CN1709974A - Antioxidant silver hybrid polyimide reflective film and its preparing method - Google Patents
Antioxidant silver hybrid polyimide reflective film and its preparing method Download PDFInfo
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- CN1709974A CN1709974A CN 200510012044 CN200510012044A CN1709974A CN 1709974 A CN1709974 A CN 1709974A CN 200510012044 CN200510012044 CN 200510012044 CN 200510012044 A CN200510012044 A CN 200510012044A CN 1709974 A CN1709974 A CN 1709974A
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Abstract
The invention provides a kind of anti-oxidable silver intermixed reflecting membrane. Firstly produce silver intermixed reflecting membrane of high surface reflectivity through in-situ one step metallized method, and smear anti-oxidation coat on reflecting surface of the reflection membrane, to produce silver intermixed reflecting membrane of high reflectivity and anti-oxidation. Its total reflectivity at 530 nm wavelength can get 93%, and the effect of anti-oxidation coat to reflectivity. The reflectivity of reflecting membrane without smearing anti-oxidation coat will have a certain extent reduction after placed in air at room temperature for 48 hours, and has no reflectivity after exposal by oxygen atom for 20 hours; the reflectivity of reflecting membrane smeared by anti-oxidation coat won't reduce after placed in air at room temperature for 48 hours, and still has high reflectivity after exposal by oxygen atom for 20 hours. Therefore the anti-oxidation coat has good anti-oxidation effect.
Description
Technical field
The present invention relates to a kind of antioxidant silver hybrid polyimide reflective film, specifically, be meant that (1) utilizes one step of original position self-metallization legal system to be equipped with the silver hybrid polyimide reflective film that the surface has highly reflective; (2), prepare the silver hybrid polyimide reflective film that not only has highly reflective but also have oxidation-resistance in the certain thickness oxidation resistant coating of silver hybrid polyimide reflective film surface-coated.
Background technology
Along with the development of aerospace cause and the raising of advanced optics accuracy of instrument requirement, people are devoted to seek a kind of lightweight, high-strength, high temperature resistant always, and the surface has the thin-film material of excellent optical property, and therefore the research of polymer surfaces metalized synthetic material also receive publicity.Because polyimide (PI) has excellent thermal characteristics, mechanical property, radiation resistance and chemical resistance, and argent (Ag) has high luminous reflectance factor (reflectivity of silverskin when wavelength 800nm can reach 99.2%), therefore, PI/Ag composite reflection mould material is the multifunctional material that this field has research future and using value most.This material not instrument be expected effectively to solve and avoid spacecraft leave and the process of Returning ball in the major accident that comes off and cause between owing to outer cover metallic reflection face and refractory layer, but also show huge application potential in other many fields, as huge speculum in the heat control material of spacecraft, lightweight optical frames, the sun dynamic power equipment, rely on the reverberator on the workable gamma ray telescope of the sun in the space, can also be applied to reach as flexible reverberator and lightweight flexible optical frames in adaptivity or the elastooptics equipment.
In the research work in the past, the reflectance coating that uses one step of original position self-metallization legal system to be equipped with surperficial patina has been obtained certain progress.1963, (US 3 in patent for Endrey, 073,784) in first with silver (I) carboxylate salt join in-situ reducing in the polyamic acid, claim in the patent silver salt of multiple carboxylic acid such as formic acid, acetate, propionic acid, Succinic Acid, toxilic acid, citric acid etc. is joined in different types of polyamic acid solution, yet silver salt has only silver acetate, sad silver in example, polyamic acid is pyromellitic acid dianhydride (PMDA)/4,4 '-two amido ditane (p, p '-MDA) and PMDA/ mphenylenediamine (m-PDA), solvent is DMF.X-ray diffraction shows that silver (I) is reduced to Ag (0), but does not mention reflexive test data in the patent.1997, United States Patent (USP) prepared the self-metallization polyimide reflective film in (US5,677,418).The special case of the silver carboxylate compound that contains 1-6 carbon atom in the patent is a silver acetate; The solubilizing agent special case of Ag-containing compound is a hexafluoroacetylacetone; The polyimide resin solution that uses comprises polyamic acid solution and soluble polyimide resin solution.Use the Ag-containing compound hybrid polyimide resin of solubilising, obtain the Kapton that the surface has highly reflective after the curing.This patent has used 2 in example, 2 '-two (3, the 4-dicarboxylic acid) two (3-amino-benzene oxygen) benzene (6FDA/APB) and 3 of hexafluoropropane dianhydride/3-, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride/4, two kinds of polyamic acid solutions of 4 '-diamines yl diphenyl ether (BTDA/ODA), the high-reflectivity of the reflectance coating that obtains is respectively 83% and 79%.
