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CN1254508C - Method for improving antigen oxygen peeling of aircraft by adding nanometer partical material - Google Patents

Method for improving antigen oxygen peeling of aircraft by adding nanometer partical material Download PDF

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Publication number
CN1254508C
CN1254508C CNB2004100091539A CN200410009153A CN1254508C CN 1254508 C CN1254508 C CN 1254508C CN B2004100091539 A CNB2004100091539 A CN B2004100091539A CN 200410009153 A CN200410009153 A CN 200410009153A CN 1254508 C CN1254508 C CN 1254508C
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atomic oxygen
polymer
resin
composite material
ablation
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CN1583874A (en
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沈志刚
赵小虎
王明珠
蔡楚江
麻树林
邢玉山
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Beihang University
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Beihang University
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Abstract

本发明公开了一种通过添加纳米颗粒材料来提高航天器用聚合物和聚合物基复合材料抗原子氧剥蚀性能的方法,其按照比例,在反应釜中将聚合物或聚合物基复合材料的树脂基体、稀释剂和/或固化剂搅拌混合均匀,制得树脂溶液;再将经表面改性处理后的不与原子氧反应的纳米颗粒材料,在搅拌状态下加入到树脂溶液中,制得抗原子氧剥蚀复合材料溶液;将抗原子氧剥蚀复合材料溶液经成型工艺可制备出抗原子氧剥蚀的颗粒复合材料或者制备出抗原子氧剥蚀的纤维颗粒复合材料。本发明的复合材料通过原子氧效应试验表明,具有较好的抗原子氧剥蚀性能,从而较好地解决了航天器用高分子材料受原子氧剥蚀严重的问题,能够满足航天工程的使用要求。材料的整个制备过程采用常规的制备方法,具有很好的工程适用性,同时,使用这种材料也不会给航天器结构带来复杂化。The invention discloses a method for improving the anti-atomic oxygen ablation performance of polymers and polymer-based composite materials for spacecraft by adding nanoparticle materials. According to the proportion, the polymer or the resin of the polymer-based composite materials The matrix, diluent and/or curing agent are stirred and mixed evenly to obtain a resin solution; then the surface-modified nanoparticle material that does not react with atomic oxygen is added to the resin solution under stirring to obtain an antigen Anti-atomic oxygen ablation composite material solution; the anti-atomic oxygen ablation composite material solution can be prepared through a molding process to prepare an anti-atomic oxygen ablation particle composite material or to prepare an anti-atomic oxygen ablation fiber particle composite material. The atomic oxygen effect test shows that the composite material of the present invention has better anti-atomic oxygen erosion performance, thereby better solving the problem that the polymer materials used in spacecraft are severely eroded by atomic oxygen, and can meet the use requirements of aerospace engineering. The entire preparation process of the material adopts a conventional preparation method, which has good engineering applicability, and at the same time, the use of this material will not bring complexity to the structure of the spacecraft.

Description

A kind of by adding the method for nano-particle material raising spacecraft material antigen oxygen peeling
Technical field
The present invention relates to a kind of method that improves spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance, specifically, be meant in the resin matrix of polymkeric substance and polymer matrix composite and add the antigen oxygen peeling performance that does not improve the spacecraft material with the nano-particle material of atomic oxygen reaction.
Background technology
Polymkeric substance and polymer matrix composite have a wide range of applications on spacecraft.When spacecraft moves in the Low Earth Orbit environment of space, most of polymkeric substance and polymer matrix composite can be subjected to seriously degrading of atomic oxygen in the environment, the thickness of material and quality can be lost, and performance also can degenerate, thereby have influenced the works better and the work-ing life of spacecraft.In order to ensure moving reliably and with long-term at rail of spacecraft, and prolong its work-ing life, improving spacecraft is very important and necessary with the antigen oxygen peeling performance of polymkeric substance and polymer matrix composite.
