CN103214846B - Hybrid material that a kind of elemental oxygen of resistance to spatial environments degrades and preparation method - Google Patents
Hybrid material that a kind of elemental oxygen of resistance to spatial environments degrades and preparation method Download PDFInfo
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Abstract
The hybrid material that a kind of elemental oxygen of resistance to spatial environments degrades, it is by following components: (A) polymer, and consumption is 100 parts; (B) sol-gel precursor, consumption is 20��150 parts; (C) consumption is respectively different solvent, firming agent and catalyst are constituted. The preparation method of the hybrid material that a kind of elemental oxygen of resistance to spatial environments degrades, has five big steps: one, weigh polymer and sol-gel precursor in mass ratio; Two, sol-gel precursor solution is prepared; Three, polymer solution is prepared; Four, the hybrid material solution that the elemental oxygen of resistance to spatial environments degrades is prepared; Five, the hybrid material that the elemental oxygen of resistance to spatial environments degrades is made. The present invention utilizes the hydrolysis-condensation reaction of sol-gel process, and the inorganic phase that in-situ preparation does not react with elemental oxygen in the polymer prepares organic-inorganic/inorganic hybrid material. This hybrid material has good resistance to elemental oxygen and degrades performance, solves spacecraft macromolecular material preferably and is degraded serious problem by elemental oxygen.
Description
Technical field
The present invention relates to hybrid material and preparation method that a kind of elemental oxygen of resistance to spatial environments degrades, it is the novel organic/inorganic hybridization material that degrades of a kind of resistance to elemental oxygen and a kind of improves spacecraft polymer and method that the resistance to elemental oxygen of polymer matrix composite degrades performance, specifically, refer to and pass through sol-gel process in the polymer, the inorganic micro-nano phase that in-situ preparation does not react with elemental oxygen, improves spacecraft polymer, the resistance to elemental oxygen of polymer matrix composite degrades performance. It belongs to Spacecraft Material elemental oxygen guard technology field.
Background technology
Polymer and polymer matrix composite excellent performance, have a wide range of applications on spacecraft.
Low Earth Orbit is one of main operation track of spacecraft, and elemental oxygen is content constituent of atomsphere the highest, most active in Low earth orbit environment, has very strong oxidisability. When spacecraft runs in space Low earth orbit environment high speed, due to relative motion, the elemental oxygen effect of impact energy in spacecraft surface and flux are all relatively larger.
The most of polymer used on spacecraft and polymer matrix composite, comparatively serious degrading is had under the effect of orbital environment induced by atomic oxygen, the thickness of material and quality can be lost, surface topography changes, power, heat, the performance such as optical, electrical also there will be degeneration, thus have impact on the normal work and use life-span of spacecraft. In order to ensure the long-term reliability service in-orbit of spacecraft, and extending its service life, it is particularly significant and necessary that the resistance to elemental oxygen of raising spacecraft polymer and polymer matrix composite degrades performance.
At present; resistance to elemental oxygen conventional on spacecraft degrades method mainly to be had: (one) elemental oxygen protective coating: it is to be coated with or spraying plating last layer protection coating at the material surface being subject to degrade; elemental oxygen and material surface are kept apart, thus reaching the effect that protection material is not degraded by elemental oxygen.This method of elemental oxygen protective coating occurs the earliest, is also the most frequently used at present, and it is more stable that coating material is typically chosen in atomic oxygen environment, such as silicones, oxide, metal and composite coating etc. The protected effect of these protective coatings, has been obtained for the confirmation of space flight test, and is widely used in spacecraft surface. As international space station just employed protective coating in a large number to guarantee that its high reliability and long-life are run. But this method can bring the complication of spacecraft structure, the difficulty of parts-moulding and processing also can be increased. Additionally, easily there is the defect such as crackle, hole in protective coating, as: 1. when spacecraft runs in track, its surface temperature changes between about �� 80 �� of C that (this is referred to as thermal cycle, about 90 minutes cycles), owing to coating is different with the thermal coefficient of expansion of primer, under the effect of long term thermal circulation, thermal stress between the two may make coating surface crackle occur; 2. the shock of space micrometeorite and waste particles, also can make coating surface the defects such as hole occur; 3., when the deposition process of coating and component processing molding, coating surface is also possible to produce defect. As can be seen here, it is many-sided that coating surface produces the reason of defect, also unpredictable and be difficult to avoid. These defects are once be formed, and elemental oxygen will pass these defects and primer