CN1865350A - Organic-inorganic hybridized nano composite material resisting atomic oxygen denudation and its preparation method - Google Patents
Organic-inorganic hybridized nano composite material resisting atomic oxygen denudation and its preparation method Download PDFInfo
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- CN1865350A CN1865350A CN 200510011722 CN200510011722A CN1865350A CN 1865350 A CN1865350 A CN 1865350A CN 200510011722 CN200510011722 CN 200510011722 CN 200510011722 A CN200510011722 A CN 200510011722A CN 1865350 A CN1865350 A CN 1865350A
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Abstract
The invention discloses an anti-oxygen atom denudation organic-inorganic hybridization nanometer composite material and preparing method, which comprises the following steps: blending modified surface disposed nanometer inorganics or priority with polymer solution or priority solution according to certain proportion; producing anti-oxygen atom denudation polymerization and inorganic nanometer hybridization material through fitful moulding technology. The method can reduce the atom oxygen denudation rate than non-hybridization inorganic nanometer particle material by 80-5 percent when the oxygen atom accumulating quantity is 5.05*1020atom/cm2, which solves serious problem that the spacecraft polymerization material is eroded by oxygen atom.
Description
Technical field
The present invention relates to inorganic-organic hybridization nano matrix material of a kind of antigen oxygen peeling and preparation method thereof, specifically, be meant, obtain the polymer-based carbon hybrid composite material that the antigen oxygen peeling performance improves inorganic nano-particle and polymer hybrid.
Background technology
Growing along with exploitation, the demand of utilizing space resources, the quantity of Low Earth Orbit spacecrafts such as man-made satellite, space station increases gradually, and abominable space environment has also proposed more harsh requirement to the spacecraft of long life and high reliability.Compare with traditional metallic substance, polymer materials is all even better at aspects such as weight, specific tenacity, specific rigidity, reliability, thermal expansivity, wearing quality and wear resistancies, the operational efficiency that more help reducing launch cost, improves spacecraft is so polymer materials is more and more widely as spacecraft surfacing and structured material.Yet most of polymkeric substance and polymer matrix composite can be subjected to seriously degrading of atomic oxygen in the Low Earth Orbit environment, and the thickness of material and quality can be lost, and performance also can be degenerated, thereby influences the works better and the work-ing life of spacecraft.In order to ensure that spacecraft moves reliably and with long-term at rail, 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, the means of defence of raising spacecraft material antigen oxygen peeling performance mainly contains:
(1) applies the anti-atomic oxygen protective coating.Applying protective coating is a convenient valid approach, but the coating performance that the space is used is strict, specifically comprises: (1) can provide the ability of good antigen oxygen peeling, and should not change the fundamental property of body material; (2) not only thin but also light and firm with matrix bond; (3) there are not defective, pore and slight crack; (4) has good counter-bending and antistrip performance; (5) when Low Earth Orbit environment long-term exposure, can keep stability; (6) has very low volatility and should satisfy the vacuum exhaust requirement; (7) technology of preparation coating satisfies with low cost and the efficient height, and easily expands on the large-size workpiece.U.S. Pat 4939031, US4980206, US5312685 and US6872457 etc. disclose the sub-oxygen protective coating of several effective antigens, but still can not satisfy above-mentioned requirements simultaneously, subject matter is: the thermal expansivity of (1) coating and primer is different can to cause material interlayer division under the effect of long term thermal round-robin, thereby makes coatingsurface crackle occur; (2) 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.So an important research direction of protective coating is that development half organic or inorganic polymkeric substance is main self-healing protective coating, can produce the stable oxide-base top layer with protective value or other stable surface tissues when reacting with atomic oxygen.
(2) change the elementary composition of material surface.Mainly be to melt by ion implantation, electron irradiation, laser to cover etc. that method metallizes to material surface or silanization is handled the surface-element that changes material and formed, make its surface contain abundant aluminium, silicon plasma, thereby make material under the effect of space atomic oxygen, 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 exists at material surface, equally also can lose efficacy when suffering the bump of micrometeorite and rubbish fragment; 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, as the described method of U.S. Pat 6841652 B2.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.