More than study the silver hybrid polyimide reflective film of preparation, do not consider the easy problem of oxidation of argent.In air, during room temperature, the Δ G of silver and oxygen reaction
θ(T) be negative value, show that this reaction can carry out, show that also silver and oxygen are easy to combine the generation silver suboxide, temperature is elevated to 408K when above, its Δ G
θ(T) be on the occasion of, under standard conditions, silver is the regeneration silver suboxide not; Simultaneously, have the hydrogen sulfide of trace in the air, silver and hydrogen sulfide reaction generate the silver sulfide of black; In addition, be mingled with the ozone of trace in the air, it can directly act on the silver suboxide that generates black with silver.In space, silver is easy to action of atomic oxygen and generates silver suboxide.Therefore, when silver uses under air at room temperature and in the space, slowly deepening of surface meeting, blackout.In the silver hybrid polyimide reflective film, the univalent silver salt is reduced to silver in the imidization process, and accumulates in polyimide surface with nano level.These silver particles are very easily oxidized, thereby make reflectance coating surface reflection reduction, influence its works better and work-ing life.In order to ensure that spacecraft moves reliably and with long-term at rail, and prolong its work-ing life, the normal use of some flexible speculums and reverberator in the guarantee air, it is very important and necessary improving its oxidation-resistance when keeping the performance of silver hybrid polyimide reflective film own.
At present, the means of defence of raising antioxidant property is mainly and applies the antioxidant defense coating.Spray one deck silicon in the U.S. Pat 4011055 on base material graphite, electronickelling thereon and chromium can play good antioxidant effect then, but this coating is opaque, is not suitable for the oxidation resistant coating of reflectance coating.Patent US5472787 deposits one deck non-crystalline silicon on the jewel base material, deposit aluminum nitride or yttrium oxide etc. then, and coating had not only had good oxidation-resistance but also had not covered gloss of jewel itself; Among the patent US5332619 on silicon carbide ceramics depositing silicon or silicon-dioxide, between basic 1 material and anti oxidation layer, at first deposit one deck aluminum oxide in order to improve its associativity; Some data also are presented in and at first deposit one deck aluminum oxide on the metal silverskin, and then depositing silicon or silicon dioxide layer, can play the metallic reflection that good oxidation-resistance keeps silverskin simultaneously.Anti oxidation layer in the above patent is inorganics, though have good oxidation-resistance, also have following shortcoming: the fragility of (1) inorganic coating, not matching with the thermal expansivity of base material causes material crackle can take place when crooked with base material in processing, processing and application process; (2) in the deposition process of coating, 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.
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 anti-oxidant (atomic oxygen erodes), 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) technology of preparation coating satisfies with low cost and the efficient height, and easily expands on the large-size workpiece.On base material such as PI, spray in the atomic oxygen shielding layer in the U.S. Pat 5312685, as silver, gold, platinum, rhenium or silver suboxide, rhenium oxide etc., the effect of catalyzer is to make to strike lip-deep atomic oxygen and be combined into the molecule state to the spraying discontinuous phase as catalyzer.This method can obtain good anti-atomic oxygen layer, but coating has the fragility and the unmatched problem of thermal expansivity of inorganics equally.US6872457 discloses the anti-atomic oxygen layer of a kind of organic coating as PI, and this coating comprises Polyimidesiloxane, thermosetting resin and thermosetting resin cured dose.This coating is the sub-oxygen protective coating of effective antigens, but still can not satisfy above-mentioned space application requiring simultaneously, and subject matter is that the space junk bump makes coating produce the hole, and then the formation sapping causes coating to lose efficacy.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.
Summary of the invention
The objective of the invention is at silver hybrid polyimide reflective film in its application process easy problem of oxidation and the deficiency of existing anti-oxidation tech, provide a kind of and not only had highly reflective but also have silver hybrid polyimide reflective film material of oxidation-resistance and preparation method thereof.
The present invention relates to a kind of antioxidant silver hybrid polyimide reflective film material and preparation method thereof: (1) utilizes one step of original position self-metallization legal system to be equipped with the silver hybrid polyimide reflective film that the surface has highly reflective; (2), prepare the silver hybrid polyimide reflective film that not only has highly reflective but also have oxidation-resistance in the certain thickness oxidation resistant coating of silver hybrid polyimide reflective film surface-coated.
Consisting of of anti-oxidant reflectance coating of the present invention:
(a) polyimide resin; (b) silver; (c) oxidation resistant coating.