and react, and form sapping, and ultimately result in coating and lose protective effect and even come off, thus bringing the destruction outside expected design to spacecraft. This illustrates that the effectiveness of protective coating depends on the integrity of coating, and must avoid the defect Forming Mechanism such as impact from space debris as far as possible, otherwise can bring serious hidden danger to spacecraft equally. (2) surface modification of material: change the surface-element composition of material mainly by surface silanization or ion implanting (aluminum, silicon, yttrium plasma) both approach, its surface is made to contain the elements such as abundant aluminum, silicon, so that material can form oxide skin(coating) (silicon oxide, aluminium oxide etc.) under the effect of spatial environments induced by atomic oxygen. Owing to these oxides are not react with elemental oxygen, and being covered in material surface, thus being reduced by the elemental oxygen denudation degree of material, the resistance to elemental oxygen that improve material degrades performance. This method is actually and changes the elementary composition of material surface certain depth, and then under given conditions, material surface just can generate new construction or the protective layer of resistance to elemental oxygen. Spacecraft Material after the process of this method, protective layer is only exist within the scope of material surface certain thickness, if suffering the shock of micrometeorite and waste particles, equally also can lose efficacy. Meanwhile, the spacecraft current difficulty of outer surface larger part is processed in this way or relatively larger adopting. (3) matrix strengthening technology: mainly by the method such as blended, doping, copolymerization, sol-gel, introduces in polymer by the group of resistance to elemental oxygen or resistance to elemental oxygen component, to obtain the new material of resistance to elemental oxygen. Such as on the main chain of polymer, add some be capable of withstanding the element of elemental oxygen, group or component, such as silicon, fluorine, zirconium, stannum, phosphorus-oxygen groups etc. or SiO2��Al2O3, nano imvite, ZrO2��TiO2Etc. inorganic resistance to elemental oxygen component, the resistance to elemental oxygen to improve material degrades performance. Compared with coating and surface modification, if matrix strengthening has the advantage that 1. surface is destroyed, fault location remains to form new overcoat, has self-repair function; 2. the elemental oxygen sapping through holiday is avoided; 3. thin film, block can be made, it is possible to as the resin matrix of composite. Therefore it than protective coating and surface modification more advantageously, is the developing direction improving the resistance to elemental oxygen performance of material at present, and research trends in recent years also demonstrate this point both at home and abroad.
Summary of the invention
1, purpose: it is an object of the invention to be degraded serious problem and the deficiency of the existing Ablation Technique of resistance to elemental oxygen by Low earth orbit environment elemental oxygen for the polymer used on spacecraft and polymer matrix composite, reaction characteristics according to elemental oxygen and polymer and polymer matrix composite and rule, thering is provided hybrid material and preparation method that a kind of elemental oxygen of resistance to spatial environments degrades, it is that a kind of resistance to elemental oxygen of spacecraft polymer-based material that can significantly improve degrades the new method of performance and novel organic/inorganic hybridization material.
The present invention a kind of improves spacecraft polymer by the inorganic micro-nano phase of sol-gel process in-situ preparation in the polymer and method that the resistance to elemental oxygen of polymer matrix composite degrades performance, it is proportionally, in a kettle. polymer precursor or polymer, solvent, firming agent, sol-gel precursor, catalyst, coupling agent etc. are uniformly mixed, preparing mixed solution, this is one-step method. Or polymer precursor or polymer, solvent etc. are uniformly mixed by (1) in a kettle., prepare polymer solution; (2) sol-gel precursor, solvent, catalyst etc. are uniformly mixed, after standing a period of time, treat that it is hydrolyzed, prepare sol-gel liquid solution. Then being mixed by two kinds of solution, this is two-step method. One-step method and two-step method all can obtain the hybrid material mixed solution that resistance to elemental oxygen degrades; After hybrid material mixed solution Homogeneous phase mixing, utilize predetermined moulding process, prepare the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
2, technical scheme:
1) hybrid material that a kind of elemental oxygen of resistance to spatial environments of the present invention degrades, this hybrid material consist of (by weight),
(A) polymer, consumption is 100 parts, and this polymer is the one in polyimide resin, polyamide, polyester resin, epoxy resin, phenolic resin, polysulfones, polyether-ether-ketone, polymethyl methacrylate;