(4) add the antigen oxygen peeling component by blend or copolymerization.This method is used convenient, and suitability is good, has become present invention focus.For example, Chinese patent CN 1583874A discloses a kind of method that improves spacecraft usefulness polymkeric substance and polymer matrix composite antigen oxygen peeling performance by the interpolation nano-particle material; U.S. Pat 5073607 discloses a kind of organosilane polymer segmental polyimide component that comprises and has improved the antigen oxygen peeling performance; U.S. Pat 5304627 discloses a kind of new type polyimide PISOX that contains the siloxanes active end group, can significantly improve the antigen oxygen peeling performance of material.But the common issue with that above patent exists is: change has taken place in the fundamental property of body material, and when adding inorganic particulate material, mechanical property such as bending resistance can reduce usually; When adding the siloxanes segment, tensile strength can reduce usually.
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, provide a kind of polymer/inorganic thing nano-hybrid material that can significantly improve spacecraft material antigen oxygen peeling performance and preparation method thereof.
The present invention relates to inorganic-organic hybridization nano matrix material of a kind of antigen oxygen peeling and preparation method thereof, it is according to certain ratio, make nano-inorganic substance or nano-inorganic substance presoma and polymers soln or polybenzazole precursor liquid solution uniform mixing under whipped state through surface modification treatment, utilize proper molding then, prepare the polymer/inorganic thing nano-hybrid material of antigen oxygen peeling.
The consisting of of the hybrid material of described antigen oxygen peeling (by weight),
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～45 part, be preferably 5～20 parts, more preferably 10～15 parts, this inorganic nano-particle be not with the oxide compound of atomic oxygen reaction, specifically can be silicon-dioxide, titanium dioxide, aluminium sesquioxide etc., be preferably silicon-dioxide, titanium dioxide, generated by its presoma original position in polymeric matrix, particle diameter is 5～100 nanometers.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by the hybridized nanometer oxide particle
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms and homodisperse.
The consisting of of the hybrid material of described antigen oxygen peeling (by weight),
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～10 part, be preferably 2～8 parts, more preferably 3～5 parts, this inorganic nano-particle be not with the nitride of atomic oxygen reaction, specifically can be aluminium nitride, boron nitride, silicon nitride etc., be preferably aluminium nitride, boron nitride, be dispersed in after surface modification treatment in the polymeric matrix, particle diameter is 5～100 nanometers.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by the hybridized nanometer nitride particles
(a) preparation inorganic nano-particle and it is carried out surface modification treatment, employed surface-modifying agent can be silane coupling agent or titanate coupling agent, wherein silane coupling agent such as vinyltriethoxysilane A151 or γ-An Jibingjisanyiyangjiguiwan KH550, titanate coupling agent such as tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester NDZ-401, the coupling agent consumption is 1% (by weight) of inorganic nano-particle;
(b) preparation polymers soln or polybenzazole precursor liquid solution, and even with inorganic nano-particle thorough mixing through surface modification treatment;
(c) utilize proper molding to make the antigen oxygen peeling hybrid material.
The consisting of of the hybrid material of described antigen oxygen peeling (by weight),
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～25 part, be preferably 3～10 parts, more preferably 5～7 parts, this inorganic nano-particle be with or not with the monoatomic metal of atomic oxygen reaction, specifically can be silver, aluminium, gold, copper etc., be preferably silver, aluminium, generated by its presoma original position in polymeric matrix, particle diameter is 5～100 nanometers.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by hybridized nanometer monoatomic metal particle
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms.