The typical preparation method of anti-oxidant reflectance coating of the present invention is:
(a) preparation polyamic acid solution;
(b) solubility organic silver salts or the inorganic silver salt of solubility are dissolved in the polyimide resin solution, apply film forming;
(c) the process hot-imide prepares the polyimide reflective film of silver-colored hydridization;
(d) in silver hybrid polyimide reflective film surface-coated oxidation resistant coating, obtain antioxidant silver hybrid polyimide reflective film.
Among the present invention, polyimide resin is homopolymerization polyimide or copolyimide.
Among the present invention, silver particles is to be generated by its presoma original position in polyimide matrix, and particle diameter is 5～100 nanometers.
Among the present invention, the presoma of silver is solubility organic silver salts or the inorganic silver salt of solubility, and the solubility organic silver salts is selected from: one or more in trifluoroacetylacetone silver, hexafluoroacetylacetone silver, trifluoroacetic acid silver, cyclooctadiene hexafluoroacetylacetone silver, thenoyltrifluoroacetone silver, the silver citrate; Inorganic silver salt is selected from: one or more in Silver Nitrate, silver fluoride, the silver tetrafluoroborate.
Among the present invention, the thickness of oxidation resistant coating is 1～50nm, is preferably 5～40nm, and more preferably 10～30nm is preferably 15～25nm.
Among the present invention, this anti oxidation layer can be polysiloxane, poly-fluorosilicone, poly-silicon fluoride, poly-fluorine silazane, poly-fluorine phosphorus nitrogen and organic-inorganic nano hybrid composite material.
Among the present invention, the organic-inorganic nano hybrid composite material is selected from: one or more in nano ceramics hybridized polymer based composites, clay hybridized polymer based composites, the molecular sieve hybrid polymer matrix composite.
In the organic-inorganic nano hybrid composite material of the present invention, polymkeric substance is the soluble precursor of soluble polymer and insoluble polymer, is selected from: one or more in polymeric amide, polyimide, Resins, epoxy, unsaturated polyester, urethane, acrylic resin, polysiloxane, poly-fluorosilicone, poly-silicon fluoride, poly-fluorine silazane, the poly-fluorine phosphorus nitrogen.
In the inorganic-organic hybridization nano matrix material of the present invention, the content of inorganic nano-particle is 0.01～50wt%, is preferably 0.1～30wt%, and more preferably 1～20wt% is preferably 2～10wt%.
In the nano ceramics hybridized polymer based composites of the present invention, the nano ceramics particle is selected from: one or more in silicon-dioxide, titanium dioxide, aluminium sesquioxide, magnesium oxide, zirconium white, stannic oxide, aluminium nitride, silicon nitride, boron nitride, titanium nitride, molybdenum disilicide, zirconium boride 99.5004323A8ure, the barium titanate.
In the clay hybridized polymer based composites of the present invention, clay is selected from: one or more in hectorite, talcum powder, polynite, the mica.
In the molecular sieve hybrid polymer matrix composite of the present invention, molecular screening one or more in borosilicate, ZSM-5.
In the present invention, the compound technology of organic-inorganic nano hybrid composite material is selected from direct dispersion method, graft process, the sol-gel method one or more.
The recombining process of anti oxidation layer of the present invention and silver hybrid polyimide reflective film is: spin coating, dip-coating, spraying, brushing, roller coat.
The oxidation resistant reflectance coating of the present invention has the following advantages: (1) this reflective film material not only has higher reflectivity, and has oxidation-resistance, is suitable for secular application; (2) anti oxidation layer of this reflective film material closely is connected with the silver hybrid polyimide reflective film layer, and the two has close thermal expansivity, is difficult for peeling off phenomenon under the thermal cycling effect; (3) preparation technology is simple, is easy to realize having good versatility.
Embodiment
Embodiment 1:
Polyimide resin 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride/4,13 parts of preparations of 100 parts of 4 '-diamines yl diphenyl ethers (BTDA/ODA) and nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BTDA and 4 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates required solvent N according to institute's resulting solution solid content, and the amount of N '-N,N-DIMETHYLACETAMIDE (DMAC) is also measured.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and BTDA adds this solution in batches, stirs 6h, obtains uniform presoma polyamic acid (PAA) solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt silver acetate (AgAc) and take by weighing according to the expection silver content, TFAH is added among the AgAc by AgAc and solubilizing agent trifluoroacetylacetone (TFAH) mol ratio 1: 1.35, and then adding a small amount of solvent DMAc.Stir, react generation trifluoroacetylacetone silver (AgTFA) down at 0～25 ℃.The PAA solution of preparation in (a) is joined among the AgTFA, and stirring is dissolved in the PAA solution AgTFA, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 74% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, the reflectance coating surface becomes the silver yellow look by silver color, reduces to 38% at the 530nm reflectivity.