(B) sol-gel precursor, consumption is 20��150 parts, this presoma is the organo-silicon compound or organic metal alkoxide cpd, the one in tetraethyl orthosilicate, methyl silicate, MTMS, aluminum isopropylate., titanium tetrachloride, tetrabutyl zirconate, butyl titanate, two acetate hydrate zinc, dimethyl cyclooctadiene platinum etc. that can be hydrolyzed and generate the inorganic component not reacted with elemental oxygen; 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 of water, ethanol or 20��60 parts of acetone; This catalyst is dilute hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc., and its consumption is 0.02��0.1 part; This coupling agent is VTES (A151) or �� aminopropyltriethoxy silane (KH550) or ��-(2,3-epoxy the third oxygen) one in propyl trimethoxy silicane (KH560) or ��-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphito ester acyl group) titanate esters (NDZ-401), its consumption by 0.005��0.05 part of generation inorganic phase quality;
2) preparation method of the hybrid material that a kind of elemental oxygen of resistance to spatial environments of the present invention degrades, the method specifically comprises the following steps that step one: weigh polymer and sol-gel precursor
By polymer: sol-gel precursor mass ratio=100:20��150 weigh;
Step 2: prepare sol-gel precursor solution
Choose the one in tetraethyl orthosilicate in organo-silicon compound or organic metal alkoxide cpd, methyl silicate, MTMS, aluminum isopropylate., titanium tetrachloride, tetrabutyl zirconate, butyl titanate, two acetate hydrate zinc, dimethyl cyclooctadiene platinum;
Choosing solvent is water and ethanol or acetone;
Choosing catalyst is the one in dilute hydrochloric acid, ammonia, p-methyl benzenesulfonic acid, benzyl dimethylamine, acetylacetone,2,4-pentanedione;
Choose the coupling agent needed for the inorganic phase not reacted with elemental oxygen, its coupling agent can be the one in VTES (A151), �� aminopropyltriethoxy silane (KH550), ��-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), ��-methacryloxypropyl trimethoxy silane (KH570), tetra isopropyl (dioctyl phosphito ester acyl group) titanate esters (NDZ-401);
By organo-silicon compound or organic metal alkoxide cpd: water: ethanol or acetone: catalyst=100:10��30:20��60:0.02��0.10 weighs above-mentioned material, by generated in-situ inorganic phase: coupling agent=100:0.5��5 weigh above-mentioned material; And put it in reactor and be uniformly mixed, prepare sol-gel precursor solution; Stirring under normal temperature and pressure, mixing speed is 400��800 revs/min;
By sol-gel precursor solution left standstill a period of time so that it is hydrolysis, time of repose is 0.5��2 hour;
Step 3: prepare polymer solution
Choose the one in polymer precursor or polymer monomer or oligomer;
Choosing solvent is the one in N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
By polymer precursor or polymer monomer or oligomer: solvent=100:100��500 weigh above-mentioned material, and put it in reactor and be uniformly mixed, prepare polymer solution;
Step 4: prepare the organic/inorganic hybridization material solution that resistance to elemental oxygen degrades
After the solution preparing above-mentioned steps three, step 3 gained solution is added in the solution obtained in above-mentioned steps two in reactor stirs, after mix homogeneously, prepare elemental oxygen degradation resistant compound organic/inorganic hybridization material solution;
Step 5: prepare the organic/inorganic hybridization material that resistance to elemental oxygen degrades
Through selecting predetermined moulding process and equipment, such as solution-cast moulding process, extrude die press technology for forming, injection moulding blow molding process etc., according to predetermined heating schedule curing molding, make the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Or the preparation method of the hybrid material that a kind of resistance to elemental oxygen of the present invention degrades, comprises the following steps:
(a) step one: weigh polymer and sol-gel precursor
By polymer: sol-gel precursor mass ratio=100:20��150 weigh;
(b) step 2: prepare the organic/inorganic hybridization material solution that resistance to elemental oxygen degrades
Choose the one in polymer precursor or monomer or oligomer;
Choosing solvent is the one in N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
Choose the one of tetraethyl orthosilicate in organo-silicon compound or organic metal alkoxide cpd, methyl silicate, MTMS, aluminum isopropylate., titanium tetrachloride, tetrabutyl zirconate, butyl titanate, two acetate hydrate zinc, dimethyl cyclooctadiene platinum;
Choosing solvent is the one in acetone and water or second alcohol and water;
Choosing catalyst is the one in dilute hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc.;
Choose the coupling agent needed for the nano-particle material not reacted with elemental oxygen, its coupling agent can be the one in VTES (A151) or �� aminopropyltriethoxy silane (KH550) or ��-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) or ��-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphito ester acyl group) titanate esters (NDZ-401);
By polymer precursor or polymer monomer or oligomer: solvent orange 2 A=100:100��500 weigh above-mentioned material, and put it in reactor; By organo-silicon compound or organic metal alkoxide: water: ethanol or acetone: catalyst=100:10��30:20��60:0.02��0.1 weighs above-mentioned material, by generated in-situ inorganic phase: coupling agent=100:0.5��5 weigh above-mentioned material; Above-mentioned material is once put in reactor and is uniformly mixed, prepare resistance to elemental oxygen and degrade organic/inorganic hybridization material solution;
(c) step 3: prepare the organic/inorganic hybridization material that resistance to elemental oxygen degrades
Through selecting predetermined moulding process and equipment, make the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
