoxide cpd, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, dimethyl cyclooctadiene platinum;
Choose solvent and be a kind of in acetone and water or the second alcohol and water;
Choose catalyzer and be a kind of in dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or the methyl ethyl diketone etc.;
Choose not the required coupling agent of nano-particle material with the atomic oxygen reaction, its coupling agent can be a kind of in vinyltriethoxysilane (A151) or γ-An Jibingjisanyiyangjiguiwan (KH550) or γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560) or γ-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (the dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
Take by weighing above-mentioned materials by polymer precursor or polymer monomer or oligopolymer: solvent orange 2 A=100:100～500, and put it in the reactor; By silicoorganic compound or organo-metallic alkoxide: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.1 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; Above-mentioned materials is once put into reactor mix, make the organic/inorganic hybridization material of anti-atomic oxygen erodes solution;
(c) step 3: the organic/inorganic hybridization material for preparing anti-atomic oxygen erodes
Through selecting predetermined moulding process and equipment for use, make the organic/inorganic hybridization material of anti-atomic oxygen erodes.
3, advantage and effect: hybrid material of a kind of anti-atomic oxygen erodes of the present invention and preparation method thereof has the following advantages: (1) adopts sol-gel method, can in matrix, original position generate inorganic phase, and there are certain chemistry, physical action between inorganic phase and the organic matrix, the interface that has guaranteed more even, inorganic phase of inorganic dispersion in matrix resin and organic phase is in conjunction with stronger, and is more favourable to the raising of the anti-atomic oxygen performance of gained hybrid material.(2) adopt sol-gel method, under liquid phase,, and carry out a series of hydrolysis, polycondensation chemical reaction, be reflected on the molecule aspect and carry out, react more complete, the condition milder, be easy to control the reaction raw materials uniform mixing; (3) in the sol-gel precursor solution, add a certain amount of catalyzer dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone etc., come the speed of control hydrolysis polycondensation by the acid-basicity of regulator solution, obtain the better organic/inorganic hybridization material of anti-atomic oxygen performance as much as possible; (4) in mixed solution system, can add surface-modifying agent/coupling agent, the inorganic phase surface that properties-correcting agent can generate with hydrolysis on the molecule aspect fully acts on, and reaches the purpose of complete modification; Make not the inorganic phase surface with the atomic oxygen reaction evenly coat one deck properties-correcting agent, guaranteed inorganic dispersion and combination in the organic resin matrix; (5) at precursor solution, resin solution in hybrid material mixing solutions preparation process, all adopt high-speed stirring, each component is mixed, fully, make the inorganic phase of generation can be in resin matrix uniform distribution; (6) gained hybrid material solution is vacuumized the processing certain hour earlier, and in the intensification solidification process, use vacuum drying oven, removed the unnecessary solvent molecule in the material effectively, made hybrid material inner, improved the anti-atomic oxygen erodes performance of material in conjunction with tightr.(7) hybrid material of preparing with this kind method of anti-the atomic oxygen erodes, the atomic oxygen erodes rate is reduced to 30%～10% of unmodified resin material, and its anti-atomic oxygen erodes performance significantly improves; (8) this method technology is simple, is easy to realize, and can not increases the complicacy of spacecraft, has good versatility, can be widely used in various polymkeric substance and polymer matrix composite commonly used on the spacecraft.
Description of drawings
Fig. 1 is preparation technology's schema of embodiment 1.
Fig. 2 is preparation technology's schema of embodiment 2.
Fig. 3 is preparation technology's schema of embodiment 3.
Fig. 4 is a FB(flow block) of the present invention.
Fig. 5 is the SEM photo that does not add the pure polyimide sample of TEOS behind the atomic oxygen test.
Fig. 6 is the SEM photo that adds 40 parts of TEOS polyimide samples behind the atomic oxygen test.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
In the present invention; inorganic be meant mutually by sol-gel precursor solution and polymers soln or polybenzazole precursor liquid solution thorough mixing evenly after; hydrolysis-condensation process in sol-gel method, in polymkeric substance generated in-situ not with the inorganic micro-nano granules or the inorganic network structure of atomic oxygen reaction.