Hybrid composite material of the present invention has the following advantages: has certain chemistry, physical action between (1) inorganic nano-particle and polymeric matrix, guaranteed inorganic abundant dispersion in organic phase, or homodisperse or dispersion in gradient; (2) when bearing atomic oxygen irradiation, can produce stable oxide compound or nitride top layer or other stable surface tissues after the top layer composition of material and the atomic oxygen reaction with protective value, promptly have self-healing ability, thereby stop the further erosion of atomic oxygen; With the antigen oxygen peeling hybrid composite material that this kind method is prepared, be 5.05 * 10 at the atomic oxygen fluence
20Atom/cm
2The time, the atomic oxygen erodes rate is reduced to 80%～5% of hybrid inorganic nanometer particle material not, 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 (a) is the FE-SEM photo (amplify 30000 times) of pure polyimide (PMDA/ODA system) film before the atomic oxygen effect test.
Fig. 1 (b) is that pure polyimide (PMDA/ODA system) film is at the FE-SEM photo (amplify 30000 times) of atomic oxygen effect test after 20 hours.
Fig. 2 (a) is 15 parts of nanometer SiO of hydridization
2The FE-SEM photo (amplify 30000 times) of polyimide (PMDA/ODA system) hybrid composite material film before the atomic oxygen effect test.
Fig. 2 (b) is 15 parts of nanometer SiO of hydridization
2Polyimide (PMDA/ODA system) hybrid composite material film at the FE-SEM photo (amplify 30000 times) of atomic oxygen effect test after 20 hours.
Fig. 3 (a) is the FE-SEM photo (amplify 30000 times) of polyimide (PMDA/ODA system) hybrid composite material film before the atomic oxygen effect test of 5 parts of nanometer AlN of hydridization.
Fig. 3 (b) is that polyimide (PMDA/ODA system) the hybrid composite material film of 5 parts of nanometer AlN of hydridization is at the FE-SEM photo (amplify 30000 times) of atomic oxygen effect test after 20 hours.
Fig. 4 (a) be copolyimide (BTDA/BPDA/3,4 '-the ODA system) the FE-SEM photo (amplify 30000 times) of film before the atomic oxygen effect test.
Fig. 4 (b) be copolyimide (BTDA/BPDA/3,4 '-the ODA system) film is at the FE-SEM photo (amplify 30000 times) of atomic oxygen effect test after 20 hours.
Fig. 5 (a) be 5 parts of nanometer Ag of hydridization copolyimide (BTDA/BPDA/3,4 '-the ODA system) the FE-SEM photo (amplify 30000 times) of hybrid composite material film before the atomic oxygen effect test.
Fig. 5 (b) be 5 parts of nanometer Ag of hydridization copolyimide (BTDA/BPDA/3,4 '-the ODA system) the hybrid composite material film is at the FE-SEM photo (amplify 30000 times) of atomic oxygen effect test after 20 hours.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
In the present invention, inorganic nano-particle be meant its presoma and polymers soln or polybenzazole precursor liquid solution thorough mixing evenly the back in the forming polymer process generated in-situ inorganic nano-particle and after surface modification treatment again with polymers soln or polybenzazole precursor liquid solution thorough mixing uniformly not with the inorganic nano-particle of atomic oxygen reaction.
Inorganic-organic hybridization nano matrix material of a kind of antigen oxygen peeling of the present invention and preparation method thereof, it is according to certain ratio, make nano-inorganic substance and polymers soln or polybenzazole precursor liquid solution uniform mixing under whipped state of nano-inorganic substance presoma or process surface modification treatment, utilize proper molding then, prepare the polymer/inorganic thing nano-hybrid material of antigen oxygen peeling.
The consisting of of the hybrid material of described antigen oxygen peeling (by weight),
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～45 part, be preferably 5～20 parts, more preferably 10～15 parts, this inorganic nano-particle be not with the oxide compound of atomic oxygen reaction, specifically can be silicon-dioxide, titanium dioxide, aluminium sesquioxide etc., be preferably silicon-dioxide, titanium dioxide, generated by its presoma original position in polymeric matrix, particle diameter is 5～100 nanometers.