3, advantage and effect: hybrid material that a kind of resistance to elemental oxygen of the present invention degrades and preparation method thereof has the advantage that (1) adopts sol-gel process, can in-situ preparation inorganic phase in the base, and between inorganic phase and organic matrix, there is certain chemistry, physical action, ensure that inorganic phase dispersion in matrix resin evenly, the interface cohesion of inorganic phase and organic facies higher, the raising of gained hybrid material resistance to elemental oxygen performance is more favourable. (2) adopting sol-gel process, by reaction raw materials Homogeneous phase mixing under liquid phase, and carry out a series of hydrolysis, polycondensation chemical reaction, reaction carries out on molecular level, and reaction is more complete, condition milder, easily controllable; (3) in sol-gel precursor solution, add a certain amount of catalyst lean hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc., carry out the speed of controlled hydrolysis polycondensation by regulating the Acidity of Aikalinity of solution, obtain resistance to elemental oxygen performance organic/inorganic hybridization material more preferably as much as possible; (4) in mixed solution system, can adding surface modifier/coupling agent, modifying agent fully can act on the inorganic phase surface of hydrolysis generation on molecular level, and reaches the purpose modifiied completely; Make the one layer of modifying agent of inorganic phase coated with uniform not reacted with elemental oxygen, it is ensured that inorganic phase dispersion in organic resin matrix and combination; (5) at precursor solution, resin solution in hybrid material mixed solution preparation process, all adopting high-speed stirred, make each component mix homogeneously, fully, enable the inorganic phase of generation to be uniformly distributed in resin matrix; (6) gained hybrid material solution is first carried out evacuation and processes certain time, and in elevated cure process, use vacuum drying oven, effectively removes the excess of solvent molecule in material, make hybrid material internal combustion tightr, the resistance to elemental oxygen that improve material degrades performance. (7) the resistance to elemental oxygen prepared by this kind of method degrades hybrid material, and elemental oxygen denudation rate is reduced to the 30%��10% of primary resin material, and its resistance to elemental oxygen degrades performance and significantly improves; (8) the method technique is simple, it is easy to accomplish, and the complexity of spacecraft will not be increased, there is good versatility, can be widely used for various polymer conventional on spacecraft and polymer matrix composite.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow chart of embodiment 1.
Fig. 2 is the preparation technology flow chart of embodiment 2.
Fig. 3 is the preparation technology flow chart of embodiment 3.
Fig. 4 is FB(flow block) of the present invention.
Fig. 5 is the SEM photograph being not added with the pure polyimides sample of TEOS after atomic oxygen test.
Fig. 6 is the SEM photograph adding 40 parts of TEOS polyimides samples after atomic oxygen test.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
In the present invention; inorganic phase refers to and is sufficiently mixed after uniformly by sol-gel precursor solution and polymer solution or polybenzazole precursor liquid solution; hydrolysis-condensation process in sol-gel process, the in the polymer generated in-situ inorganic micro-nano granules not reacted with elemental oxygen or inorganic network structure.
In sol-gel precursor solution, add a certain amount of catalyst lean hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc., carry out the speed of controlled hydrolysis polycondensation by regulating the Acidity of Aikalinity of solution, obtain resistance to elemental oxygen performance organic/inorganic hybridization material more preferably as much as possible; In mixed solution system, can adding surface modifier/coupling agent, modifying agent fully can act on the inorganic phase surface of hydrolysis generation on molecular level, and reaches the purpose modifiied completely; Make the one layer of modifying agent of inorganic phase coated with uniform not reacted with elemental oxygen, it is ensured that inorganic phase dispersion in resin matrix and combination; Employing vacuum drying oven in elevated cure process, effectively removes the excess of solvent molecule in material, make hybrid material internal combustion tightr, the resistance to elemental oxygen that improve material degrades performance.
The one of the present invention passes through sol-gel process, inorganic phase is generated at spacecraft polymeric matrix situ, improve the method that the resistance to elemental oxygen of polymer-based material degrades performance, it is proportionally, in a kettle. polymer, solvent, sol-gel precursor, catalyst, coupling agent etc. are uniformly mixed, preparing mixed solution, this is one-step method. Or sol-gel precursor, solvent, catalyst etc. are uniformly mixed by (1) in a kettle., after standing a period of time, treat that it is hydrolyzed; (2) by polymer, stirring solvent mix homogeneously, preparing resin solution, then mixed by two kinds of solution, this is two-step method. One-step method and two-step method all can obtain the hybrid material mixed solution that resistance to elemental oxygen degrades; After hybrid material mixed solution Homogeneous phase mixing, utilize suitable moulding process, prepare the organic and inorganic hybrid material that resistance to elemental oxygen degrades.