Embodiment 2:
Polyimide resin 2,2 '-two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydride/100 parts of perfluor isopropylidene diamines (6FDA/4-BDAF) and nano silicon (SiO
2) 5 parts of preparations of particle oxidation resistant coating material.
(a) preparation polymers soln or polybenzazole precursor liquid solution
The 6FDA and the 4-BDAF of amount of substance such as taking by weighing, is that 10wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, 4-BDAF fully is dissolved among the DMAc, 6FDA adds in this solution in batches, stirs 6h, obtains uniform presoma 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
The silver hybrid polyimide reflective film that obtains according to prescription among the embodiment 1 and prepared, immediately coated with last oxidation resistant coating, and through the moulding of 300 ℃/0h hot-imide, control thickness 20nm.
The antioxidant silver hybrid polyimide reflective film surface that makes is silver color, is 67% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectance coating surface no change still is a silver color, is 67% at the 530nm reflectivity.
The silver hybrid polyimide reflective film of uncoated oxidation resistant coating experiences the hot-imide process again one time, is 77% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, the reflectance coating surface becomes the silver yellow look by silver color, reduces to 40% at the 530nm reflectivity.
Embodiment 3:
Copolyimide resin 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride/BPDA/3,4 '-diamines yl diphenyl ether (BTDA/BPDA/3,4 '-ODA) 100 part and 6 parts of silver-colored hydridization copolyimide reflectance coatings of preparation of nanometer silver (Ag) particle.
(a) preparation copolyimide resin solution
Take by weighing 3.960g (0.0123mol) BTDA, 3.616g (0.0123mol) BPDA, 5g (0.0250mol) 3,4 '-ODA and 0.116g (0.0008mol) PA is that 20wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 3,4 '-ODA fully is dissolved among the DMAc, and BTDA is added extremely all dissolvings in this solution in batches, BPDA is added in batches in this solution to all dissolving again.Continue to stir 6h, obtain uniform presoma copolymerization PAA solution.
(b) solubility inorganic silver salt Silver Nitrate is dissolved in the copolyimide resin solution, applies film forming
Calculate required silver salt Silver Nitrate (AgNO according to the expection silver content
3) amount and take by weighing, with AgNO
3Join in the PAA solution of preparation in (a), stir and make AgNO
3Be dissolved in PAA solution, continue to stir 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/2h → 80 ℃/2h → 120 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
It is reflective that the silver hybrid polyimide reflective film surface that makes is bright green, is 52% at the 530nm reflectivity; After in air, placing 48h under (25 ℃ of temperature, humidity 30%) condition, reduce to 38% at the 530nm reflectivity.
According to prescription among the embodiment 2 and prepared oxidation resistant coating, on above silver hybrid polyimide reflective film, apply oxidation resistant coating immediately, and through the moulding of 300 ℃/0h hot-imide, control thickness 20nm.
The antioxidant silver hybrid polyimide reflective film that makes is 48% at the 530nm reflectivity; After in air, placing 48h under (25 ℃ of temperature, humidity 30%) condition, be 48% at the 530nm reflectivity.
Embodiment 4:
Copolyimide resin 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride // pyromellitic acid dianhydride/4,4 '-diamines yl diphenyl ether (BTDA//PMDA/4,4 '-ODA) 100 part and 8 parts of silver-colored hydridization copolyimide reflectance coatings of preparation of nanometer silver (Ag) particle.
(a) preparation copolyimide resin solution
Take by weighing 3.222g (0.01mol) BTDA, 2.181g (0.01mol) PMDA, 4.005g (0.02mol) 4,4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and BTDA is added extremely all dissolvings in this solution in batches, PMDA is added in batches in this solution to all dissolving again.Continue to stir 6h, obtain uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the copolyimide resin solution, applies film forming
Calculate required silver salt hexafluoroacetylacetone silver (AgHFA) according to the expection silver content, the PAA solution for preparing in (a) is joined among the AgHFA, stirring is dissolved in the PAA solution AgHFA, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/2h → 80 ℃/2h → 120 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
It is reflective that the silver hybrid polyimide reflective film surface that makes is sorrel, is 29% at the 530nm reflectivity; After in air, placing 48h under (25 ℃ of temperature, humidity 30%) condition, the basic no change of reflectivity.