In the sol-gel precursor solution, add a certain amount of catalyzer dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone etc., come the speed of control hydrolysis polycondensation by the acid-basicity of regulator solution, obtain the better organic/inorganic hybridization material of anti-atomic oxygen performance as much as possible; In mixed solution system, can add surface-modifying agent/coupling agent, the inorganic phase surface that properties-correcting agent can generate with hydrolysis on the molecule aspect fully acts on, and reaches the purpose of complete modification; Make not the inorganic phase surface with the atomic oxygen reaction evenly coat one deck properties-correcting agent, guaranteed inorganic dispersion and combination in resin matrix; In the intensification solidification process, used vacuum drying oven, removed the unnecessary solvent molecule in the material effectively, made hybrid material inner, improved the anti-atomic oxygen erodes performance of material in conjunction with tightr.
A kind of sol-gel method of passing through of the present invention, spacecraft with polymeric matrix in original position generate inorganic phase, improve the method for the anti-atomic oxygen erodes performance of polymer-based material, it proportionally, in reactor, polymkeric substance, solvent, sol-gel presoma, catalyzer, coupling agent etc. are mixed, make mixing solutions, this is a single stage method.Perhaps (1) mixes sol-gel presoma, solvent, catalyzer etc. in reactor, treats its hydrolysis after leaving standstill for some time; (2) polymkeric substance, stirring solvent are mixed, make resin solution, then two kinds of solution are mixed, this is a two-step approach.Single stage method and two-step approach all can obtain the hybrid material mixing solutions of anti-atomic oxygen erodes; Behind hybrid material mixing solutions uniform mixing, utilize proper molding, prepare the organic and inorganic hybrid material of anti-atomic oxygen erodes.
In the present invention, the consisting of of the hybrid material of anti-atomic oxygen erodes (by weight),
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is polyimide resin or Resins, epoxy or resol or polyamide resin or vibrin or polysulfones or polyether-ether-ketone or polymethylmethacrylate; With
(B) sol-gel presoma, consumption is 20～150 parts, this presoma is silicoorganic compound or the metallic alkoxide compound that can hydrolysis generates not with the inorganic component of atomic oxygen reaction, tetraethoxy, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, dimethyl cyclooctadiene platinum etc.; Generated in-situ inorganic phase particle diameter is 5～5000 nanometers.
In the present invention, preferable the consisting of (by weight) of the particulate composite of antigen oxygen peeling,
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a polyimide PMDA/ODA system, and wherein the PMDA:ODA mass ratio is 11:10;
(B) sol-gel presoma, consumption are 40～75 parts, and this presoma is silicoorganic compound tetraethoxy (the TEOS, (C that can hydrolysis generates silicon-dioxide
2H
5)
4SiO
4), the particle diameter of generated in-situ inorganic silicon dioxide is 20～200 nanometers.
See Fig. 4, in the present invention, the organic/inorganic hybridization material of preparing anti-atomic oxygen erodes comprises the following steps:
(a) take by weighing polymer resin matrix and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
(b) system sol-gel precursor solution
Choosing solvent is water and ethanol or acetone;
Choosing catalyzer is dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone etc.;
Choose not the required coupling agent of nano-particle material with the atomic oxygen reaction, its coupling agent can be vinyltriethoxysilane (A151) or γ-An Jibingjisanyiyangjiguiwan (KH550) or γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560) or γ-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
By silicoorganic compound or organo-metallic alkoxide: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.1 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; And put it in the reactor and mix, make precursor solution;
Precursor solution is left standstill for some time, make its hydrolysis, time of repose is 0.5～2 hour;
(c) system polymer resin solution
Choose polymer monomer or oligopolymer or polymer resin solution;
Choosing solvent is N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
Press polymkeric substance: solvent=100:100～500 take by weighing above-mentioned materials, and put it in the reactor and mix, and make polymer resin solution;
(d) the organic/inorganic hybridization material solution of the anti-atomic oxygen erodes of system
After preparing above-mentioned (c) solution, in stirring, be added into the solution in above-mentioned (b), make the hybrid material of anti-atomic oxygen erodes solution after mixing;
(e) organic/inorganic hybridization material of the anti-atomic oxygen erodes of system
Make the organic/inorganic hybridization material of anti-atomic oxygen erodes through selecting predetermined moulding process and equipment for use.