At present; antigen oxygen peeling method commonly used on the spacecraft mainly contains: (one) anti-atomic oxygen protective coating: it is to plate one deck supercoat at the material surface that is subject to degrade; atomic oxygen can't be contacted with the protected material of bottom, thereby play the effect of antigen oxygen peeling.This method of anti-atomic oxygen protective coating occurs the earliest, also is at present the most frequently used, as just having used protective coating to guarantee that it moves and work-ing life reliably and with long-term in a large number on the international space station.It is complicated that but this method brings for the structure of spacecraft, also can increase the difficulty of forming materials and processing.In addition, defective appears in coating easily, as: 1. when spacecraft moves in track, (this is called as thermal cycling to its surface temperature changing between ± 80 ℃ 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. in the deposition process of coating and during the component processing moulding, coatingsurface also might produce defective.These defectives are in case form, and atomic oxygen will pass these defectives and primer reacts, the formation sapping, and finally cause coating to lose provide protection even come off.(2) change the elementary composition of material surface: 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 abundant aluminium, silicon plasma, thereby make material under the effect of factors such as space atomic oxygen or atomic oxygen and uv-radiation, form oxide skin (silicon oxide, aluminum oxide etc.).Because these oxide compounds are not react with atomic oxygen, thereby also just reduce the atomic oxygen erodes degree of material, improved the antigen oxygen peeling 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 are to exist at material surface, if suffer the bump of micrometeorite and rubbish fragment, equally also can lose efficacy; In addition, the bump of high energy particle also can change the molecular structure and the physics-chem characteristic of material surface, and for example the surface carbonization takes place and presents burgundy or the like.(3) development of new polymer materials: the molecular composition and the structure of redesign material, construct can antigen oxygen peeling novel material.This method mainly is to add the element that some can anti-atomic oxygen on the main chain of polymkeric substance at present, as fluorine, phosphorus etc., to improve the antigen oxygen peeling performance of material.But it can relate to the change of polymer production technology, bigger difficulty is arranged, and resulting material is except having preferably the antigen oxygen peeling performance, can satisfy the service requirements (as hot optical property, mechanical property, insulating property etc.) of spacecraft others, it be not immediately clear.
Summary of the invention
The objective of the invention is the deficiency that the polymkeric substance used at spacecraft and polymer matrix composite are subjected to serious problem of Low Earth Orbit environment atomic oxygen erodes and existing antigen oxygen peeling technology, according to the reaction characteristics and the rule of atomic oxygen and polymkeric substance and polymer matrix composite, a kind of novel method and matrix material thereof that can significantly improve spacecraft material antigen oxygen peeling performance disclosed.
The present invention is a kind of method that improves spacecraft usefulness polymkeric substance and polymer matrix composite antigen oxygen peeling performance by the interpolation nano-particle material, it proportionally, resin matrix, thinner and/or solidifying agent with polymkeric substance or polymer matrix composite in reactor mix, and make resin solution; Nano-particle material that again will be after surface modification treatment joins in the resin solution under whipped state, makes antigen oxygen peeling matrix material solution; The sub-oxygen of above-mentioned antigens is degraded matrix material solution can be prepared the particulate composite of antigen oxygen peeling or prepare the fiber grain matrix material of antigen oxygen peeling through moulding process.
The composition of the particulate composite of described antigen oxygen peeling is by weight:
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is Resins, epoxy or polyimide resin or resol or polyamide resin or vibrin or polysulfones or polyether-ether-ketone or polymethylmethacrylate; With
(B) nano-particle material, consumption are 2~35 parts, this nano-particle material be not with silicon-dioxide or aluminium sesquioxide or zirconium white or the stannic oxide or the material of titanium oxide after surface modification treatment of atomic oxygen reaction, its particle diameter 5~100 nanometers.
The composition of the fiber grain matrix material of described antigen oxygen peeling is by weight:
(A) resin matrix of polymer matrix composite, consumption are 100 parts, and this resin matrix is Resins, epoxy or polyimide resin or resol or polyamide resin or vibrin or polysulfones or polyether-ether-ketone or polymethylmethacrylate; With
(B) nano-particle material, consumption are 2~35 parts, this nano-particle material be not with silicon-dioxide or aluminium sesquioxide or zirconium white or the stannic oxide or the material of titanium oxide after surface modification treatment of atomic oxygen reaction, its particle diameter 5~100 nanometers; With
(C) filamentary material: carbon fiber or glass fibre.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by adding nano-particle material
(a) preparation nano-particle material
Choose not nano-particle material with the atomic oxygen reaction;
Choose not the required surface-modifying agent of nano-particle material with the atomic oxygen reaction, its surface-modifying agent can be vinyltriethoxysilane (Al51) or γ-An Jibingjisanyiyangjiguiwan (KH550) or tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
Admit the rice particulate material: surface-modifying agent=100: 0.5~5 take by weighing above-mentioned materials, make nano-particle material;
(b) take by weighing the resin matrix and the nano-particle material of polymkeric substance or polymer matrix composite
Resin matrix by polymkeric substance or polymer matrix composite: nano-particle material=100: 2~35 take by weighing;
(c) resin solution of system polymkeric substance or polymer matrix composite
Choose the resin matrix of polymkeric substance or polymer matrix composite;
Choosing thinner is acetone;
Choosing solidifying agent is polymeric amide or triethylamine or hexanediamine or 4,4 '-two amido ditanes or glyoxal ethyline or MALEIC ANHYDRIDE;
Resin matrix by polymkeric substance or polymer matrix composite: solidifying agent: thinner=100: 0~70: 40~80 take by weighing above-mentioned materials, and put it in the reactor and mix, and make the resin solution of polymkeric substance or polymer matrix composite;
(d) system antigen oxygen peeling matrix material solution
After preparing above-mentioned (c) solution, in stirring, be added into the nano-particle material in above-mentioned (a), make antigen oxygen peeling matrix material solution;
(e) system antigen oxygen peeling particulate composite or antigen oxygen peeling fiber grain matrix material
Make antigen oxygen peeling particulate composite or antigen oxygen peeling fiber grain matrix material through moulding process.