Embodiment 5:
Copolyimide resin 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride // BPDA/4,4 '-diamines yl diphenyl ether (BTDA//BPDA/4,4 '-ODA) 100 part and 15 parts of silver-colored hydridization copolyimide reflectance coatings of preparation of nanometer silver (Ag) particle.
(a) preparation copolyimide resin solution
Take by weighing 3.222g (0.01mol) BTDA, 2.942g (0.01mol) BPDA, 4.005g (0.02mol) 4,4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and BTDA is added extremely all dissolvings in this solution in batches, BPDA is added in batches in this solution to all dissolving again.Continue to stir 6h, obtain uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the copolyimide resin solution, applies film forming
Calculate required silver salt cyclooctadiene hexafluoroacetylacetone silver and preparation according to the expection silver content, the PAA solution of preparation in (a) is joined in the cyclooctadiene hexafluoroacetylacetone silver, stirring makes it be dissolved in PAA solution, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/2h → 80 ℃/2h → 120 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silvery reflection, is 77% at the visible region maximum reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 36%.
Apply the oxidation resistant coating silicone resin immediately on the above PI/Ag reflectance coating that newly makes, control thickness 20nm makes anti-oxidant reflectance coating, and it is 72% at the visible region maximum reflectivity.Carry out the atomic oxygen effect test of sample in Low Earth Orbit environment atomic oxygen effect ground-based simulation equipment, test after 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2The result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 53% at the visible region maximum reflectivity, and silicone resin can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 6:
Polyimide resin phenyl ether tetracarboxylic dianhydride/4,18 parts of preparations of 100 parts of 4 '-diamines yl diphenyl ethers (ODPA/ODA) and nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The ODPA and 4 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates the amount of required solvent DMAc and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and ODPA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
Calculate required silver salt thenoyltrifluoroacetone silver and preparation according to the expection silver content, the PAA solution of preparation in (a) is joined in the thenoyltrifluoroacetone silver, stirring is dissolved in the PAA solution thenoyltrifluoroacetone silver, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/2h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 78% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 41%.
Apply the poly-fluorosilicone of oxidation resistant coating on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 72% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 57% at the visible region maximum reflectivity.Illustrate that poly-fluorosilicone can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 7:
Polyimide resin dihydroxyphenyl propane tetracarboxylic dianhydride/3,4 '-diamines yl diphenyl ether (BPADA/3,4 '-ODA) 100 part and 20 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BPADA and 3 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 3,4 '-ODA fully is dissolved among the DMAc, and BPADA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt silver citrate and take by weighing according to the expection silver content, will (a) in PAA solution of preparation join in the silver citrate, stir silver citrate be dissolved in the PAA solution, continue stirring 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/2h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 79% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 37%.
Apply the poly-fluorosilicone of oxidation resistant coating silicon-dioxide (15 parts) hydridization on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 69% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 64% at the visible region maximum reflectivity.
Illustrate that the poly-fluorosilicone of silicon-dioxide (15 parts) hydridization can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 8:
Polyimide resin diphenyl sulfide tetracarboxylic dianhydride/100 parts of 4,4 '-two amido diphenyl sulfides (TDPA/ASD) and 25 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The TDPA and 4 of amount of substance such as take by weighing, 4 '-ASD is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ASD fully is dissolved among the DMAc, and TDPA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt silver citrate and take by weighing according to the expection silver content, it is joined in PAA solution of preparation in (a), stir and make its dissolving, continue to stir 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/2h.Be chilled to room temperature, make the PI/Ag reflectance coating.
It is green that the silver hybrid polyimide reflective film surface that makes is, and is 51% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, the reflectance coating surface albedo reduces to 39%.
Apply oxidation resistant coating aluminium nitride (5 parts) hydridization polysiloxane on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 49% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 42% at the visible region maximum reflectivity.Illustrate that aluminium nitride (5 parts) hydridization polysiloxane can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 9:
Polyimide resin 2,2 '-two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydride/100 parts of perfluor isopropylidene diamines (6FDA/4-BDAF) and 13 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The 6FDA and the 4-BDAF of amount of substance such as taking by weighing, is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, 4-BDAF fully is dissolved among the DMAc, 6FDA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the inorganic silver salt of solubility is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt silver fluoride and take by weighing according to the expection silver content, silver fluoride is joined in PAA solution of preparation in (a), stir silver fluoride is dissolved in the PAA solution, continue to stir 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 86% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 45%.