Another the consisting of (by weight) of the hybrid material of described antigen oxygen peeling,
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～10 part, be preferably 2～8 parts, more preferably 3～5 parts, this inorganic nano-particle be not with the nitride of atomic oxygen reaction, specifically can be aluminium nitride, boron nitride, silicon nitride etc., be preferably aluminium nitride, boron nitride, be dispersed in after surface modification treatment in the polymeric matrix, particle diameter is 5～100 nanometers.
The hybrid material of described antigen oxygen peeling one consist of (by weight) again,
(A) polymkeric substance, consumption is 100 parts, this polymkeric substance is a polyimide resin, specifically can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide; With
(B) inorganic nano-particle, consumption is 1～25 part, is preferably 3～10 parts, more preferably 5～7 parts, this inorganic nano-particle is a monoatomic metal, specifically can be silver, aluminium, gold, copper etc., be preferably silver, aluminium, generated by its presoma original position in polymeric matrix, particle diameter is 5～100 nanometers.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by the hybridized nanometer oxide particle
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms and homodisperse.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by the hybridized nanometer nitride particles
(a) preparation inorganic nano-particle and it is carried out surface modification treatment, employed surface-modifying agent can be silane coupling agent or titanate coupling agent, wherein silane coupling agent such as vinyltriethoxysilane A151 or γ-An Jibingjisanyiyangjiguiwan KH550, titanate coupling agent such as tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester NDZ-401, the coupling agent consumption is 1% (by weight) of inorganic nano-particle;
(b) preparation polymers soln or polybenzazole precursor liquid solution, and even with inorganic nano-particle thorough mixing through surface modification treatment;
(c) utilize proper molding to make the antigen oxygen peeling hybrid material.
Describedly improve spacecraft with polymkeric substance and polymer matrix composite antigen oxygen peeling performance methodology, comprise the following steps: by hybridized nanometer monoatomic metal particle
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms.
Hybrid technique of the present invention is the technology of conventional preparation mixture material, just the kind and the consumption of employed monomer and/or additive is adjusted to some extent.Product of the present invention can pass through casting molding process or extruding-out process or injection molding process or blow molding technology or die press technology for forming moulding.
Embodiment 1
Polyimide resin (PMDA/ODA system) 100 parts of consumptions (by weight), nano silicon (SiO
2) 15 parts of hybrid composite materials that prepare antigen oxygen peeling of particle.
The preparation method is as described below:
(a) preparation polymers soln or polybenzazole precursor liquid solution
At first, the pyromellitic dianhydride (PMDA) and the 4 (ODA) of amount of substance such as taking by weighing, is that 20wt% calculates required solvent N according to institute's resulting solution solid content, and the amount of N '-N,N-DIMETHYLACETAMIDE (DMAC) is also measured.Secondly, under the room temperature, in the three-necked bottle, ODA fully is dissolved among the DMAc, limpid with solution, lose particulate matter and be as the criterion.The 3rd, PMDA is added in this solution in batches, each adding all needs time enough that PMDA is fully reacted, and adds next batch then, finishes until total overall reaction, continues to stir 6h, obtains even heavy-gravity presoma polyamic acid (PAA) solution.
(b) mix the presoma of inorganic nano-particle and stirring
According to expection SiO
2The amount of the required presoma tetraethyl orthosilicate of cubage (TEOS) also takes by weighing, and TEOS is joined in the PAA solution, continues to stir 12h, obtains PAA/TEOS solution.