Perhaps comprise the following steps:
(a) take by weighing polymer resin matrix and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
(b) the organic/inorganic hybridization material solution of the anti-atomic oxygen erodes of system
Choose polymer monomer or oligopolymer or polymer resin solution;
Choosing solvent is N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
Choose silicoorganic compound or organo-metallic alkoxide;
Choosing thinner is acetone and water or second alcohol and water;
Choosing catalyzer is dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone etc.;
Choose not the required coupling agent of nano-particle material with the atomic oxygen reaction, its coupling agent can be vinyltriethoxysilane (A151) or γ-An Jibingjisanyiyangjiguiwan (KH550) or γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH560) or γ-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
Take by weighing above-mentioned materials by polymkeric substance: thinner=100:100～500, and put it in the reactor; By silicoorganic compound or organo-metallic alkoxide: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.1 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; Above-mentioned materials is once put into reactor mix, make organic/inorganic hybridization material solution;
(c) organic/inorganic hybridization material of the anti-atomic oxygen erodes of system
Make the organic/inorganic hybridization material of anti-atomic oxygen erodes through selecting predetermined moulding process and equipment for use.
Hybrid technique of the present invention is the technology of conventional preparation mixture material, just when the preparation mixing solutions consumption of solvent and/or solidifying agent and/or coupling agent and/or catalyzer etc. is adjusted to some extent.
Product of the present invention can pass through solution-cast moulding process or extruding-out process or injection molded technology or blow molding technology or die press technology for forming moulding.
Embodiment 1
See Fig. 1, polyimide resin (PMDA/ODA system) consumption ODA50 part (by weight), PMDA55 part, the organic/inorganic hybridization material of 40 parts of anti-atomic oxygen erodes of preparation of TEOS consumption.
The preparation method is as described below:
(a) take by weighing polymer precursor ODA, PMDA and sol-gel presoma TEOS
Take by weighing by ODA:PMDA:TEOS mass ratio=50:55:20 or 50:55:40 or 50:55:75 or 50:55:150;
(b) preparation polyamic acid (PAA) solution
ODA50 part, solvent DMAC500 part is dissolved in ODA among the DMAC, mixes, and gets in the ODA/DMAC solution;
Under whipped state, divide 55 parts of PMDA 5 times and add in the ODA/DMAC solution, stir about 10 minutes at every turn, dissolving is complete as far as possible to make it, and dissolving back solution becomes flavous thick liquid, continues to stir 2 hours, make solution complete reaction (ageing process), obtain polyamic acid solution.
(c) preparation sol-gel precursor solution
TEOS40 part, 20 parts in water, 50 parts of ethanol.Water and ethanol are put into reactor, stir (about 500 rev/mins), drip TEOS, system is mixed, make the sol-gel precursor solution with homogenizer;
(d) preparation hybrid material solution
Under whipped state, the precursor solution of step (c) is added in the polymers soln of step (b), stir (about 500 rev/mins) with homogenizer, system is mixed, make the hybrid material of anti-atomic oxygen erodes solution.
(e) organic/inorganic hybridization material of the anti-atomic oxygen erodes of system.
Make the organic/inorganic hybridization material of anti-atomic oxygen erodes through proper molding and equipment.
The mixing solutions that above-mentioned (d) made is put into vacuum chamber and is carried out vacuum stripping and handle, about the about 400Pa of gas pressure in vacuum; After taking out mixing solutions in the vacuum chamber, solution-cast film forming on sheet glass; Film is put into 80 ° of C insulations of vacuum drying oven 1 hour, and 120 ° of C are incubated 1 hour again, and 150 ° of C are incubated 1 hour again, 180 ° of C are incubated 2 hours again, 220 ° of C are incubated 1 hour again, and 250 ° of C are incubated 2 hours again, make silica/polyimides hybrid material film; Film is cut into the square sample of 2cm * 2cm; Carry out the atomic oxygen effect test of sample in Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, the atomic oxygen fluence is 6.40 * 10
20Atoms/cm
2, the antigen oxygen peeling performance of sample is estimated and is analyzed from aspects such as outward appearance, mass loss, surface topography, surface compositions.Test-results shows: this kind SiO
2/ polyimide resin hybrid material can significantly improve the anti-atomic oxygen erodes performance of polyimide.Its anti-atomic oxygen erodes results of property sees the following form:
Last atom oxygen effect test mass loss is more little, and the anti-atomic oxygen erodes performance of material is good more.
Can see, adopt sol-gel method in polymkeric substance, to introduce the method for inorganic phase, can significantly improve the anti-atomic oxygen erodes performance of polyimide resin really.The atomic oxygen effect test mass loss of gained hybrid material is reduced to 14.8%～31.6% of former polyimide numerical value.