Apply oxidation resistant coating silicon-dioxide (5 parts) and aluminum oxide (3 parts) hydridization acrylic resin on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 79% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 59% at the visible region maximum reflectivity.Illustrate that silicon-dioxide (5 parts) and aluminum oxide (3 parts) hydridization acrylic resin can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 10:
Polyimide resin BPDA/4,16 parts of preparations of 100 parts of 4 '-diaminodiphenyl oxides (BPDA/ODA) and nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BPDA and 4 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and BPDA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
According to expecting that silver content calculates the silver-colored and preparation of required silver salt trifluoroacetic acid, the PAA solution for preparing in (a) is joined in the trifluoroacetic acid silver, stirring is dissolved in the PAA solution trifluoroacetic acid silver, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 84% at the 530nm reflectivity; After in air, placing 48h under (25 ℃ of temperature, humidity 30%) condition, reduce to 47% at the 530nm reflectivity.
Apply oxidation resistant coating silicon-dioxide (3 parts) and magnesium oxide (2 parts) hybridization epoxy resin on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 76% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 67% at the visible region maximum reflectivity.Illustrate that silicon-dioxide (3 parts) and magnesium oxide (2 parts) hybridization epoxy resin can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 11:
Polyimide resin BPDA/3,4 '-diaminodiphenyl oxide (BPDA/3,4 '-ODA) 100 part and 16 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BPDA and 3 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 3,4 '-ODA fully is dissolved among the DMAc, and BPDA adds this solution in batches, stirs 6h, obtains uniform presoma polyamic acid (PAA) solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
According to expecting that silver content calculates the silver-colored and preparation of required silver salt trifluoroacetylacetone, the PAA solution for preparing in (a) is joined in the trifluoroacetylacetone silver, stirring is dissolved in the PAA solution trifluoroacetylacetone silver, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 77% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 46%.
Apply the poly-silicon fluoride of oxidation resistant coating polynite (5 parts) hydridization on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 68% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 61% at the visible region maximum reflectivity.Illustrate that the poly-silicon fluoride of polynite (5 parts) hydridization can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 12:
Polyimide resin bis ether tetracarboxylic dianhydride/4,4 '-diaminodiphenyl oxide (HQDPA/4,4 '-ODA) 100 part and 16 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The HQDPA and 4 of amount of substance such as take by weighing, 4 '-ODA is that 15wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, with 4,4 '-ODA fully is dissolved among the DMAc, and HQDPA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the inorganic silver salt of solubility is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt silver tetrafluoroborate and take by weighing according to the expection silver content, silver tetrafluoroborate is joined in PAA solution of preparation in (a), stir silver tetrafluoroborate is dissolved in the PAA solution, continue to stir 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is the silver yellow look, is 64% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 51%.
Apply the poly-silicon fluoride of oxidation resistant coating borosilicate (5 parts) hydridization on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 57% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 51% at the visible region maximum reflectivity.Illustrate that the poly-silicon fluoride of borosilicate (5 parts) hydridization can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 13:
30 parts of preparations of 100 parts of polyimide resin BPDA/benzidines (BPDA/BZD) and nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BPDA and the BZD of amount of substance such as taking by weighing, is that 10wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, BZD fully is dissolved among the DMAc, BPDA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
Prepare required silver salt trifluoroacetylacetone silver according to the expection silver content, the PAA solution for preparing in (a) is joined in the trifluoroacetylacetone silver, stirring is dissolved in the PAA solution silver salt, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/3h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 97% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 58%.
Apply the poly-silicon fluoride of oxidation resistant coating silicon-dioxide (3 parts) hydridization on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 93% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 79% at the visible region maximum reflectivity.Illustrate that the poly-silicon fluoride of silicon-dioxide (3 parts) hydridization can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 14:
Copolyimide resin phenyl ether tetracarboxylic dianhydride // BPDA/100 parts of benzidines (ODPA//BPDA/BZD) and 40 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
Taking by weighing 0.01mol BPDA, 0.01mol ODPA and 0.02mol BZD, is that 25wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, BZD fully is dissolved among the DMAc, ODPA adds this solution in batches, and BPDA adds in batches then, stirs 6h, obtains uniform copolyamide acid (PAA) solution.
(b) the inorganic silver salt of solubility is dissolved in the polyimide resin solution, applies film forming
Calculate the amount of required silver salt Silver Nitrate and take by weighing according to the expection silver content, Silver Nitrate is joined in PAA solution of preparation in (a), stir it is dissolved in the PAA solution, continue to stir 5h, obtain PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/2h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is silver color, is 84% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity reduces to 51%.
Apply oxidation resistant coating magnesium oxide (2 parts) and aluminum oxide (2 parts) hydridization polysiloxane on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 76% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 68% at the visible region maximum reflectivity.Illustrate that magnesium oxide (2 parts) and aluminum oxide (2 parts) hydridization polysiloxane can significantly improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Embodiment 15:
Polyimide resin dihydroxyphenyl propane dianhydride/100 parts of dihydroxyphenyl propane diamines (BPADA/BAPP) and 2 parts of preparations of nanometer silver (Ag) particle silver hybrid polyimide reflective film.