In the present invention, the hybrid material that resistance to elemental oxygen degrades consist of (by weight),
(A) polymer, consumption is 100 parts, and this polymer is polyimide resin or epoxy resin or phenolic resin or polyamide or polyester resin or polysulfones or polyether-ether-ketone or polymethyl methacrylate; With
(B) sol-gel precursor, consumption is 20��150 parts, this presoma is the organo-silicon compound or metallic alkoxide compound, tetraethyl orthosilicate, methyl silicate, MTMS, aluminum isopropylate., titanium tetrachloride, tetrabutyl zirconate, butyl titanate, two acetate hydrate zinc, dimethyl cyclooctadiene platinum etc. that can be hydrolyzed and generate the inorganic component not reacted with elemental oxygen; Generated in-situ inorganic phase particle diameter is 5��5000 nanometers.
In the present invention, the particulate composite of elemental oxygen degradation resistant preferably consist of (by weight),
(A) polymer, consumption is 100 parts, and this polymer is polyimides PMDA/ODA system, and wherein PMDA:ODA mass ratio is 11:10;
(B) sol-gel precursor, consumption is 40��75 parts, and this presoma is organo-silicon compound tetraethyl orthosilicate (TEOS, (C that can be hydrolyzed and generate silicon dioxide2H5)4SiO4), the particle diameter of generated in-situ inorganic silicon dioxide is 20��200 nanometers.
See Fig. 4, in the present invention, prepare the organic/inorganic hybridization material that resistance to elemental oxygen degrades and comprise the following steps:
A () weighs polymer resin matrix and sol-gel precursor
By polymer: sol-gel precursor mass ratio=100:20��150 weigh;
(b) sol-gel precursor solution processed
Choosing solvent is water and ethanol or acetone;
Choosing catalyst is dilute hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc.;
Choose the coupling agent needed for the nano-particle material not reacted with elemental oxygen, its coupling agent can be VTES (A151) or �� aminopropyltriethoxy silane (KH550) or ��-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) or ��-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphito ester acyl group) titanate esters (NDZ-401);
By organo-silicon compound or organic metal alkoxide: water: ethanol or acetone: catalyst=100:10��30:20��60:0.02��0.1 weighs above-mentioned material, by generated in-situ inorganic phase: coupling agent=100:0.5��5 weigh above-mentioned material; And put it in reactor and be uniformly mixed, prepare precursor solution;
Precursor solution being stood a period of time so that it is hydrolysis, time of repose is 0.5��2 hour;
(c) polymer resin solution processed
Choose polymer monomer or oligomer or polymer resin solution;
Choosing solvent is N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
By polymer: solvent=100:100��500 weigh above-mentioned material, and put it in reactor and be uniformly mixed, prepare polymer resin solution;
D () makes the organic/inorganic hybridization material solution that resistance to elemental oxygen degrades
After preparing above-mentioned (c) solution, stirring is added into the solution in above-mentioned (b), prepares resistance to elemental oxygen after mix homogeneously and degrade hybrid material solution;
E () makes the organic/inorganic hybridization material that resistance to elemental oxygen degrades
Through selecting predetermined moulding process and equipment to make the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Or comprise the following steps:
A () weighs polymer resin matrix and sol-gel precursor
By polymer: sol-gel precursor mass ratio=100:20��150 weigh;
B () makes the organic/inorganic hybridization material solution that resistance to elemental oxygen degrades
Choose polymer monomer or oligomer or polymer resin solution;
Choosing solvent is N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP) or acetone or alcohol;
Choose organo-silicon compound or organic metal alkoxide;
Choosing diluent is acetone and water or second alcohol and water;
Choosing catalyst is dilute hydrochloric acid or ammonia or p-methyl benzenesulfonic acid or benzyl dimethylamine or acetylacetone,2,4-pentanedione etc.;
Choose the coupling agent needed for the nano-particle material not reacted with elemental oxygen, its coupling agent can be VTES (A151) or �� aminopropyltriethoxy silane (KH550) or ��-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) or ��-methacryloxypropyl trimethoxy silane (KH570) or tetra isopropyl (dioctyl phosphito ester acyl group) titanate esters (NDZ-401);
By polymer: diluent=100:100��500 weigh above-mentioned material, and put it in reactor;By organo-silicon compound or organic metal alkoxide: water: ethanol or acetone: catalyst=100:10��30:20��60:0.02��0.1 weighs above-mentioned material, by generated in-situ inorganic phase: coupling agent=100:0.5��5 weigh above-mentioned material; Above-mentioned material is once put in reactor and is uniformly mixed, prepare organic/inorganic hybridization material solution;
C () makes the organic/inorganic hybridization material that resistance to elemental oxygen degrades
Through selecting predetermined moulding process and equipment to make the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
The hybrid technique of the present invention is the technique that routine prepares mixture material, simply when preparing mixed solution, the consumption of solvent and/or firming agent and/or coupling agent and/or catalyst etc. is adjusted to some extent.