Matrix material of the present invention has the following advantages: (1) with the modification of aerosol surface modification equipment handle not with the nano-particle material of atomic oxygen reaction, properties-correcting agent and particulate material surface can fully act on, and reach the purpose of complete modification; Make not the nano-particle material coated with uniform one deck properties-correcting agent with the atomic oxygen reaction, guaranteed dispersion and the combination of nano-particle material in resin matrix; (2) in the process of high-speed stirring, nano-particle material is joined in the resin matrix, make nano-particle material can be in resin matrix uniform distribution; With the antigen oxygen peeling matrix material that this kind method is prepared, the atomic oxygen erodes rate is reduced to and does not add 50%~5% of nanometer particulate material, and its antigen oxygen peeling performance significantly improves; (3) 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 does not adopt aerosol surface modification technology schema with the material of atomic oxygen reaction.
Fig. 2 is preparation technology's schema of embodiment 1.
Fig. 3 is preparation technology's schema of embodiment 2.
Fig. 4 (a) does not add 15 parts of SiO 2The field emission SEM photo of Resins, epoxy E51.
Fig. 4 (b) adds 15 parts of SiO 2The field emission SEM photo of Resins, epoxy E51.
Fig. 5 (a) does not add 15 parts of SiO 2The field emission SEM photo of/polyimide resin BMP316.
Fig. 5 (b) adds 15 parts of SiO 2The field emission SEM photo of/polyimide resin BMP316.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
In the present invention, nano-particle material be meant after surface modification treatment not with atomic oxygen reaction receive particulate material.Its processing technology for surface modification and equipment are the inventor's disclosed devices in the patent application that proposed on December 26th, 2002, publication number CN1424136A, application number 02158690X, denomination of invention " adopts aerosol processing that nanometer and micron particle material are disperseed technology and device thereof with surface modification treatment ".The aerosol processing nanometer of this technology or micron particle dispersion of materials and processing technology for surface modification mainly comprise: nanometer or micron particle material are broken up in the strong turbulence field with high velocity air, spray in the nanometer or micron particle material system of having been broken up with the properties-correcting agent atomizing or after gasifying by spraying gun, by the fully mixed aerosol that gets, properties-correcting agent is fully contacted with nanometer or micron particle material surface; The temperature and the pressure of control aerosol system behind the certain hour, come out this aerosol spray by nozzle; Adopt the method for injecting atmospheric air then, the aerosol that gushes out is cooled off rapidly, make properties-correcting agent can be coated on nanometer or micron particle material surface preferably, reach the purpose that makes nanometer or micron particle dispersion of materials and surface modification; Finish collection by collector at last to nanometer or micron particle material.Technical process is clearly referring to shown in Figure 1, particulate material surface after this art breading can fully act on properties-correcting agent, and reach the purpose of complete modification, make not the nano-particle material coated with uniform one deck properties-correcting agent with the atomic oxygen reaction, guaranteed dispersion and the combination of nano-particle material in resin matrix solution.
A kind of method that improves spacecraft usefulness polymkeric substance and polymer matrix composite antigen oxygen peeling performance by the interpolation nano-particle material of the present invention, it proportionally, resin matrix, thinner and/or solidifying agent with polymkeric substance or polymer matrix composite in reactor mix, and make resin solution; Again will be after surface modification treatment not with the nano-particle material of atomic oxygen reaction, under whipped state, join in the resin solution, make antigen oxygen peeling matrix material solution; Antigen oxygen peeling matrix material solution can be prepared the particulate composite of antigen oxygen peeling or prepared the fiber grain matrix material of antigen oxygen peeling through moulding process.