(a) preparation polyimide resin solution
The BPADA and the BAPP of amount of substance such as taking by weighing, is that 20wt% calculates the amount of required solvent DMAC and measures according to institute's resulting solution solid content.Under 0～25 ℃, BAPP fully is dissolved among the DMAc, BPADA adds this solution in batches, stirs 6h, obtains uniform presoma PAA solution.
(b) the solubility organic silver salts is dissolved in the polyimide resin solution, applies film forming
According to amount and the preparation that the expection silver content calculates required silver salt trifluoroacetic acid silver, trifluoroacetic acid silver is joined in the PAA solution of preparation in (a), stirring is dissolved in the PAA solution it, continues to stir 5h, obtains PAA/Ag (I) solution.PAA/Ag (I) solution coating, coating thickness is 400 μ m, makes PAA/Ag (I) film.
(c) silver original position in the hot-imide process forms and migrates to the polyimide top layer and forms silver hybrid polyimide reflective film
PAA/Ag (I) film that makes is carried out hot-imide, and heating schedule is: room temperature/1h → 35 ℃/1h → 60 ℃/1h → 80 ℃/1h → 100 ℃/1h → 135 ℃/1h → 175 ℃/1h → 200 ℃/1h → 225 ℃/1h → 275 ℃/1h → 300 ℃/1h.Be chilled to room temperature, make the PI/Ag reflectance coating.
The silver hybrid polyimide reflective film surface that makes is sorrel, is 35% at the 530nm reflectivity; Place 48h under (25 ℃ of temperature, humidity 30%) condition in air after, reflectivity does not have noticeable change.
Apply the poly-fluorosilicone of oxidation resistant coating silicon nitride (1 part) hydridization on the above PI/Ag reflectance coating that newly makes immediately, control thickness 20nm makes anti-oxidant reflectance coating, and it is 31% at the visible region maximum reflectivity.Behind the effect test of anti-atomic oxygen the 20 hours, the atomic oxygen fluence is 5.05 * 10
20Atom/cm
2, the result shows: the reflectance coating surface of uncoated oxidation resistant coating becomes furvous, and the reflectance coating that applies oxidation resistant coating is still had a reflectivity, is 26% at the visible region maximum reflectivity.Illustrate that the poly-fluorosilicone of silicon nitride (1 part) hydridization can improve the anti-atomic oxygen performance of silver hybrid polyimide reflective film.
Claims (15)
1. antioxidant silver hybrid polyimide reflective film is characterized in that: contain the polyimide reflective film of silver-colored hydridization in the described polyimide reflective film, and the oxidation resistant coating that is coated in the polyimide reflective film surface of silver-colored hydridization.
2. anti-oxidant silver hybrid polyimide reflective film as claimed in claim 1, it is characterized in that: the matrix of described polyimide reflective film is homopolymerization polyimide or copolyimide.
3. one kind as each described anti-oxidant silver hybrid polyimide reflective film among the claim 1-2, it is characterized in that: the particle diameter of silver is about 5～100nm in the polyimide reflective film of described silver-colored hydridization.
4. one kind as each described anti-oxidant silver hybrid polyimide reflective film among the claim 1-3, it is characterized in that: the content of silver is about 0.01～50wt% in the polyimide reflective film of described silver-colored hydridization.
5. one kind as each described anti-oxidant silver hybrid polyimide reflective film among the claim 1-4, and it is characterized in that: the thickness of described oxidation resistant coating is about 1～50nm.
6. one kind as each described anti-oxidant silver hybrid polyimide reflective film among the claim 1-5, it is characterized in that: described anti oxidation layer is polysiloxane, poly-fluorosilicone, poly-silicon fluoride, poly-fluorine silazane, poly-fluorine phosphorus nitrogen or organic-inorganic nano hybrid composite material.
7. anti-oxidant silver hybrid polyimide reflective film as claimed in claim 6, it is characterized in that: described organic-inorganic nano hybrid composite material is selected from: one or more in nano ceramics hybridized polymer based composites, clay hybridized polymer based composites, the molecular sieve hybrid polymer matrix composite.
8. anti-oxidant silver hybrid polyimide reflective film as claimed in claim 7, it is characterized in that: described polymkeric substance is selected from: one or more in polymeric amide, polyimide, Resins, epoxy, unsaturated polyester, urethane, acrylic resin, polysiloxane, poly-fluorosilicone, poly-silicon fluoride, poly-fluorine silazane, the poly-fluorine phosphorus nitrogen.