Under same preparation flow, the umber difference of TEOS, the anti-atomic oxygen performance of gained hybrid material is also different.Originally the TEOS addition is big more, and the anti-atomic oxygen performance of hybrid material is good more; Behind certain umber, anti-atomic oxygen performance remains unchanged substantially.
Hybrid material is behind atomic oxygen test, and the surface has formed the cubic network structure that contains Si, the effect that can play the protection primer, reduces to degrade, so the denudation rate of hybrid material reduces.See also the SEM photo that adds 40 parts of TEOS polyimide samples behind pure polyimide sample of TEOS and the atomic oxygen test shown in Figure 6 that do not add behind the atomic oxygen test shown in Figure 5.Clearly, the pattern characteristics of the two are different fully, and the polyimide surface that does not add TEOS degrades more serious, presents the characters and appearances of polymkeric substance behind atomic oxygen erodes; And the polyimide material behind the interpolation TEOS, under the effect of atomic oxygen, the surface has formed contains network structure element silicon, that certain anti-atomic oxygen ability is arranged, has played the certain protection effect, and therefore anti-atomic oxygen erodes performance improves.
Embodiment 2
See Fig. 2, polyimide resin (PMDA/ODA system) consumption ODA50 part (by weight), PMDA55 part, the organic/inorganic hybridization material of 40 parts of anti-atomic oxygen erodes of preparation of TEOS consumption.
The preparation method is as described below:
(a) take by weighing polymer precursor ODA, PMDA and sol-gel presoma TEOS
Press ODA:PMDA:TEOS mass ratio=50:55:40;
(b) preparation polyamic acid (PAA) solution
ODA50 part, solvent DMAC500 part is dissolved in ODA among the DMAC, mixes, and gets in the ODA/DMAC solution;
Under whipped state, divide 55 parts of PMDA 5 times and add in the ODA/DMAC solution, stir about 10 minutes at every turn, dissolving is complete as far as possible to make it, and dissolving back solution becomes flavous thick liquid, continues to stir 2 hours, make solution complete reaction (ageing process), obtain polyamic acid solution.
(c) preparation sol-gel precursor solution
TEOS40 part, 20 parts in water, 50 parts of ethanol.Water and ethanol are put into reactor, stir (about 500 rev/mins), drip TEOS, system is mixed, make the sol-gel precursor solution with homogenizer;
(d) preparation hybrid material solution
Under whipped state, the precursor solution of step (c) is added in the polymers soln of step (b), stir (about 500 rev/mins) with homogenizer, system is mixed, make the hybrid material of anti-atomic oxygen erodes solution.
(e) organic/inorganic hybridization material of the anti-atomic oxygen erodes of system.
Make the organic/inorganic hybridization material of anti-atomic oxygen erodes through proper molding and equipment.
The above-mentioned mixing solutions that makes is put into vacuum chamber carry out the vacuum stripping processing, about the about 400Pa of gas pressure in vacuum; After taking out mixing solutions in the vacuum chamber, solution-cast film forming on sheet glass; Film is put into 80 ° of C insulations of vacuum drying oven 1 hour, and 120 ° of C are incubated 1 hour again, and 150 ° of C are incubated 1 hour again, 180 ° of C are incubated 2 hours again, 220 ° of C are incubated 1 hour again, and 250 ° of C are incubated 2 hours again, make silica/polyimides hybrid material film; Film is cut into the square sample of 2cm * 2cm; Carry out the atomic oxygen effect test of sample in Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, atomic oxygen flux is 6.40 * 10
20Atoms/cm
2, the antigen oxygen peeling performance of sample is estimated and is analyzed from aspects such as outward appearance, mass loss, surface topography, surface compositions.Test-results shows: this kind SiO
2/ polyimide resin hybrid material can significantly improve the anti-atomic oxygen erodes performance of polyimide.Its anti-atomic oxygen erodes results of property sees the following form:
Under same preparation flow, adopt the vacuum suction technology to remove unnecessary solvent molecule in the hybrid material solution, the atomic oxygen effect test mass loss of gained hybrid material is about 15.8% of polyimide virgin resin; The atomic oxygen effect test mass loss of not adopting the vacuum suction technology to make hybrid material is about 27.8% of polyimide virgin resin.Adopt suitable technique to remove unnecessary solvent molecule, favourable to the anti-atomic oxygen erodes performance of gained hybrid material.