In the present invention, the composition of the particulate composite of antigen oxygen peeling is by weight:
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is Resins, epoxy or polyimide resin or resol or polyamide resin or vibrin or polysulfones or polyether-ether-ketone or polymethylmethacrylate; With
(B) nano-particle material, consumption are 2~35 parts, this nano-particle material be not with silicon-dioxide or aluminium sesquioxide or zirconium white or the stannic oxide or the material of titanium oxide after surface modification treatment of atomic oxygen reaction, its particle diameter 5~100 nanometers.
In the present invention, the another composition of the particulate composite of antigen oxygen peeling is by weight:
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is Resins, epoxy or polyimide resin; With
(B) nano-particle material, consumption are 2~20 parts, this nano-particle material be not with the material of silicon-dioxide after surface modification treatment of atomic oxygen reaction, its particle diameter 20~30 nanometers.
In the present invention, the composition of the fiber grain matrix material of antigen oxygen peeling is by weight:
(A) resin matrix of polymer matrix composite, consumption are 100 parts, and this resin matrix is Resins, epoxy or polyimide resin or resol or polyamide resin or vibrin or polysulfones or polyether-ether-ketone or polymethylmethacrylate; With
(B) nano-particle material, consumption are 2~35 parts, this nano-particle material be not with silicon-dioxide or aluminium sesquioxide or zirconium white or the stannic oxide or the material of titanium oxide after surface modification treatment of atomic oxygen reaction, its particle diameter 5~100 nanometers; With
(C) filamentary material: carbon fiber or glass fibre.
In the present invention, the another composition of the fiber grain matrix material of antigen oxygen peeling is by weight:
(A) resin matrix of polymer matrix composite, consumption are 100 parts, and this resin matrix is Resins, epoxy or polyimide resin; With
(B) nano-particle material, consumption are 2~20 parts, this nano-particle material be not with the material of silicon-dioxide after surface modification treatment of atomic oxygen reaction, its particle diameter 20~30 nanometers; With
(C) filamentary material: glass fibre.
In the present invention, the fiber grain matrix material of preparing the particulate composite of antigen oxygen peeling or preparing antigen oxygen peeling comprises the following steps:
(a) preparation nano-particle material
Choose not nano-particle material with the atomic oxygen reaction;
Choose not the required surface-modifying agent of nano-particle material with the atomic oxygen reaction, its surface-modifying agent can be vinyltriethoxysilane (A151) or γ-An Jibingjisanyiyangjiguiwan (KH550) or tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester (NDZ-401);
By nano-particle material: surface-modifying agent=100: 0.5~5 take by weighing above-mentioned materials, make nano-particle material;
(b) take by weighing the resin matrix and the nano-particle material of polymkeric substance or polymer matrix composite
Resin matrix by polymkeric substance or polymer matrix composite: nano-particle material=100: 2~35 take by weighing;
(c) resin solution of system polymkeric substance or polymer matrix composite
Choose the resin matrix of polymkeric substance or polymer matrix composite;
Choosing thinner is acetone;
Choosing solidifying agent is polymeric amide or triethylamine or hexanediamine or 4,4 '-two amido ditanes or glyoxal ethyline or MALEIC ANHYDRIDE;
Resin matrix by polymkeric substance or polymer matrix composite: solidifying agent: thinner=100: 0~70: 40~80 take by weighing above-mentioned materials, and put it in the reactor and mix, and make the resin solution of polymkeric substance or polymer matrix composite;
(d) system antigen oxygen peeling matrix material solution
After preparing above-mentioned (c) solution, in stirring, be added into the nano-particle material in above-mentioned (a), make antigen oxygen peeling matrix material solution;
(e) system antigen oxygen peeling particulate composite or antigen oxygen peeling fiber grain matrix material
Make antigen oxygen peeling particulate composite or antigen oxygen peeling fiber grain matrix material through moulding process.
In the method for preparing the antigen oxygen peeling matrix material in the present invention, solution in (d) step is made membranaceous antigen oxygen peeling particulate composite by solution-cast technology; Perhaps solution in (d) step is made lamination template antigen oxygen peeling fiber grain matrix material by technology laminated into type.
Hybrid technique of the present invention is the technology of conventional preparation mixture material, just when the resin matrix solution of preparation polymkeric substance or polymer matrix composite to thinner and/or solidify neat consumption and adjust to some extent.Carrying out surface modification treatment for nano-particle material carries out in " adopting aerosol processing nanometer and micron particle material to be disperseed technology and device thereof with surface modification treatment ".