(c) inorganic nano-particle original position in the forming polymer process forms and homodisperse
Under room temperature state, with above-mentioned precursor solution, water on the sheet glass that casts from cleaning, use to be tied with the uniform fluid film of thickness that glass stick wiry scrapes the about 0.25mm of one deck; Level is transferred in the far infrared drying oven after placing vacuum drying oven to carry out room temperature vacuum-drying 24h, begins to heat up, and heating schedule is: 50 ℃/1h → 100 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/0.5h → 300 ℃/0.5h.After heat up finishing, the sample furnace cooling takes out to room temperature, and demoulding can obtain the polyimide/silicon dioxide nano hybrid composite material film of antigen oxygen peeling; Film is cut into the square sample of 1cm * 1cm, 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 microscopic topographic, surface compositions.Test after 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: this kind hybridized nanometer Si0
2The hybrid composite material film of antigen oxygen peeling can significantly improve the antigen oxygen peeling performance of polyimide resin.Its antigen oxygen peeling results of property is seen
Following table:
| Type of polymer | The hybrid particle kind | Atomic oxygen erodes rate (* 10 -24cm 3/atom) | Test shows (being reduced to) | ||
| Before the hydridization | After the hydridization | ||||
| Polyimide resin (PMDA/ODA system) | Nano silicon | 2.829 | 5 parts | 0.919 | 32.48％ |
| 10 parts | 0.778 | 27.50％ | |||
| 15 parts | 0.448 | 15.82％ | |||
Last atom oxygen denudation rate is more little, and the antigen oxygen peeling performance of material is good more.
Hydridization has the polyimide hybrid matrix material sample of 15 parts of nano-silicon dioxide particles, and its denudation rate is about 15.82% of pure polyimide resin, shows that this method can significantly improve the antigen oxygen peeling performance of polyimide really.
Referring to the FE-SEM photo before and after Fig. 1, the hydridization shown in Figure 2, hybrid film is behind the atomic oxygen effect test, and the surface has formed fine and close from level to level SiO
2Network, the polyimide resin matrix of protection bottom is not subjected to atomic oxygen erosion.
The polyimide hybrid matrix material sample of 5 parts or 10 parts nano-silicon dioxide particles of hydridization after the same method, the result of test in 20 hours shows that its denudation rate is about 32.48% or 27.50% of pure polyimide resin respectively.
Polyimide resin (PMDA/ODA system) 100 parts of consumptions (by weight), the hybrid composite material of 5 parts of preparations of nano aluminum nitride (AlN) particle antigen oxygen peeling.
The preparation method is as described below:
(a) take by weighing desired raw material
The pyromellitic dianhydride (PMDA) and the 4 (ODA) of amount of substance such as taking by weighing, is that 20wt% calculates required N according to institute's resulting solution solid content, and the amount of N '-N,N-DIMETHYLACETAMIDE (DMAC) is also measured; According to the amount of expection nanometer AlN cubage required nanometer AlN and take by weighing; (nanometer AlN: ratio coupling agent) was measured surface-modifying agent γ-An Jibingjisanyiyangjiguiwan KH550 according to 100: 1 according to the amount of nanometer AlN.
(b) inorganic nano-particle is carried out surface modification treatment
Under the room temperature, in the three-necked bottle, add nanometer AlN, KH550 and DMAc, under the effect that ultrasonic wave and high speed machine stir, nanometer AlN is dispersed among the DMAc, the reference time is 30min, and is limpid with solution, lose or almost lose pale powder and be as the criterion.
(c) preparation polymers soln or polybenzazole precursor liquid solution
In the above-mentioned suspension that nanometer AlN is carried out surface modification treatment, add ODA, under the effect that high speed machine stirs, ODA fully is dissolved among the DMAc, limpid with solution, lose particulate matter and be as the criterion; PMDA is added in batches, and each adding all needs time enough that PMDA is fully reacted, and adds next batch then, finishes until total overall reaction, continues to stir 6h, obtains even, heavy-gravity nano-AlN/PAA/DMAc emulsion.
(d) utilize proper molding to make the antigen oxygen peeling hybrid material
Under room temperature state, with above-mentioned precursor solution, water on the sheet glass that casts from cleaning, use to be tied with the uniform fluid film of thickness that glass stick wiry scrapes the about 0.25mm of one deck; Level is transferred in the far infrared drying oven after placing vacuum drying oven to carry out room temperature vacuum-drying 24h, begins to heat up, and heating schedule is: 50 ℃/1h → 100 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/0.5h → 300 ℃/0.5h.After heat up finishing, the sample furnace cooling takes out to room temperature, and demoulding can obtain the polyimide/aluminum nitride nanometer hybrid composite material film of antigen oxygen peeling; Film is cut into the square sample of 1cm * 1cm, 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 microscopic topographic, surface compositions.Test after 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the hybrid composite material film of the antigen oxygen peeling of this kind hybridized nanometer AlN can significantly improve the antigen oxygen peeling performance of polyimide resin.Its antigen oxygen peeling results of property is seen
Following table:
Last atom oxygen denudation rate is more little, and the antigen oxygen peeling performance of material is good more.