Embodiment 3
See Fig. 3,100 parts of Resins, epoxy E51 consumptions (by weight), the organic/inorganic hybridization material of 20 parts of anti-atomic oxygen erodes of preparation of TEOS consumption.
The preparation method is as described below:
(a) take by weighing polymer resin matrix and sol-gel presoma TEOS
By polymkeric substance: sol-gel presoma mass ratio=100:20 takes by weighing;
(b) preparation sol-gel precursor solution
With TEOS20 part, 20 parts in water, 25 parts in ethanol or acetone are put into reactor, stir (about 500 rev/mins) with homogenizer, and system is mixed; Drip massfraction in the whipping process and be about 3.7% dilute hydrochloric acid solution 0.2g, make the sol-gel precursor solution as catalyzer;
(c) prepared polymer solution
With Resins, epoxy E51100 part, 50 parts in thinner acetone, solidifying agent polymeric amide PA65160 part is put into reactor, stirs (about 500 rev/mins) with homogenizer, and system is mixed, and makes polymer resin solution;
(d) the organic/inorganic hybridization material solution of the anti-atomic oxygen erodes of preparation
Under whipped state, the precursor solution of step (b) is added in the resin solution of step (c), stir (about 500 rev/mins) with homogenizer, system is mixed, make the hybrid material of anti-atomic oxygen erodes solution.
(e) organic/inorganic hybridization material of the anti-atomic oxygen erodes of system
Make the organic/inorganic hybridization material of anti-atomic oxygen erodes through selecting predetermined moulding process and equipment for use.
The above-mentioned mixing solutions that makes is put into vacuum chamber carry out the vacuum stripping processing, about the about 400Pa of gas pressure in vacuum; After taking out mixing solutions in the vacuum chamber, solution-cast film forming on sheet glass; Film is put into 60 ° of C insulations of vacuum drying oven 1 hour, and 100 ° of C are incubated 1 hour again, and 140 ° of C are incubated 1 hour again, and 180 ° of C are incubated 1 hour again, get silicon-dioxide/epoxy hybrid material film; Film is cut into the square sample of 2cm * 2cm; Carry out the atomic oxygen effect test of sample in Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, atomic oxygen flux is 6.40 * 10
20Atoms/cm
2, the antigen oxygen peeling performance of sample is estimated and is analyzed from aspects such as outward appearance, mass loss and atomic oxygen erodes rate, surface topography, surface compositions.Test-results shows: this kind SiO
2/ E51 Resins, epoxy hybrid material can significantly improve the anti-atomic oxygen erodes performance of Resins, epoxy E51.Its anti-atomic oxygen erodes results of property sees the following form:
Can see, adopt sol-gel method in polymkeric substance, to introduce the inorganic method that makes organic/inorganic hybridization material mutually, can significantly improve the antigen oxygen peeling performance of Resins, epoxy really; In the sol-gel solution preparation process, drip dilute hydrochloric acid as catalyzer, can effectively control the hydrolysis reaction of TEOS, favourable to the anti-atomic oxygen erodes performance that improves the Resins, epoxy hybrid material.
Claims (3)
1. the hybrid material of the atomic oxygen erodes of anti-the space environment is characterized in that: the consisting of of this hybrid material: by weight,
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a kind of in polyimide resin, polyamide resin, vibrin, Resins, epoxy, resol, polysulfones, polyether-ether-ketone, the polymethylmethacrylate;
(B) sol-gel presoma, consumption is 20～150 parts, this presoma is silicoorganic compound or the organo-metallic alkoxide cpd that can hydrolysis generates not with the inorganic component of atomic oxygen reaction, a kind of as in tetraethoxy, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, the dimethyl cyclooctadiene platinum; Generated in-situ inorganic phase particle diameter is 5～5000 nanometers;
(C) this solvent orange 2 A is that N,N-dimethylacetamide is that DMAC or N-Methyl pyrrolidone are NMP or acetone or alcohol, and its consumption is 100～500 parts; This solvent B is water and ethanol or water and acetone, and its consumption is 10～30 parts in a water, 20～60 parts in ethanol or acetone; This catalyzer is dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or methyl ethyl diketone, and its consumption is 0.02～0.1 part; This coupling agent is that vinyltriethoxysilane is that A151 or γ-An Jibingjisanyiyangjiguiwan are KH550 or γ-2; the 3-glycidoxy-propyltrimethoxy silane is that KH560 or γ-methacryloxypropyl trimethoxy silane KH570 or tetra isopropyl are that dioctyl phosphorous acid ester acyl titanate is a kind of among the NDZ-401, its consumption by 0.005～0.05 part of the inorganic phase quality of generation.