Embodiment 1
100 parts of Resins, epoxy E51 consumptions (by weight), the particulate composite of 15 parts of preparations of earth silicon material antigen oxygen peeling.
The preparation method is as described below:
(a) preparation nanometer titanium dioxide silicon materials
Take by weighing not with the particle diameter of atomic oxygen reaction is 100 parts of the earth silicon materials and the required surface-modifying agent vinyltriethoxysilane A151 of 25 nanometers, consumption is 3 parts, through " aerosol surface modification device " silicon-dioxide is carried out surface modification treatment, make the nanometer silicon dioxide particle material;
(b) take by weighing 15 parts of 100 parts of Resins, epoxy E51 and nanometer titanium dioxide silicon materials;
(c) preparation Resins, epoxy E51 solution
With 100 parts of Resins, epoxy E51,50 parts in thinner acetone, solidifying agent polymeric amide PA651 puts into reactor for 60 parts, stirs (about 500 rev/mins) with homogenizer, and system is mixed, and makes Resins, epoxy E51 solution;
(d) preparation antigen oxygen peeling matrix material solution
Under whipped state, the earth silicon material of step (a) is added in the Resins, epoxy E51 solution of step (c), stir (about 500 rev/mins) with homogenizer, system is mixed, make antigen oxygen peeling matrix material solution.
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, on sheet glass, adopt solution-cast technology made membrane; And film put into 40 ℃ in loft drier insulation 7 hours, and then 80 ℃ of insulations 7 hours, nano silicon/Resins, epoxy E51 composite material film can be obtained after the curing; Film is cut into the square sample of 2cm * 2cm, in Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, carry out the atomic oxygen effect test of sample, the antigen oxygen peeling performance of sample is estimated and 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/ Resins, epoxy E51 epoxy composite material can significantly improve the antigen oxygen peeling performance of Resins, epoxy E51.Its antigen oxygen peeling results of property sees the following form:
Polymkeric substance Atomic oxygen erodes rate (cm 3/atom) Test shows
Before the interpolation After the interpolation (being reduced to)
Resins, epoxy E51 4.64×10 -24 5 parts 1.78×10 -24 38.36%
10 parts 0.82×10 -24 17.67%
15 parts 0.44×10 -24 9.48%
Last atom oxygen denudation rate is more little, and the antigen oxygen peeling performance of material is good more.
Be added with the Resins, epoxy E51 matrix material sample of 15 parts of nanometer titanium dioxide silicon materials, its denudation rate is about 9.48% of Resins, epoxy E51 virgin resin, shows that this method can significantly improve the antigen oxygen peeling performance of Resins, epoxy E51 really.See also the forward and backward SEM photo of interpolation shown in Figure 4.
Add the Resins, epoxy E51 matrix material sample of 5 parts or 10 parts nanometer titanium dioxide silicon materials after the same method, test-results shows that its denudation rate is about 38.36% or 17.67% of Resins, epoxy E51 virgin resin respectively.
Embodiment 2
100 parts of polyimide resin BMP316 consumptions (by weight), the fiber grain matrix material of 15 parts of preparations of earth silicon material antigen oxygen peeling.
The preparation method is as described below:
(a) preparation nanometer titanium dioxide silicon materials
Take by weighing not with the particle diameter of atomic oxygen reaction is 100 parts of the earth silicon materials and the required surface-modifying agent vinyltriethoxysilane A151 of 25 nanometers, consumption is 3 parts, through " aerosol surface modification device " silicon-dioxide is carried out surface modification treatment, make the nanometer silicon dioxide particle material;
(b) take by weighing 15 parts of 100 parts of polyimide resin BMP316 and nanometer titanium dioxide silicon materials;
(c) resin solution of prepared polymer based composites
With 100 parts of polyimide resin BMP316,60 parts in thinner acetone is put into reactor, stirs (about 500 rev/mins) with homogenizer, and system is mixed, and makes the resin solution of polymer matrix composite;
(d) preparation antigen oxygen peeling matrix material solution
Under whipped state, the earth silicon material of step (a) is added in the resin solution of step (c), stir (about 500 rev/mins) with homogenizer, system is mixed, make the fiber grain matrix material solution of antigen oxygen peeling.