| Type of polymer | The hybrid particle kind | Atomic oxygen erodes rate (* 10 -24cm 3/atom) | Test shows (being reduced to) | ||
| Before the hydridization | After the hydridization | ||||
| Polyimide resin (PMDA/ODA system) | Nano aluminum nitride | 2.829 | 2 parts | 2.263 | 80.00％ |
| 3 parts | 1.626 | 57.48％ | |||
| 5 parts | 1.273 | 45.00％ | |||
Hydridization has the polyimide hybrid matrix material sample of 5 parts of nano silicon nitride aluminum particulates, and its denudation rate is about 45.00% of pure polyimide resin, shows that this method can significantly improve the antigen oxygen peeling performance of polyimide really.
Referring to the FE-SEM photo before and after Fig. 1, the hydridization shown in Figure 3, hybrid film is behind the atomic oxygen effect test, and the surface has formed the AlN tectum of one deck densification, and the polyimide resin matrix of protection bottom is not subjected to atomic oxygen erosion.
The polyimide hybrid matrix material sample of 2 parts or 3 parts nano-silicon dioxide particles of hydridization after the same method, the result of test in 20 hours shows that its denudation rate is about 80.00% or 57.48% of pure polyimide resin respectively.
Polyimide resin (BTDA/BPDA/3,4 '-the ODA copolymerization system) 100 parts of consumptions (by weight), the hybrid composite material of 5 parts of preparations of nanometer silver (Ag) particle antigen oxygen peeling.
The preparation method is as described below:
(a) preparation polymers soln or polybenzazole precursor liquid solution
At first, ratio according to the amount of substance of expection molecular weight (25000) and two kinds of dianhydrides calculates required 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 3,3 ', 4,4 '-amount of benzophenone tetracarboxylic acid anhydride (BTDA), biphenyl tetracarboxylic acid anhydrides (BPDA) and end-capping reagent Tetra hydro Phthalic anhydride (PA) and taking by weighing, according to institute's resulting solution solid content is that 20wt% calculates required solvent N, and the amount of N '-N,N-DIMETHYLACETAMIDE (DMAC) is also measured.Secondly, under the ice-water bath cooling, in the three-necked bottle, make 3,4 '-ODA fully is dissolved among the DMAc, and is limpid with solution, lose particulate matter and be as the criterion.The 3rd, ODPA, BPDA are added in this solution successively in batches, each adding all needs time enough that BTDA or BPDA are fully reacted, and adds next batch then, finishes until total overall reaction.The 4th, keep the ice-water bath cooling, slowly add PA, continue to stir 8h, obtain presoma polyamic acid (PAA) solution.
(b) mix the presoma of inorganic nano-particle and stirring
Calculate required presoma Silver Nitrate (AgNO according to expection Ag particle content
3) amount and take by weighing.Remove the ice-water bath of above-mentioned solution when synthetic, treat that solution returns to room temperature, AgNO
3Join in the PAA solution, continue to stir 4h, obtain PAA/AgNO
3Solution.
Because AgNO
3See that light easily decomposes, therefore need take corresponding lucifuge measure in this stage.