The product of the present invention can pass through solution-cast moulding process or extruding-out process or the injection forming process or blow molding process or die press technology for forming molding.
Embodiment 1
Seeing Fig. 1, polyimide resin (PMDA/ODA system) consumption ODA50 part (by weight), PMDA55 part, TEOS consumption 40 parts prepares the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Preparation method is as described below:
A () weighs polymer precursor ODA, PMDA and sol-gel precursor TEOS
Weigh 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, ODA is dissolved in DMAC, be uniformly mixed, obtain in ODA/DMAC solution;
Under stirring, 55 parts of PMDA are divided 5 times and add in ODA/DMAC solution, every time stirring about 10 minutes, making it dissolve completely, after dissolving, solution becomes flavous thick liquid, continues stirring 2 hours as far as possible, make solution complete reaction (ageing process), obtain polyamic acid solution.
(c) preparation sol-gel precursor solution
TEOS40 part, 20 parts of water, ethanol 50 parts. Water and ethanol are put in reactor, stirs (about 500 revs/min) with homogenizer, drip TEOS, make system mix homogeneously, prepare sol-gel precursor solution;
(d) preparation hybrid material solution
Under stirring, the precursor solution of step (c) is added in the polymer solution of step (b), stir (about 500 revs/min) with homogenizer, make system mix homogeneously, prepare resistance to elemental oxygen and degrade hybrid material solution.
E () makes the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
The organic/inorganic hybridization material that resistance to elemental oxygen degrades is made through suitable moulding process and equipment.
Being put into by mixed solution prepared to above-mentioned (d) in vacuum chamber and carry out vacuum degassing process, gas pressure in vacuum is about about 400Pa; After vacuum chamber takes out mixed solution, solution-cast film forming on plate glass; Thin film is put into 80 �� of C in vacuum drying oven and is incubated 1 hour, then 120 �� of C are incubated 1 hour, then 150 �� of C are incubated 1 hour, 180 �� of C are incubated 2 hours again, 220 �� of C are incubated 1 hour again, then 250 �� of C are incubated 2 hours, prepare silica/polyimides hybrid material thin film; Thin film is cut into the square coupons of 2cm �� 2cm; Carrying out the atomic oxygen effects test of sample in Low earth orbit environment atomic oxygen effects ground-based simulation equipment, elemental oxygen fluence is 6.40 �� 1020atoms/cm2, from aspects such as outward appearance, mass loss, surface topography, surface compositions, the elemental oxygen degradation resistant performance of sample is evaluated and is analyzed.Result of the test shows: this kind of SiO2/ polyimide resin hybrid material can significantly improve the resistance to elemental oxygen of polyimides and degrade performance. Its resistance to elemental oxygen degrades results of property sees following table:
The loss of upper atom oxygen effect test mass is more little, and it is more good that the resistance to elemental oxygen of material degrades performance.
It will be seen that adopt the method that sol-gel process introduces inorganic phase in the polymer, the resistance to elemental oxygen that can actually significantly improve polyimide resin degrades performance. The atomic oxygen effects test mass loss of gained hybrid material is reduced to the 14.8%��31.6% of former polyimides numerical value.
Under same preparation flow, the number of TEOS is different, and the resistance to elemental oxygen performance of gained hybrid material is also different. Originally TEOS addition is more big, and the resistance to elemental oxygen performance of hybrid material is more good; After certain number, resistance to elemental oxygen performance remains unchanged substantially.