2. the preparation method of the hybrid material of the atomic oxygen erodes of anti-the space environment, it is characterized in that: these method concrete steps are as follows:
Step 1: take by weighing polymkeric substance and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
Step 2: choose a kind of in tetraethoxy in silicoorganic compound or the organo-metallic alkoxide cpd, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, the dimethyl cyclooctadiene platinum;
Choosing solvent is water and ethanol or acetone;
Choose catalyzer and be a kind of in dilute hydrochloric acid, ammoniacal liquor, tosic acid, benzyldimethylamine, the methyl ethyl diketone;
Choose not inorganic mutually required coupling agent with the atomic oxygen reaction, its coupling agent is that vinyltriethoxysilane is that A151, γ-An Jibingjisanyiyangjiguiwan are KH550, γ-2, and the 3-glycidoxy-propyltrimethoxy silane is that KH560, γ-methacryloxypropyl trimethoxy silane are that KH570, tetra isopropyl dioctyl phosphorous acid ester acyl titanate are a kind of among the NDZ-401;
By silicoorganic compound or organo-metallic alkoxide cpd: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.10 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; And put it in the reactor and mix, make the sol-gel precursor solution; Normal temperature and pressure stirs down, and stirring velocity is 400～800 rev/mins;
The sol-gel precursor solution is left standstill for some time, make its hydrolysis, time of repose is 0.5～2 hour;
Step 3: preparation polymers soln
Choose a kind of in polymer precursor or polymer monomer or the oligopolymer;
Choose solvent and be N,N-dimethylacetamide and be DMAC or N-Methyl pyrrolidone and be a kind of in NMP or the acetone or alcohol;
Take by weighing above-mentioned materials by polymer precursor or polymer monomer or oligopolymer: solvent=100:100～500, and put it in the reactor and mix, make polymers soln;
Step 4: the organic/inorganic hybridization material solution for preparing anti-atomic oxygen erodes
Behind the solution for preparing above-mentioned steps three, step 3 gained solution in stirring, reactor is added in the solution that obtains in the above-mentioned steps two, make the compound organic/inorganic hybridization material solution of antigen oxygen peeling after mixing;
Step 5: the organic/inorganic hybridization material for preparing anti-atomic oxygen erodes
Through selecting predetermined moulding process and equipment for use, as the solution-cast moulding process, extrude die press technology for forming, injection moulding blow molding technology,, make the organic/inorganic hybridization material of anti-atomic oxygen erodes according to predetermined heating schedule curing molding.
3. the preparation method of the hybrid material of a kind of atomic oxygen erodes of anti-space environment the according to claim 2, it is characterized in that: these method concrete steps are as follows:
Step 1: take by weighing polymkeric substance and sol-gel presoma
By polymkeric substance: sol-gel presoma mass ratio=100:20～150 take by weighing;
Step 2: the organic/inorganic hybridization material solution for preparing anti-atomic oxygen erodes
Choose a kind of in polymer precursor or monomer or the oligopolymer;
Choose solvent and be N,N-dimethylacetamide and be DMAC or N-Methyl pyrrolidone and be a kind of in NMP or the acetone or alcohol;
Choose a kind of in tetraethoxy in silicoorganic compound or the organo-metallic alkoxide cpd, methyl silicate, methyltrimethoxy silane, aluminum isopropylate, titanium tetrachloride, tetrabutyl zirconate, tetrabutyl titanate, two hydration zinc acetates, the dimethyl cyclooctadiene platinum;
Choose solvent and be a kind of in acetone and water or the second alcohol and water;
Choose catalyzer and be a kind of in dilute hydrochloric acid or ammoniacal liquor or tosic acid or benzyldimethylamine or the methyl ethyl diketone;
Choose not the required coupling agent of nano-particle material with the atomic oxygen reaction, its coupling agent is that vinyltriethoxysilane is that A151 or γ-An Jibingjisanyiyangjiguiwan are KH550 or γ-2, and the 3-glycidoxy-propyltrimethoxy silane is that KH560 or γ-methacryloxypropyl trimethoxy silane are that KH570 or tetra isopropyl are that dioctyl phosphorous acid ester acyl titanate is a kind of among the NDZ-401;