(c) inorganic nano-particle original position in the forming polymer process forms
Under room temperature state, with above-mentioned precursor solution, water on the sheet glass that casts from cleaning, use to be tied with the uniform fluid film of thickness that glass stick wiry scrapes the about 0.25mm of one deck; After level places and carries out drying at room temperature 18h on the lucifuge experiment table, (far-infrared radiation source needs to cover with division board to be transferred to far infrared drying oven, avoid its direct radiation to film) in, begin to heat up, heating schedule is: 50 ℃/1h → 100 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/1h → 300 ℃/1h.After heat up finishing, the sample furnace cooling takes out to room temperature, and demoulding can obtain the polyimide/silver nano hybrid composite material film of antigen oxygen peeling; Film is cut into the square sample of 1cm * 1cm, 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 microscopic topographic, surface compositions.Test after 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the hybrid composite material film of the antigen oxygen peeling of this kind hybridized nanometer Ag can significantly improve the antigen oxygen peeling performance of polyimide resin.Its antigen oxygen peeling results of property sees the following form:
| Type of polymer | The hybrid particle kind | Atomic oxygen erodes rate (* 10 -24cm 3/atom) | Test shows (being reduced to) | ||
| Before the hydridization | After the hydridization | ||||
| Polyimide resin (BTDA/BPDA/3,4 '-the ODA copolymerization system) | Nanometer silver | 2.192 | 5 parts | 1.131 | 51.60％ |
| 6 parts | 1.011 | 46.12％ | |||
| 7 parts | 0.919 | 41.92％ | |||
Last atom oxygen denudation rate is more little, and the antigen oxygen peeling performance of material is good more.
Hydridization has the polyimide hybrid matrix material sample of 5 parts of nano silver particles, and its denudation rate is about 51.60% of pure polyimide resin, shows that this method can significantly improve the antigen oxygen peeling performance of polyimide really.
Referring to the FE-SEM photo before and after Fig. 4, the hydridization shown in Figure 5, hybrid film is behind the atomic oxygen effect test, and the surface has formed fine and close from level to level Ag
2The O tectum, the polyimide resin matrix of protection bottom is not subjected to atomic oxygen erosion.
The polyimide hybrid matrix material sample of 6 parts or 7 parts nano silver particles of hydridization after the same method, the result of test in 20 hours shows that its denudation rate is about 46.12% or 41.92% of pure polyimide resin respectively.
Claims (10)
1. inorganic-organic hybridization nano matrix material of an antigen oxygen peeling and preparation method thereof, it is characterized in that: according to certain ratio, make nano-inorganic substance or nano-inorganic substance presoma and polymers soln or polybenzazole precursor liquid solution uniform mixing under whipped state through surface modification treatment, utilize proper molding then, prepare the polymer/inorganic thing nano-hybrid material of antigen oxygen peeling.
2. method according to claim 1 is characterized in that: the consisting of of the hybrid material of described antigen oxygen peeling, each component concentration by weight,
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a polyimide resin; With
(B) inorganic nano-particle, consumption are 1～45 part, this inorganic nano-particle be not with the oxide compound of atomic oxygen reaction, generate by its presoma original position in polymeric matrix, particle diameter is 5～100 nanometers.
3. method according to claim 1 is characterized in that: the consisting of of the hybrid material of described antigen oxygen peeling, each component concentration by weight,
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a polyimide resin; With
(B) inorganic nano-particle, consumption are 1～10 part, this inorganic nano-particle be not with the nitride of atomic oxygen reaction, after surface modification treatment, be dispersed in the polymeric matrix, particle diameter is 5～100 nanometers.
4. method according to claim 1 is characterized in that: the consisting of of the hybrid material of described antigen oxygen peeling, each component concentration by weight,
(A) polymkeric substance, consumption are 100 parts, and this polymkeric substance is a polyimide resin; With
(B) inorganic nano-particle, consumption are 1～25 part, and this inorganic nano-particle is a monoatomic metal, are generated by its presoma original position in polymeric matrix, and particle diameter is 5～100 nanometers.
5. according to each described method in the claim 1～4, it is characterized in that: polyimide resin can be various thermoplastic polyimide or Thermocurable polyimides such as equal benzene type polyimide, biphenyl polyimide, PMR type polyimide, bismaleimides, polyetherimide, polyetherketone imide, polyamidoimide, copolyimide.