Under room temperature state, the fiber grain matrix material solution of the above-mentioned antigen oxygen peeling that makes is soaked on glasscloth, and it was left standstill 48 hours in airiness place; Cutting at room temperature and lay-up carry out hot-forming (hot pressing condition is pressurize 1h under 80 ℃ of temperature, the pressure 7MPa) in the forming mould that scribbles releasing agent; In air, cool off the back demoulding, can obtain the glass fiber compound material thin plate of antigen oxygen peeling; Thin plate is cut into the square sample of 2cm * 2cm; In Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, carry out the atomic oxygen effect test of sample then, the antigen oxygen peeling performance of sample is estimated and analyzed from aspects such as outward appearance, mass loss and atomic oxygen erodes rate, surface topography, surface compositions.Test-results shows: this kind adds nanometer SiO 2The glass fibre thin plate of antigen oxygen peeling can significantly improve the antigen oxygen peeling performance of glass fibre/polyimide resin BMP316.Its antigen oxygen peeling results of property sees the following form:
Fiber/resin matrix Atomic oxygen erodes rate (cm 3/atom) Test shows
Before the interpolation After the interpolation (being reduced to)
Glass fibre/polyimide resin BMP316 1.40×10 -24 5 parts 0.77×10 -24 55.00%
10 parts 0.35×10 -24 25.00%
15 parts 0.20×10 -24 14.29%
Last atom oxygen denudation rate is more little, and the antigen oxygen peeling performance of material is good more.
Be added with the polyimide resin BMP316 complex fiber material sample of 15 parts of nanometer titanium dioxide silicon materials, its denudation rate is about 14.29% of polyimide resin BMP316 virgin resin, shows that this method can significantly improve the antigen oxygen peeling performance of polyimide resin BMP316 really.See also the forward and backward SEM photo of interpolation shown in Figure 5.
Add the polyimide resin BMP316 fibre composite sample of 5 parts or 10 parts nanometer titanium dioxide silicon materials after the same method, test-results shows that its denudation rate is about 55.00% or 25.00% of fiber/polyimide resin BMP316 respectively.
Embodiment 3
Choosing filamentary material is glasscloth,
Nano-particle material is SiO 2, properties-correcting agent is vinyltriethoxysilane A151
Polymer matrix composite is resol PF401, and the preparation method of employing embodiment 2 prepares the fiber grain matrix material of antigen oxygen peeling.
Fiber/resin matrix Atomic oxygen erodes rate (cm 3/atom) Test shows (being reduced to)
Before the interpolation After the interpolation
Glass fibre/resol PF401 2.50×10 -24 5 parts 1.05×l0-24 42.00%
15 parts 0.67×10 -24 26.80%
Embodiment 4
Nano-particle material is Al 2O 3, properties-correcting agent is γ-An Jibingjisanyiyangjiguiwan KH550,
Polymkeric substance is Resins, epoxy E51, and the preparation method of employing embodiment 1 prepares the particulate composite of antigen oxygen peeling.
Polymkeric substance Atomic oxygen erodes rate (cm 3/atom) Test shows (being reduced to)
Before the interpolation After the interpolation
Resins, epoxy E51 4.64×10 -24 5 parts 1.93×10 -24 41.59%
10 parts 1.02×l0 -24 21.98%
15 parts 0.53×10 -24 11.42%

Claims (7)