Take by weighing above-mentioned materials by polymer precursor or polymer monomer or oligopolymer: solvent orange 2 A=100:100～500, and put it in the reactor; By silicoorganic compound or organo-metallic alkoxide: water: ethanol or acetone: catalyzer=100:10～30:20～60:0.02～0.1 takes by weighing above-mentioned materials, and by generated in-situ inorganic phase: coupling agent=100:0.5～5 take by weighing above-mentioned materials; Above-mentioned materials is once put into reactor mix, make the organic/inorganic hybridization material of anti-atomic oxygen erodes solution;
Step 3: the organic/inorganic hybridization material for preparing anti-atomic oxygen erodes
Through selecting predetermined moulding process and equipment for use, make the organic/inorganic hybridization material of anti-atomic oxygen erodes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892929A (en) * | 2018-07-13 | 2018-11-27 | 江南大学 | A kind of toughening reinforced epoxy resin combination |
| CN109021565A (en) * | 2018-06-24 | 2018-12-18 | 北京化工大学 | A kind of method that in-situ hydrolysis method prepares the polyimide material of resistance to elemental oxygen |
| CN109244159A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | A kind of production line of flexible base board elemental oxygen protective layer |
| CN111499911A (en) * | 2020-06-02 | 2020-08-07 | 中国科学技术大学 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
| CN112831076A (en) * | 2021-02-04 | 2021-05-25 | 浙江中科玖源新材料有限公司 | Preparation method of high-water-resistance transparent polyimide film |
| CN114149700A (en) * | 2021-11-30 | 2022-03-08 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
| CN115572479A (en) * | 2022-11-03 | 2023-01-06 | 贵州省材料产业技术研究院 | Inorganic nanoparticle reinforced polyamide 12 powder and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583874A (en) * | 2004-05-31 | 2005-02-23 | 北京航空航天大学 | Method for improving antigen oxygen peeling of aircraft by adding nanometer partical material |
-
2013
- 2013-03-21 CN CN201310091125.5A patent/CN103214846B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583874A (en) * | 2004-05-31 | 2005-02-23 | 北京航空航天大学 | Method for improving antigen oxygen peeling of aircraft by adding nanometer partical material |
Non-Patent Citations (2)
| Title |
|---|
| 王鑫等: "硅有机物提高航天器树脂材料抗原子氧剥蚀性能", 《宇航学报》 * |
| 袁剑等: "溶胶-凝胶法提高树脂抗原子氧性能的试验", 《北京航空航天大学学报》 * |
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| CN109244159A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | A kind of production line of flexible base board elemental oxygen protective layer |
| CN109021565A (en) * | 2018-06-24 | 2018-12-18 | 北京化工大学 | A kind of method that in-situ hydrolysis method prepares the polyimide material of resistance to elemental oxygen |
| CN109021565B (en) * | 2018-06-24 | 2020-06-19 | 北京化工大学 | Method for preparing atomic oxygen resistant polyimide material by in-situ hydrolysis method |
| CN108892929A (en) * | 2018-07-13 | 2018-11-27 | 江南大学 | A kind of toughening reinforced epoxy resin combination |
| CN108892929B (en) * | 2018-07-13 | 2020-01-21 | 江南大学 | Toughened and reinforced epoxy resin composition |
| CN111499911A (en) * | 2020-06-02 | 2020-08-07 | 中国科学技术大学 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
| CN111499911B (en) * | 2020-06-02 | 2021-03-09 | 中国科学技术大学 | Extreme environment tolerance double-layer structure polyimide composite material and preparation method thereof |
| CN112831076A (en) * | 2021-02-04 | 2021-05-25 | 浙江中科玖源新材料有限公司 | Preparation method of high-water-resistance transparent polyimide film |
| CN112831076B (en) * | 2021-02-04 | 2022-12-02 | 浙江中科玖源新材料有限公司 | Preparation method of high-water-resistance transparent polyimide film |
| CN114149700A (en) * | 2021-11-30 | 2022-03-08 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
| CN114149700B (en) * | 2021-11-30 | 2022-07-05 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
| CN115572479A (en) * | 2022-11-03 | 2023-01-06 | 贵州省材料产业技术研究院 | Inorganic nanoparticle reinforced polyamide 12 powder and preparation method thereof |
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