6. according to each described method in the claim 1～4, it is characterized in that: at the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2The time, the atomic oxygen erodes rate is reduced to 80%～5% of hybrid inorganic nanometer particle material not.
7. method according to claim 1 and 2 is characterized in that: described method comprises the following steps:
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms and homodisperse.
8. according to claim 1 or 3 described methods, it is characterized in that comprising the following steps:
(a) preparation inorganic nano-particle and it is carried out surface modification treatment, employed surface-modifying agent can be silane coupling agent or titanate coupling agent, wherein silane coupling agent such as vinyltriethoxysilane A151 or γ-An Jibingjisanyiyangjiguiwan KH550, titanate coupling agent such as tetra isopropyl (dioctyl phosphorous acid ester acyl group) titanic acid ester NDZ-401, the coupling agent consumption is 1% (by weight) of inorganic nano-particle;
(b) preparation polymers soln or polybenzazole precursor liquid solution, and even with inorganic nano-particle thorough mixing through surface modification treatment;
(c) utilize proper molding to prepare the antigen oxygen peeling hybrid material.
9. method according to claim 1 is characterized in that: described method comprises the following steps:
(a) preparation polymers soln or polybenzazole precursor liquid solution;
(b) mix the presoma of inorganic nano-particle and stirring;
(c) inorganic nano-particle original position in the forming polymer process forms.
10. according to each described method for preparing the antigen oxygen peeling matrix material in the claim 6～8, it is characterized in that: proper molding is casting molding process, extruding-out process, injection molding process, blow molding technology or die press technology for forming.
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| CN102093713B (en) * | 2009-12-10 | 2013-02-13 | 财团法人工业技术研究院 | Heat dissipation composite material |
| CN105151324A (en) * | 2015-09-22 | 2015-12-16 | 上海卫星工程研究所 | Space-based imaging radar satellite elemental oxygen shielding device and using method thereof |
| CN107201034A (en) * | 2017-04-24 | 2017-09-26 | 中国科学院宁波材料技术与工程研究所 | A kind of anti-reflection polymer composite film with elemental oxygen degradation resistant and preparation method thereof |
| CN111732869A (en) * | 2020-07-03 | 2020-10-02 | 北京航空航天大学 | Composition for resisting atomic oxygen denudation and preparation method and application thereof |
| CN114149700A (en) * | 2021-11-30 | 2022-03-08 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
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| CN102093713B (en) * | 2009-12-10 | 2013-02-13 | 财团法人工业技术研究院 | Heat dissipation composite material |
| CN105151324A (en) * | 2015-09-22 | 2015-12-16 | 上海卫星工程研究所 | Space-based imaging radar satellite elemental oxygen shielding device and using method thereof |
| CN107201034A (en) * | 2017-04-24 | 2017-09-26 | 中国科学院宁波材料技术与工程研究所 | A kind of anti-reflection polymer composite film with elemental oxygen degradation resistant and preparation method thereof |
| CN107201034B (en) * | 2017-04-24 | 2019-10-18 | 中国科学院宁波材料技术与工程研究所 | A kind of anti-reflection polymer composite film and preparation method thereof with elemental oxygen degradation resistant |
| CN111732869A (en) * | 2020-07-03 | 2020-10-02 | 北京航空航天大学 | Composition for resisting atomic oxygen denudation and preparation method and application thereof |
| CN114149700A (en) * | 2021-11-30 | 2022-03-08 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
| CN114149700B (en) * | 2021-11-30 | 2022-07-05 | 北京卫星制造厂有限公司 | Atomic oxygen resistant coating prepared by sol-gel method and method |
| CN115772363A (en) * | 2022-12-27 | 2023-03-10 | 山西碳中和战略创新研究院有限公司 | Nano coating with high radiation heat exchange capacity and construction method |
| CN115772363B (en) * | 2022-12-27 | 2024-02-13 | 山西碳中和战略创新研究院有限公司 | Nano coating with high radiation heat exchange capability and construction method |
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