1、一种通过添加纳米颗粒材料来提高航天器用聚合物和聚合物基复合材料抗原子氧剥蚀性能的方法,其特征在于:按照比例,在反应釜中将聚合物或聚合物基复合材料的树脂基体、稀释剂和/或固化剂搅拌混合均匀,制得树脂溶液;再将经表面改性处理后的不与原子氧反应的纳米颗粒材料,在搅拌状态下加入到树脂溶液中,制得抗原子氧剥蚀复合材料溶液;将抗原子氧剥蚀复合材料溶液经成型工艺可制备出抗原子氧剥蚀的颗粒复合材料或者制备出抗原子氧剥蚀的纤维颗粒复合材料;1. A method for improving the anti-atomic oxygen ablation performance of polymers and polymer-based composite materials for spacecraft by adding nanoparticle materials, characterized in that: according to the proportion, the polymer or polymer-based composite materials are mixed in the reaction kettle Stir and mix the resin matrix, diluent and/or curing agent evenly to prepare a resin solution; then add the surface-modified nanoparticle material that does not react with atomic oxygen into the resin solution under stirring to obtain a The anti-atomic oxygen ablation composite material solution; the anti-atomic oxygen ablation composite material solution can be prepared through the molding process to prepare the anti-atomic oxygen ablation particle composite material or the anti-atomic oxygen ablation fiber particle composite material; 所述的抗原子氧剥蚀的颗粒复合材料的组成以重量计为:The composition of the particle composite material resistant to atomic oxygen ablation is by weight: (A)聚合物,用量为100份,该聚合物为环氧树脂或聚酰亚胺树脂或酚醛树脂或聚酰胺树脂或聚酯树脂或聚砜或聚醚醚酮或聚甲基丙烯酸甲酯;和(A) polymer, consumption is 100 parts, and this polymer is epoxy resin or polyimide resin or phenolic resin or polyamide resin or polyester resin or polysulfone or polyether ether ketone or polymethyl methacrylate ;and (B)纳米颗粒材料,用量为2~35份,该纳米颗粒材料为不与原子氧反应的二氧化硅或三氧化二铝或氧化锆或氧化锡或氧化钛经表面改性处理后的材料,其粒径5~100纳米;(B) nanoparticle material, the dosage is 2 to 35 parts, the nanoparticle material is silicon dioxide or aluminum oxide or zirconium oxide or tin oxide or titanium oxide that does not react with atomic oxygen after surface modification , with a particle size of 5 to 100 nanometers; 所述的抗原子氧剥蚀的纤维颗粒复合材料的组成以重量计为:The composition of the anti-atomic oxygen denudation fiber particle composite material is by weight: (A)聚合物基复合材料的树脂基体,用量为100份,该树脂基体为环氧树脂或聚酰亚胺树脂或酚醛树脂或聚酰胺树脂或聚酯树脂或聚砜或聚醚醚酮或聚甲基丙烯酸甲酯;和(A) The resin matrix of polymer matrix composite material, consumption is 100 parts, and this resin matrix is epoxy resin or polyimide resin or phenolic resin or polyamide resin or polyester resin or polysulfone or polyether ether ketone or polymethyl methacrylate; and (B)纳米颗粒材料,用量为2~35份,该纳米颗粒材料为不与原子氧反应的二氧化硅或三氧化二铝或氧化锆或氧化锡或氧化钛经表面改性处理后的材料,其粒径5~100纳米;和(B) nanoparticle material, the dosage is 2 to 35 parts, the nanoparticle material is silicon dioxide or aluminum oxide or zirconium oxide or tin oxide or titanium oxide that does not react with atomic oxygen after surface modification , with a particle size of 5 to 100 nanometers; and (C)纤维材料:碳纤维或玻璃纤维。(C) Fiber material: carbon fiber or glass fiber. 2、根据权利要求1所述的方法,其特征在于所述的抗原子氧剥蚀的颗粒复合材料的组成以重量计为:2. The method according to claim 1, characterized in that the composition of the particle composite material resistant to atomic oxygen ablation is by weight: (A)聚合物,用量为100份,该聚合物为环氧树脂或聚酰亚胺树脂;和(A) polymer, consumption is 100 parts, and this polymer is epoxy resin or polyimide resin; And (B)纳米颗粒材料,用量为2~20份,该纳米颗粒材料为不与原子氧反应的二氧化硅经表面改性处理后的材料,其粒径20~30纳米。(B) Nano particle material, the dosage is 2-20 parts, the nano particle material is silicon dioxide which does not react with atomic oxygen after surface modification treatment, and its particle size is 20-30 nanometers. 3、根据权利要求1所述的方法,其特征在于所述的抗原子氧剥蚀的纤维颗粒复合材料的组成以重量计为:3. The method according to claim 1, characterized in that the composition of the fiber particle composite material resistant to atomic oxygen denudation is by weight: (A)聚合物基复合材料的树脂基体,用量为100份,该树脂基体为环氧树脂或聚酰亚胺树脂或酚醛树脂;和(A) the resin matrix of the polymer-based composite material, the dosage is 100 parts, and the resin matrix is epoxy resin or polyimide resin or phenolic resin; and (B)纳米颗粒材料,用量为2~20份,该纳米颗粒材料为不与原子氧反应的二氧化硅经表面改性处理后的材料,其粒径20~30纳米;和(B) nanoparticle material, the dosage is 2 to 20 parts, the nanoparticle material is silicon dioxide that does not react with atomic oxygen after surface modification treatment, and its particle size is 20 to 30 nanometers; and (C)纤维材料:玻璃纤维。