9. anti-oxidant silver hybrid polyimide reflective film as claimed in claim 7, it is characterized in that: described nano ceramics particle is selected from one or more in silicon-dioxide, titanium dioxide, aluminium sesquioxide, magnesium oxide, zirconium white, stannic oxide, aluminium nitride, silicon nitride, boron nitride, titanium nitride, molybdenum disilicide, zirconium boride 99.5004323A8ure, the barium titanate.
10. anti-oxidant silver hybrid polyimide reflective film as claimed in claim 7, it is characterized in that: described clay is selected from one or more in hectorite, talcum powder, polynite, the mica.
11. an anti-oxidant silver hybrid polyimide reflective film as claimed in claim 7 is characterized in that: described molecular screening one or more in borosilicate, ZSM-5.
12. the preparation method of each described antioxidant silver hybrid polyimide reflective film among the claim 1-11 is characterized in that: described method comprises the steps:
(a) preparation polyamic acid solution;
(b) soluble silver salt is dissolved in the polyamic acid solution, the back casting film stirs;
(c) the film hot-imide that step (b) is obtained obtains the Kapton of silver-colored hydridization;
(d) in silver hybrid polyimide reflective film surface-coated oxidation resistant coating, obtain antioxidant silver hybrid polyimide reflective film.
13. the preparation method of an antioxidant silver hybrid polyimide reflective film as claimed in claim 11 is characterized in that: described soluble silver salt is selected from: one or more in trifluoroacetylacetone silver, hexafluoroacetylacetone silver, trifluoroacetic acid silver, cyclooctadiene hexafluoroacetylacetone silver, thenoyltrifluoroacetone silver, silver citrate, Silver Nitrate, silver fluoride, the silver tetrafluoroborate.
14. the preparation method of an antioxidant silver hybrid polyimide reflective film as claimed in claim 11 is characterized in that: the coating processes of anti oxidation layer can be spin coating, dip-coating, spraying, brushing or roller coat.
15. each described anti-oxidant silver hybrid polyimide reflective film application in the protective layer of space light flexible reverberator, space amplitude transformer or aerospacecraft among the claim 1-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102253442A (en) * | 2010-05-20 | 2011-11-23 | 罗福高技术薄膜股份有限公司 | Reflecting films obtained by solvent casting and their use |
| CN103881121A (en) * | 2014-03-18 | 2014-06-25 | 常州大学 | Preparation method of antibacterial polyimide film |
| CN104878393A (en) * | 2015-05-22 | 2015-09-02 | 苏州市贝克生物科技有限公司 | Cultural relics surface oxidation resistant coating and preparation method of cultural relics surface oxidation resistant coating |
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| CN110387040A (en) * | 2019-07-17 | 2019-10-29 | 中国科学院上海硅酸盐研究所 | A kind of black polyamide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102253442A (en) * | 2010-05-20 | 2011-11-23 | 罗福高技术薄膜股份有限公司 | Reflecting films obtained by solvent casting and their use |
| CN103881121A (en) * | 2014-03-18 | 2014-06-25 | 常州大学 | Preparation method of antibacterial polyimide film |
| CN104878393A (en) * | 2015-05-22 | 2015-09-02 | 苏州市贝克生物科技有限公司 | Cultural relics surface oxidation resistant coating and preparation method of cultural relics surface oxidation resistant coating |
| CN106433552A (en) * | 2016-09-27 | 2017-02-22 | 四川省新材料研究中心 | Platinum catalyst for photocuring liquid silicone rubber and LED package resin composition |
| CN106433552B (en) * | 2016-09-27 | 2019-12-31 | 四川省新材料研究中心 | Platinum catalyst for photocuring liquid silicone rubber and LED packaging adhesive composition |
| CN108455995A (en) * | 2018-02-09 | 2018-08-28 | 青海大学 | A kind of silicon carbide fibre enhancing aluminum phosphate ceramic matric composite and preparation method thereof |
| CN108774333A (en) * | 2018-06-25 | 2018-11-09 | 北京化工大学 | A kind of resistance to elemental oxygen polyimide film layer material and preparation method thereof |
| CN110387040A (en) * | 2019-07-17 | 2019-10-29 | 中国科学院上海硅酸盐研究所 | A kind of black polyamide film |
| CN110600557A (en) * | 2019-09-17 | 2019-12-20 | 湖南纵横空天能源科技有限公司 | Method for manufacturing front film coating of flexible solar module for satellite |
| 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 |
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