Hybrid material is after atomic oxygen test, and surface defines the dimensional network structure containing Si, it is possible to playing protection primer, reduce the effect degraded, therefore the denudation rate of hybrid material reduces. Being not added with after atomic oxygen test shown in Figure 5 adds the SEM photograph of 40 parts of TEOS polyimides samples after atomic oxygen test shown in the pure polyimides sample of TEOS and Fig. 6. It is obvious that the pattern feature of the two is entirely different, being not added with the polyimide surface of TEOS, to degrade ratio more serious, presents polymer characters and appearances after elemental oxygen degrades; And add the polyimide material after TEOS, under the effect of elemental oxygen, surface defines containing element silicon, the network structure that has certain resistance to elemental oxygen ability, serves certain protective effect, and therefore resistance to elemental oxygen degrades performance and improves.
Embodiment 2
Seeing Fig. 2, polyimide resin (PMDA/ODA system) consumption ODA50 part (by weight), PMDA55 part, TEOS consumption 40 parts prepares the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Preparation method is as described below:
A () weighs polymer precursor ODA, PMDA and sol-gel precursor TEOS
By ODA:PMDA:TEOS mass ratio=50:55:40;
(b) preparation polyamic acid (PAA) solution
ODA50 part, solvent DMAC500 part, ODA is dissolved in DMAC, be uniformly mixed, obtain in ODA/DMAC solution;
Under stirring, 55 parts of PMDA are divided 5 times and add in ODA/DMAC solution, every time stirring about 10 minutes, making it dissolve completely, after dissolving, solution becomes flavous thick liquid, continues stirring 2 hours as far as possible, make solution complete reaction (ageing process), obtain polyamic acid solution.
(c) preparation sol-gel precursor solution
TEOS40 part, 20 parts of water, ethanol 50 parts. Water and ethanol are put in reactor, stirs (about 500 revs/min) with homogenizer, drip TEOS, make system mix homogeneously, prepare sol-gel precursor solution;
(d) preparation hybrid material solution
Under stirring, the precursor solution of step (c) is added in the polymer solution of step (b), stir (about 500 revs/min) with homogenizer, make system mix homogeneously, prepare resistance to elemental oxygen and degrade hybrid material solution.
E () makes the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
The organic/inorganic hybridization material that resistance to elemental oxygen degrades is made through suitable moulding process and equipment.
Being put into by above-mentioned prepared mixed solution and carry out vacuum degassing process in vacuum chamber, gas pressure in vacuum is about about 400Pa;After vacuum chamber takes out mixed solution, solution-cast film forming on plate glass; Thin film is put into 80 �� of C in vacuum drying oven and is incubated 1 hour, then 120 �� of C are incubated 1 hour, then 150 �� of C are incubated 1 hour, 180 �� of C are incubated 2 hours again, 220 �� of C are incubated 1 hour again, then 250 �� of C are incubated 2 hours, prepare silica/polyimides hybrid material thin film; Thin film is cut into the square coupons of 2cm �� 2cm; Carrying out the atomic oxygen effects test of sample in Low earth orbit environment atomic oxygen effects ground-based simulation equipment, atomic oxygen flux is 6.40 �� 1020atoms/cm2, from aspects such as outward appearance, mass loss, surface topography, surface compositions, the elemental oxygen degradation resistant performance of sample is evaluated and is analyzed. Result of the test shows: this kind of SiO2/ polyimide resin hybrid material can significantly improve the resistance to elemental oxygen of polyimides and degrade performance. Its resistance to elemental oxygen degrades results of property sees following table:
Under same preparation flow, adopting vacuum suction technology to remove solvent molecule unnecessary in hybrid material solution, the atomic oxygen effects test mass loss of gained hybrid material is about the 15.8% of polyimides virgin resin; The atomic oxygen effects test mass loss being provided without the prepared hybrid material of vacuum suction technology is about the 27.8% of polyimides virgin resin. Adopt suitable technology to remove excess of solvent molecule, the resistance to elemental oxygen of gained hybrid material is degraded performance favourable.
Embodiment 3
Seeing Fig. 3, epoxy resin E51 consumption 100 parts (by weight), TEOS consumption 20 parts prepares the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Preparation method is as described below:
A () weighs polymer resin matrix and sol-gel precursor TEOS
By polymer: sol-gel precursor mass ratio=100:20 weighs;
(b) preparation sol-gel precursor solution
By TEOS20 part, 20 parts of water, ethanol or 25 parts of acetone, put in reactor, stir (about 500 revs/min) with homogenizer, make system mix homogeneously; Whipping process drips mass fraction and is about the dilute hydrochloric acid solution 0.2g of 3.7% as catalyst, prepare sol-gel precursor solution;
(c) prepared polymer solution
By epoxy resin E51100 part, 50 parts of diluent acetone, firming agent polyamide PA65160 part is put in reactor, stirs (about 500 revs/min) with homogenizer, makes system mix homogeneously, prepares polymer resin solution;
D () prepares the organic/inorganic hybridization material solution that resistance to elemental oxygen degrades
Under stirring, the precursor solution of step (b) is added in the resin solution of step (c), stir (about 500 revs/min) with homogenizer, make system mix homogeneously, prepare resistance to elemental oxygen and degrade hybrid material solution.