(C) Fiber material: glass fiber. 4、根据权利要求1所述的方法,其特征在于:原子氧剥蚀率降低为未添加纳米颗粒材料的50%~5%。4. The method according to claim 1, characterized in that the atomic oxygen ablation rate is reduced to 50%-5% of that of the non-added nanoparticle material. 5、根据权利要求2或3所述的方法,其特征在于:原子氧剥蚀率降低为未添加纳米颗粒材料的9.48%。5. The method according to claim 2 or 3, characterized in that the atomic oxygen ablation rate is reduced to 9.48% of that of the material without adding nanoparticles. 6、根据权利要求1所述的方法,其特征在于包括下列步骤:6. The method of claim 1, comprising the steps of: (a)制备纳米颗粒材料(a) Preparation of nanoparticle materials 选取不与原子氧反应的纳米颗粒材料;Select nanoparticle materials that do not react with atomic oxygen; 选取不与原子氧反应的纳米颗粒材料所需的表面改性剂,其表面改性剂是乙烯基三乙氧基硅烷或者γ-氨基丙基三乙氧基硅烷或者四异丙基(二辛基亚磷酸酯酰基)钛酸酯;Select the surface modifier required for the nanoparticle material that does not react with atomic oxygen, and its surface modifier is vinyltriethoxysilane or γ-aminopropyltriethoxysilane or tetraisopropyl (dioctyl Phosphite acyl) titanate; 按纳米颗粒材料∶表面改性剂=100∶0.5~5称取上述材料,制得纳米颗粒材料;Take the above-mentioned materials according to nanoparticle material: surface modifier=100: 0.5~5, make nanoparticle material; (b)称取聚合物或聚合物基复合材料的树脂基体和纳米颗粒材料(b) Weighing the resin matrix and nanoparticle material of the polymer or polymer-based composite 按聚合物或聚合物基复合材料的树脂基体∶纳米颗粒材料=100∶2~35称取;Take by weighing the resin matrix of polymer or polymer-based composite material: nano particle material = 100: 2~35; (c)制聚合物或聚合物基复合材料的树脂溶液(c) Resin solutions for polymers or polymer-based composites 选取聚合物或聚合物基复合材料的树脂基体;Select the resin matrix of the polymer or polymer-based composite; 选取稀释剂为丙酮;Choose thinner to be acetone; 选取固化剂为聚酰胺或三乙胺或己二胺或4,4’-二胺基二苯甲烷或2-甲基咪唑或顺丁烯二酸酐;Select curing agent to be polyamide or triethylamine or hexamethylenediamine or 4,4'-diaminodiphenylmethane or 2-methylimidazole or maleic anhydride; 按聚合物或聚合物基复合材料的树脂基体∶固化剂∶稀释剂=100∶0~70∶40~80称取上述材料,并将其放入反应釜中搅拌混合均匀,制得聚合物或聚合物基复合材料的树脂溶液;According to the resin matrix of the polymer or polymer-based composite material: curing agent: diluent = 100: 0~70: 40~80, weigh the above-mentioned materials, put them into the reaction kettle and stir and mix them evenly to obtain the polymer or Resin solutions for polymer matrix composites; (d)制抗原子氧剥蚀复合材料溶液(d) Preparation of atomic oxygen ablation composite material solution 在配制好上述(c)溶液后,在搅拌中添加入上述(a)中的纳米颗粒材料,制得抗原子氧剥蚀复合材料溶液;After preparing the above (c) solution, add the nanoparticle material in the above (a) while stirring to prepare the anti-atomic oxygen ablation composite material solution; (e)制抗原子氧剥蚀颗粒复合材料或抗原子氧剥蚀纤维颗粒复合材料(e) Preparation of anti-atomic oxygen ablation particle composite material or anti-atomic oxygen ablation fiber particle composite material 经成型工艺制出抗原子氧剥蚀颗粒复合材料或抗原子氧剥蚀纤维颗粒复合材料。Anti-atomic oxygen ablation granule composite material or anti-atomic oxygen ablation fiber particle composite material is produced through molding process. 7、根据权利要求6所述的制备抗原子氧剥蚀复合材料的方法,其特征在于:通过溶液浇铸工艺将(d)步骤中溶液制得膜状抗原子氧剥蚀颗粒复合材料;或者通过层压成型工艺将(d)步骤中溶液制得层压板型抗原子氧剥蚀纤维颗粒复合材料。7. The method for preparing an anti-atomic oxygen ablation composite material according to claim 6, characterized in that: the film-like anti-atomic oxygen ablation particle composite material is prepared from the solution in step (d) through a solution casting process; or by lamination Forming process The solution in step (d) is used to prepare a laminated plate type anti-atomic oxygen ablation fiber particle composite material.
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