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.
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% |