E () makes the organic/inorganic hybridization material that resistance to elemental oxygen degrades
Through selecting predetermined moulding process and equipment to make the organic/inorganic hybridization material that resistance to elemental oxygen degrades.
Being put into by above-mentioned prepared mixed solution and carry out vacuum degassing process in vacuum chamber, gas pressure in vacuum is about about 400Pa; After vacuum chamber takes out mixed solution, solution-cast film forming on plate glass; Thin film is put into 60 �� of C in vacuum drying oven and is incubated 1 hour, then 100 �� of C are incubated 1 hour, then 140 �� of C are incubated 1 hour, then 180 �� of C are incubated 1 hour, obtain silicon dioxide/epoxy hybrid material thin film; Thin film is cut into the square coupons of 2cm �� 2cm; Carrying out the atomic oxygen effects test of sample in Low earth orbit environment atomic oxygen effects ground-based simulation equipment, atomic oxygen flux is 6.40 �� 1020atoms/cm2, from aspects such as outward appearance, mass loss and elemental oxygen denudation rate, surface topography, surface compositions, the elemental oxygen degradation resistant performance of sample is evaluated and is analyzed.Result of the test shows: this kind of SiO2/ E51 epoxy resin hybrid material can significantly improve the resistance to elemental oxygen of epoxy resin E51 and degrade performance. Its resistance to elemental oxygen degrades results of property sees following table:
It will be seen that adopt sol-gel process to introduce the method that inorganic phase prepares organic/inorganic hybridization material in the polymer, the elemental oxygen degradation resistant performance of epoxy resin can actually be significantly improved; Sol-gel solution preparation process drips dilute hydrochloric acid as catalyst, it is possible to effectively control the hydrolysis of TEOS, the resistance to elemental oxygen improving epoxy resin hybrid material is degraded performance favourable.
Claims (1)
1. the preparation method of the hybrid material that the elemental oxygen of resistance to spatial environments degrades, it is characterised in that: preparing, with polyimide resin, the organic/inorganic hybridization material that resistance to elemental oxygen degrades, preparation method is as described below:
A () weighs polymer precursor ODA, PMDA and sol-gel precursor TEOS and weighs by ODA:PMDA:TEOS mass ratio=50:55:40;
(b) preparation polyamic acid PAA solution
ODA50 part, solvent DMAC500 part, ODA is dissolved in DMAC, be uniformly mixed, obtain in ODA/DMAC solution;
Under stirring, 55 parts of PMDA are divided 5 times and add in ODA/DMAC solution, every time stirring about 10 minutes, making it dissolve completely, after dissolving, solution becomes flavous thick liquid, continues stirring 2 hours as far as possible, make solution complete reaction, obtain polyamic acid solution;
(c) preparation sol-gel precursor solution
TEOS40 part, 20 parts of water, ethanol 50 parts; Water and ethanol are put in reactor, stirs with blender, 500 revs/min, drip TEOS, make system mix homogeneously, prepare sol-gel precursor solution;
(d) preparation hybrid material solution
Under stirring, the precursor solution of step (c) is added in the polymer solution of step (b), stir with blender, 500 revs/min, make system mix homogeneously, prepare resistance to elemental oxygen and degrade hybrid material solution;
E () prepares the resin hybridized material film of silica/polyimides
Being put into by mixed solution prepared to above-mentioned (d) in vacuum chamber and carry out vacuum degassing process, gas pressure in vacuum is 400Pa; After vacuum chamber takes out mixed solution, solution-cast film forming on plate glass; Thin film is put in vacuum drying oven 80 DEG C and is incubated 1 hour, then 120 DEG C are incubated 1 hour, then 150 DEG C are incubated 1 hour, 180 DEG C are incubated 2 hours again, 220 DEG C are incubated 1 hour again, then 250 DEG C are incubated 2 hours, prepare the resin hybridized material film of silica/polyimides.
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| CN109244159B (en) * | 2017-07-11 | 2020-03-17 | 中国科学院上海硅酸盐研究所 | Production line of flexible substrate atomic oxygen protective layer |
| 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 |
| CN108892929B (en) * | 2018-07-13 | 2020-01-21 | 江南大学 | Toughened and reinforced epoxy resin composition |
| 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 |
| 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 |
| 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 |
| CN115572479B (en) * | 2022-11-03 | 2023-06-16 | 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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